FULLTEXT01 Coating

PhD Thesis
Production Technology
2018 No. 20
Design of Suspension Plasma

Sprayed Thermal Barrier Coatings
Ashish Ganvir
Tryck: BrandFactory, april 2018.
PhD Thesis
Production Technology
2018 No. 20
Design of Suspension Plasma

Sprayed Thermal Barrier Coatings
Ashish Ganvir
University West
SE-46186 Trollhättan
Sweden
+46 52022 30 00
www.hv.se
© Ashish Ganvir 2018

ISBN 978-91-87531-92-7 (Printed version)
978-91-87531-91-0 (Electronic version)
Trollhättan, Sweden, 2018

Dedicated to all those who financially supported my education!
III
Acknowledgements
It is with immense gratitude that I acknowledge the financial support provided by

the Västra Götalandsregionen, Sweden, to accomplish this research work.
First and foremost, I wish to thank my supervisors Prof. Nicolaie Markocsan, Dr.
Mohit Gupta and Prof. Per Nylen for the continuous support in my PhD study,
for their patience and immense knowledge. Their guidance helped me in doing a
great research and writing of this thesis. I could not have imagined having better
supervisors for my PhD study. It’s a privilege to be your student and I wish I keep
learning from you all. Thank you for always motivating and offering me an
immense freedom during this research!
My sincere thanks also go to Dr. Nicholas Curry, Mr. Jonas Olsson and Mr. Stefan
Björklund for their immense help with spraying and sharing their vital knowledge
to enhance my practical skills. It’s been a pleasure to work with you all! Thanks
to Prof. Shrikant Joshi, Prof. Robert Vassen and Prof. Uta Klement for their
valuable collaboration and feedback during my research. Also, thanks to Ms.
Johanna Ekberg, a former PhD student at Chalmers University of Technology
for making this collaborative project ‘PROSAM’ between Chalmers University of
Technology and University West more successful.
I must also acknowledge the support from various partners associated with my
research: GKN Aerospace, Trollhättan, Sweden; Innovnano Coimbra, Portugal;
IPP, Prague, Czech Republic; Swerea IVF, Gothenburg, Sweden; and Chalmers
University of Technology, Gothenburg, Sweden.
I would like to thank all my friends and colleagues at PTC for making these days
so enjoyable. It’s been a great fun to be around you.
I am grateful to my family: my parents, brother and sisters who have provided me

moral and emotional support so far in my life. I am also lucky and grateful to have
very special people in my life who always loved and believed in me.
I must thank to all my seniors and teachers right from the school times till now
for constantly believing in me and guiding me.
And finally, to all those individuals/institutions/government agencies back in

India who supported me financially when it was needed the most. Thank you!
Ashish Ganvir
15th of June 2018, Trollhättan
V
Populärvetenskaplig Sammanfattning
Nyckelord: Mikrostruktur; Termiska barriärbeläggningar; Axialmatning;

Suspensionsplasmasprutning; Värmeledningsförmåga; Brotthållfastheten; Livstid
Titel: Design av suspensionsplasmasprutade termiska värmebarriärbeläggningar
Termiska värmebarriärbeläggningar (TBC) används i stor utsträckning på

gasturbinkomponenter för att åstadkomma termisk isolering och
oxidationsskydd. TBCs, i kombination med avancerad kylning, möjliggör högre
förbränningstemperaturer i gasturbinen även över smälttemperaturen för
metalliska material. Det finns ett ständigt behov, främst av miljöskäl, för att både
minska bränsleförbrukning och emissioner och att öka förbränningstemperaturen
vilket kräver nya typer av TBC-lösningar.
Genom att använda en suspension vid termisk sprutning, kan nya typer av TBC
framställas. Suspensionsplasmasprutning och lösningsbaserad plasmasprutning är
exempel på tekniker som kan användas. Dessa tillvägagångssätt, som är alternativ
till den konventionella tekniken med tillsatsmaterial i fast form, röner ett allt större
forskningsintresse: Anledningen till det stora forskningsintresset är möjligheten
att producera beläggningar med överlägsna funktionella egenskaper.
Syftet med detta avhandlingsarbete var att undersöka samband mellan

processparametrar, beläggningarnas mikrostruktur, beläggningarnas
värmeledningsförmåga och beläggningarnas livstid för termisk sprutade
värmebarriärbeläggningar där tillsatsmaterialet införs i lågan i flytande form. Ett
ytterligare syfte var att utnyttja denna kunskap för att producera en
värmebarriärbeläggning med lägre värmeledningsförmåga jämfört med state-of-
the-art inom industrin idag, det vill säga då tillsatsmaterialet tillförs i fast form.
Olika spruttekniker såsom suspensionssprutning med plasma, lösningsbaserad
sprutning med plasma, suspension med höghastighetsflamsprutning undersöktes
och jämfördes med plasmasprutning där tillsatsmaterialet införts i fast form.
En mängd olika mikrostrukturer, såsom mycket porösa, strukturer med vertikal

sprickor och kolumnära strukturer erhölls. Det visades att det finns starka
samband mellan mikrostrukturerna, de termo-mekaniska egenskaperna och de
funktionella egenskaperna hos beläggningarna. Specifikt axiell
suspensionsplasmasprutning visades som en mycket lovande teknik för att
producera olika mikrostrukturer samt beläggningar med lång hållbarhet. Baserat
på experimentella resultat föreslås också en skräddarsydd kolumnär mikrostruktur
för en överlägsen TBC-prestanda.
VII
Abstract
Title: Design of Suspension Plasma Sprayed Thermal Barrier Coatings
Thermal barrier coatings (TBCs) are widely used on gas turbine components to
provide thermal insulation, which in combination with advanced cooling, can
enable the gas turbine to operate at significantly higher temperatures even above
the melting temperature of the metallic components. There is a permanent need,
mainly due to environmental reasons, to increase the combustion temperature in
turbines, hence new TBC solutions are needed.
By using a liquid feedstock in thermal spraying, new types of TBCs can be

produced. Suspension plasma/flame or solution precursor plasma spraying are
examples of techniques that can be utilized for liquid feedstock thermal spraying.
This approach of using suspension and solution feedstock, which is an alternative
to the conventional solid powder feedstock spraying, is gaining increasing
research interest since it has been shown to be capable of producing coatings with
superior performance.
The objective of this research work was to identify relationships between process
parameters, coating microstructure, thermal conductivity and lifetime in
suspension plasma sprayed TBCs. A further objective was to utilize these
relationships to enable tailoring of the TBC microstructure for superior
performance compared to state-of-the-art TBC used in industry today, i.e. solid
feedstock plasma sprayed TBCs. Different spraying techniques, namely
suspension high velocity oxy fuel, solution precursor plasma and suspension
plasma spraying (with axial and radial feeding) were explored and compared to
solid feedstock plasma spraying.
A variety of microstructures, such as highly porous, vertically cracked and

columnar, were produced and investigated. It was shown that there are strong
relationships between microstructure, thermo-mechanical properties and
performance of the coatings. Specifically, axial suspension plasma spraying was
shown as a very promising technique to produce various microstructures as well
as highly durable coatings. Based on the experimental results, a tailored columnar
microstructure design for a superior TBC performance is also proposed.
Keywords: Microstructure; Thermal Barrier Coatings; Axial Injection; Suspension

Plasma Spraying; Porosity; Thermal Conductivity; Fracture Toughness; Lifetime.
ISBN: 978-91-87531-92-7
IX
Preface
The experimental research performed in this thesis work was primarily conducted
at the Production Technology Centre within the Thermal Spray research group at
University West, Trollhättan, Sweden. Additional experiments required for this
work were performed at several research partners namely Chalmers University of
Technology, Gothenburg, Sweden; Jönköping University, Jönköping, Sweden;
GKN Aerospace, Trollhättan, Sweden; Swerea IVF, Gothenburg, Sweden;
Forschungszentrum Jülich, Germany; Institute of Plasma Physics (IPP), Prague,
Czech Republic and Innovnano Materials, Coimbra, Portugal.
The research conducted in this thesis work was performed in two parts:
1. The first part was dedicated towards screening of several existing liquid
feedstock thermal spray techniques and comparing the different resultant
microstructures. Techniques such as Solution Precursor Plasma Spraying
(SPPS), Suspension High Velocity Oxy Fuel Spraying (S-HVOF),
Suspension Plasma Spraying with radial injection (SPS) and axial injection
(ASPS) were employed to produce TBCs with different microstructures.
In addition, conventional powder feedstock plasma spraying (APS) was
utilized as a reference process.
2. The second part of this work was primarily dedicated towards

establishing the relationships between process characteristics–
microstructure-properties and performance of ASPS produced TBCs to
enable designing highly durable TBCs for gas turbine applications.
Additional efforts were made during this part of the work to establish a
reliable and easy way of porosity measurement procedure for such in-
homogeneously porous new microstructures produced by ASPS.
Moreover, the much sought after column formation shadowing theory
that is widely used in SPS was also experimentally proved with a
systematic progressive microstructure evolution study.
XI
List of Appended Publications
Paper A. Characterization of thermal barrier coatings produced by

various thermal spray techniques using solid powder, suspension
and solution precursor feedstock material
Ashish Ganvir, Nicholas Curry, Sivakumar Govindarajan, Nicolaie
Markocsan
International Journal of Applied Ceramic Technology, vol. 13, no. 7, pp.
324-332, September 2015
Ashish Ganvir has performed all experimental characterization, analyzed all results,
designed the structure of the article and had the main responsibility in writing the
article. Co-authors contributed in formulating concepts and ideas, planning the project,
spraying and article editing. In addition, Nicholas Curry also contributed in writing
the article.
Paper B. Comparative study of suspension plasma sprayed and

suspension high velocity oxy-fuel sprayed YSZ thermal barrier
coatings
Ashish Ganvir, Nicholas Curry, Nicolaie Markocsan, Per Nylen,
Filofteia-Laura Toma
Journal of Surface and Coating Technology, vol. 268, pp. 70–76, April
2015
spraying and article editing.
Paper C. Characterization of microstructure and thermal properties of

YSZ coatings obtained by axial suspension plasma spraying
(ASPS)
Ashish Ganvir, Nicholas Curry, Stefan Björklund, Nicolaie Markocsan,
Per Nylen
Journal of Thermal Spray Technology, vol. 24, no. 7, pp. 1195-1204, June
2015
spraying and article editing.
XIII
Paper D. Influence of microstructure on thermal properties of axial
suspension plasma sprayed YSZ thermal barrier coatings
Ashish Ganvir, Nicholas Curry, Nicolaie Markocsan, Per Nylen, Shrikant
Joshi, Monika Vilemova, Zdenek Pala
Journal of Thermal Spray Technology, vol. 25, no. 1, pp. 202-212,
November 2015
Ashish Ganvir has performed all experimental characterization except mercury

intrusion porosimetry (MIP) and x-ray diffraction (XRD), analyzed all results,
spraying and article editing. MIP and XRD were carried out by co-authors Monika
Vilemova and Zdenek Pala respectively.
Paper E. Influence of isothermal heat treatment on porosity and

crystallite size in axial suspension plasma sprayed thermal barrier
coatings for gas turbine applications
Ashish Ganvir, Nicolaie Markocsan, Shrikant Joshi
Journal of Coatings, vol. 7, no. 1, pp. 1-14, December 2016
article. Co-authors contributed in planning the project and article editing.
Paper F. Experimental visualization of microstructure evolution

during suspension plasma spraying of thermal barrier coatings
Ashish Ganvir, Rosa Calinas, Nicolaie Markocsan, Nicholas Curry,
Shrikant Joshi
Submitted to Journal of Materials and Design, in Apr. 2018
article. Co-authors contributed in planning the project, suspension fabrication, spraying
of suspensions, article structuring and editing.
XIV
LIST OF APPENDED PUBLICATIONS
Paper G. Failure analysis of thermally cycled columnar thermal barrier

coatings produced by high-velocity-air fuel and axial-suspension-
plasma spraying: A design perspective
Ashish Ganvir, Venkateswaran Vaidhyanathan, Nicolaie Markocsan,
Mohit Gupta, Zdenek Pala, Frantisek Lukac
Journal of Ceramics International, vol. 44, no. 3, pp. 3161-3172, February
2018
Ashish Ganvir performed all experimental characterization except image analysis

(IA) and X-ray diffraction (XRD), analyzed all results, designed the structure of the
article and had the main responsibility in writing the article. Co-authors contributed
in formulating concepts and ideas, planning the project, and article editing. IA and
XRD were carried out by co-authors Venkateswaran Vaidhyanathan and Frantisek
Lukac and Zdenek Pala respectively.
Paper H. Tailoring columnar microstructure of axial suspension

plasma sprayed TBCs for superior thermal shock performance
Ashish Ganvir, Shrikant Joshi, Nicolaie Markocsan, Robert Vassen
Journal of Materials and Design, vol. 144, no. 15, pp. 192-208, April 2018
Ashish Ganvir has performed all experimental characterization except mercury

intrusion porosimetry (MIP) and X-ray diffraction (XRD), analyzed all results,
and article structuring and editing.
XV
Relevant Non-Appended Publications
1. A. Ganvir, C. Kumara, M. Gupta, P. Nylen, “Thermal Conductivity in

Suspension Sprayed Thermal Barrier Coatings: Modeling and
Experiments,” Journal of Thermal Spray Technology, vol. 26, no. 1-2,
pp. 71–82, January 2017
2. U. Klement, J. Ekberg, A. Ganvir, “EBSD Analysis and Assessment of

Porosity in Thermal Barrier Coatings Produced by Axial Suspension
Plasma Spraying (ASPS),” Material Science Forum, vol. 879, pp. 972–
977, 2017
3. J. Ekberg, A. Ganvir, U. Klement, S. Creci, L. Nordstierna, “The

influence of heat treatments on the porosity of suspension plasma
sprayed yttria-stabilized zirconia coatings” Journal of Thermal Spray
Technology, vol. 27, no. 3, pp. 391–401, February 2018
XVII
Table of Content
Acknowledgements......................................................................... V
Populärvetenskaplig Sammanfattning ........................................... VII
Abstract ......................................................................................... IX
Preface .......................................................................................... XI
List of Appended Publications ...................................................... XIII
Relevant Non-Appended Publications......................................... XVII
Table of Content .......................................................................... XIX
Abbreviations / Nomenclature .................................................... XXIII
1 Introduction ........................................................................ 1
1.1 Thesis outline ....................................................................... 1
1.2 Objective and research questions ........................................ 2
1.3 Scope .................................................................................. 2
1.4 Limitations............................................................................ 3
2 Background ........................................................................ 5
2.1 Thermal Barrier Coating (TBC) ............................................ 7
2.1.1 Bond Coat (BC) ................................................................ 7
2.1.2 Thermally grown oxide (TGO) .......................................... 8
2.1.3 Top Coat (TC) .................................................................. 8
2.2 Thermal spraying of a TBC ................................................ 10
2.2.1 High velocity oxy fuel spraying (HVOF) .......................... 12
2.2.2 High velocity air fuel spraying (HVAF) ............................ 12
2.2.3 Atmospheric Plasma spraying (APS) .............................. 13
2.3 Liquid feedstock spraying ................................................... 15
2.3.1 Suspension and Solution ................................................ 16
2.3.2 Solution Precursor Plasma Spraying (SPPS).................. 17
2.3.3 Suspension High Velocity Oxy Fuel (S-HVOF) ............... 17
2.3.4 Suspension Plasma Spraying (SPS) .............................. 18
3 Process characteristics of SPS ...................................... 19
3.1 Type of solvent .................................................................. 19
XIX
3.2 Initial size of the solute powder particles ............................ 19
3.3 Solid load in the suspension............................................... 20
3.4 Injection of suspension....................................................... 20
3.4.1 Axial injection versus radial injection .............................. 21
3.5 Sequence of events in SPS coating formation ................... 22
Stage 1: Injection ...................................................................... 23
Stage 2: Atomization ................................................................. 24
Stage 3: Evaporation of the solvent ........................................... 25
Stage 4: Agglomeration of the solute particles .......................... 26
Stage 5: Melting of the solute particles ...................................... 26
Stage 6: Deposition of the molten droplets ................................ 27
3.6 Coating formation in SPS ................................................... 27
4 Characteristics of TBC .................................................... 31
4.1 Microstructure .................................................................... 31
4.1.1 Solid powder feedstock APS sprayed coatings ............... 31
4.1.2 Suspension plasma sprayed coatings ............................ 32
4.2 Porosity .............................................................................. 35
4.3 Thermal conductivity .......................................................... 37
4.3.1 Heat transfer in conventional APS & SPS TCs ............... 37
4.4 Mechanical properties ........................................................ 39
4.5 Sintering of ceramic TC in TBCs ........................................ 40
4.6 Lifetime of TBCs ................................................................ 41
4.6.1 Lifetime and failure associated with the BC and TGO ..... 42
4.6.2 Lifetime and failure associated with the ceramic TC ....... 44
5 Experimental techniques used to characterize TBCs .. 47
5.1 Microstructure evaluation ................................................... 47
5.2 Porosity measurement ....................................................... 48
5.3 Evaluation of thermal conductivity ...................................... 49
5.4 Evaluation of mechanical properties................................... 51
5.5 Evaluation of sintering behaviour ....................................... 53
XX
TABLE OF CONTENT
5.6 Evaluation of thermal cyclic fatigue (TCF) lifetime .............. 53

5.7 Evaluation of thermal-shock (TS) lifetime ........................... 54
6 Microstructure selection and coating design for TBC
applications using SPS ......................................................... 55
6.1 Processing and microstructure ........................................... 55
6.1.1 Influence of process parameters on TC microstructure ... 57
6.1.2 Tailoring of porosity in a SPS TC microstructure ............ 59
6.2 Effect of SPS TC microstructure on thermal conductivity ... 63
6.3 Sintering behaviour of SPS TCs in TBCs ........................... 66
6.4 Designing SPS TBCs for superior TCF performance ......... 68
6.5 Designing SPS TBCs for superior TS performance ............ 69
7 Conclusions ..................................................................... 73
8 Future work ...................................................................... 75
9 Summary of appended publications .............................. 77
References .............................................................................. 83
APPENDED PUBLICATIONS ................................................. 95
XXI
Abbreviations / Nomenclature
APS: Atmospheric Plasma Spraying
ASPS: Axial Suspension Plasma Spraying
BC: Bond Coat
C: Columns
CMAS (Calcia-Magnesia-Alumina-Silica or molten silicate)
CSN: Chromia, Spinel and Nickel oxide
CTE: Coefficient of Thermal Expansion
D50: Median size (diameter) of a particle in a certain particle size distribution.
DSC: Differential Scanning Calorimetry
DVC: Dense Vertically Cracked
EBPVD: Electron Beam Physical Vapor Deposition
FC: Fine cracks
HVAF: High Velocity Air Fuel
HVOF: High Velocity Oxy Fuel
HVSFS: High Velocity Suspension Flame Spraying
IA: Image analysis
IC: Inter-columnar spacing
IGTs: Industrial Gas Turbines
LFA: Laser Flash Analysis
LPPS: Low Pressure Plasma Spray
MIP: Mercury Intrusion Porosimetry
MP: Micron Pores
XXIII
NP: Nano pores
OM: Optical Microscopy
S: Spherical particles
SEM: Scanning Electron Microscopy
S-HVOF: Suspension-High Velocity Oxy Fuel
SP: Sub-micron Pores
SPPS: Solution Precursor Plasma Spraying
SPS: Suspension Plasma Spraying
TBC: Thermal Barrier Coating
TC: Top Coat
TCF: Thermal Cyclic Fatigue
TGO: Thermally Grown Oxide
TS: Thermal shock
VPS: Vacuum Plasma Spray
XRD: X-ray Diffraction
YSZ: Yttria Stabilized Zirconia
XXIV
1 Introduction
A brief introduction to the outline of this thesis, objective of this work and
research questions are presented in this chapter. Additionally, the scope and
limitations of this thesis work are also described in brief.
1.1 Thesis outline

This thesis is organized in nine chapters. The coverage in each chapter is briefly
summarized below:
Chapter 1 provides a brief outline of the thesis, discusses the objective, research
questions and also the scope and limitations of the research work. Chapter 2
provides a detailed background of the overall motivation behind this research and
why the research work is important to the scientific society, specifically to the
thermal spray community. Additionally, this chapter also provides a brief
description of a thermal barrier coating (TBC) and its deposition, and
furthermore, outlines the advantages of spraying a fine structured powder
feedstock instead of a conventional coarse solid powder feedstock. In addition,
the chapter also talks about the necessity of using liquid feedstock instead of solid
powder feedstock. Finally, this chapter also provides details about different liquid
feedstock processes used in this work. Chapter 3 outlines the process
characteristics of suspension plasma spraying (SPS) and the theory behind coating
formation in SPS.
Chapter 4 presents the main characteristics of the TBCs in general, and especially
highlights the microstructure, porosity, thermal conductivity, mechanical
properties, sintering behaviour and lifetime. Chapter 5 describes the
characterization techniques utilized to investigate the TBCs produced in this
work.
Chapter 6 is the core of this work. The chapter starts with briefly describing the
several critical challenges faced so far in understanding the SPS microstructures
as pointed out in the literature. Building upon those challenges, the chapter then
describes the microstructural selection and design route for obtaining highly
durable SPS TBC for various gas turbine applications. A complete design cycle
right from the processing-microstructure-properties to TBCs performance is
discussed in brief summarizing the major findings from all the appended articles
in this work. Chapter 7 provides the conclusions of this thesis work.
1
Finally, the future work for this research and a summary of all the journal papers
included in this thesis are given in Chapter 8 and 9 respectively.
1.2 Objective and research questions

The objective of this research work was to explore relationships between process
parameters, coating microstructure, thermal properties, mechanical properties
and performance in suspension plasma sprayed TBCs. A further objective was to
utilize this knowledge to produce a SPS TBC with lower thermal conductivity
compared to state-of-the-art thermal spray TBCs used in industry and propose a
tailored microstructure design of SPS TBC for achieving a superior performance.
The work was accomplished by trying to answer the following research questions:
1. How is the TBC microstructure produced by liquid feedstock thermal

spraying affected by changing spraying techniques and process
parameters?
2. What are the microstructural features present in SPS TBCs and how can
these microstructural features be characterized and quantified?
3. How can thermal conductivity of plasma sprayed TBCs be reduced by
using liquid feedstock instead of solid feedstock?
4. How do different microstructural features influence the lifetime and
sintering behaviour of SPS TBCs?
1.3 Scope
The work was mainly focused on TBCs for industrial gas turbines (IGTs) and
aero engine turbines applications. However, the screening study also revealed that
varying microstructural features and porosity could result in a wide variety of
coating microstructures, which could be applicable for various other applications
ranging from solid oxide fuel cells to rocket nozzles.
The work was mainly focused on studying the columnar type microstructures and
understanding the influence of various microstructural features present in those
microstructures on the performance of suspension plasma sprayed 8 wt. % yttria
partially stabilised zirconia (8YSZ) TBC. However, the results and knowledge
gained from this study can also be utilized for studying such a relationship
between microstructure and performance for any other possible types of
microstructures, produced by any liquid feedstock thermal spray techniques using
8YSZ or any other ceramic materials such as gadolinium zirconate or dysprosia
stabilized zirconia etc.
2
INTRODUCTION
1.4 Limitations
The major limitations of this work can be briefly summarized as follows:
i. Material
Only one ceramic top coat (TC) material, namely 8YSZ, was used in various forms
(powder/suspension/solution precursor). For bond coat (BC) a material of a
composition NiCoCrAlY/CoNiCrAlY was used, and for substrate Hastelloy® X
(Ni-based super alloy) was used. However, use of alternative ceramic TC materials
needs to be investigated in order to understand their role in further improving the
performance of TBCs.
ii. Spraying techniques and process parameters

Various liquid feedstock thermal spray techniques were utilized in this work
however only axial suspension plasma spraying (ASPS) was explored in more
detail. Techniques such as solution precursor plasma spraying (SPPS), suspension
high velocity oxy fuel spraying (S-HVOF) and SPS that were used in this work
can also be further explored in greater detail.
While exploring the ASPS process, systematic experimental design was used to
understand the influence of individual feedstock (suspension) properties in
microstructure formation and coating performance. However, no such systematic
study was conducted in studying the role of individual plasma spray parameters,
and plasma gun hardware aspects which can also potentially affect the
microstructure and performance in SPS TBCs.
iii. Characterization techniques

Several characterization techniques were utilized in this work to investigate
coating microstructure, properties and performance. The limitations of those
techniques are described here:
Microstructure was analysed using low and medium high resolution microscopes.
Use of high resolution microscopy to observe very fine scale pores and/or grains
and grain boundaries would provide even better insights to further refine the
correlations between coating microstructure and performance.
Water impregnation and mercury intrusion porosimetry (MIP) used for porosity
analysis can only measure the open pores (pores which can be accessible by water
or mercury). MIP can over-predict the porosity at low pressure regime due to the
significant influence of TC surface roughness. In addition, MIP can also introduce
errors in measuring the pore size of pores/cracks that have a narrow opening to
the coating surface but then widens-up later through the coating thickness which
can under-predict the mean pore size. Image analysis can reveal both open and
3
closed pores, but is sensitive to sample preparation. The above constraints should
be borne in mind while utilizing the results of the present study, although the
broad qualitative trends involving porosity are expected to remain valid.
Laser flash analysis (LFA), which was utilised for thermal diffusivity
measurements, is prone to uncertainty in measurements due to the transparent
nature of zirconia to the wavelengths of light produced in the LFA laser. This
issue was minimized by coating a very thin layer of graphite in order to allow the
laser light to be absorbed.
Instrumented micro-indentation was used for measuring fracture toughness. The

indents were made at half of the TC thickness and in the centre of the column
(away from the inter-columnar spacing (IC)). The measured toughness can only
provide the local toughness and can be considered to be the upper bounds of
effective toughness in coatings investigated.
Lifetime was investigated using isothermal thermal cyclic fatigue (TCF) test and
thermal shock (TS) using burner rig test. The failure in the TCF test is mainly
driven by the nature of the BC (oxidation of the BC) whereas in the latter one it
is mainly driven by the TC nature. However, combination of both BC oxidation
as well as TC effect should be considered simultaneously as it can be the case in
real life (e.g. in commercial aircrafts). Hence, a modified lifetime testing procedure
combining these two factors could also provide more information about coatings
lifetime, especially for commercial aircraft applications.
iv. TBC performance

The performance of a TBC is driven by its low thermal conductivity and high
lifetime. Thermal conductivity is discussed in more depth however in case of
lifetime many more aspects were not considered which could have further
strengthened this work if considered. For instance, the influence of BC
preparation, that is, by varying BC spraying techniques, varying the BC roughness,
post treatment of the BC by shot peening or by heat treating etc. Additionally,
measurement of residual stresses in the ceramic TC could have also given more
information about the lifetime of SPS TBCs.
Other performance related aspects such as sintering resistance, erosion, wear and
high temperature corrosion could have further strengthened this work by adding
more information regarding TBCs’ overall performance.
4
2 Background
Over the past 40 years, the gas turbine manufacturing industry has extensively
used TBCs in various sectors, such as power generation and aero engines for high
temperature applications [1], [2]. The hot sections in gas turbines include the
combustor, turbine blades and vanes, and the afterburner which can be seen in
Figure 1 (the parts in red and orange).
Figure 1: Schematic of gas turbine RM-12 aero engine [courtesy: GKN Aerospace]
In today’s aero engines, the hot gas temperature exceeds by more than 150 ᵒC the
softening point of the metallic structure of the turbine material, which usually is
a Ni-based super-alloy [1], [2]. This requires extensive cooling, which reduces the
efficiency of the engine [3]–[5]. Thermodynamics suggest that the efficiency of
gas turbine engines can be increased by increasing the combustion temperature
[3]. However increase in combustion temperature is limited by the inherent
temperature capability of the Ni-based super-alloys. There is a continuous desire
to increase combustion temperature to achieve higher gas turbine engine
efficiencies [3]. TBCs play a key role in enabling this [1], [2]. Enhancing their
insulating capability and augmenting their durability is a continuous challenge.
Due to its thermal insulation properties, there is a transient temperature drop

across the TBC in-service conditions. This drop allows higher turbine entry
temperatures and hence, higher engine efficiency [1]–[3]. The extent of
temperature drop can be increased either by lowering the thermal conductivity of
the insulating layer of ceramic TC or by increasing the TC thickness (see section
2.1.3 for TC definition). This temperature drop also prolongs the component life
in extreme operating conditions. The thickness of the TC is mainly limited by the
5
weight penalties, coating durability and cost issues. Though there are some
regions such as combustor where thicker coatings are applied; thicker coatings
may result in lower lifetime due to the increased residual stresses in the coating
[6], especially if they are used on turbine blades and vanes where coatings can
experience excessive thermo-mechanical loading. Hence, reduction in thermal
conductivity with optimal coating thickness remains the most feasible option.
In general, thermal conductivity of a TBC can be reduced if a low thermal

conductivity TC material is used. However, this is limited by the availability of the
materials that fulfil the necessary requirements of a TC, e.g. low thermal
conductivity, high thermal expansion matching with the metallic BC, thermal and
phase stability at elevated temperatures, high fracture toughness etc. Although
there has been significant progress in developing new TC materials, the most used
material so far is YSZ, a ceramic [7] that was introduced in the late ‘70s [8].
Another possible route of reducing the thermal conductivity is by changing the
microstructure of the deposited TC [9], [10], since the microstructure, i.e.
microstructural features such as pores and cracks strongly affect the thermal
properties of the TC.
Presence of various microstructural features in different microstructures of TCs,

such as pores and cracks of different shape, size and orientation [5], [11]–[13],
make these microstructures significantly different from each other. It’s these
microstructural features that, as previously stated, can significantly influence the
heat transfer through the coating [5], [10], [13]. Higher total porosity can for
instance significantly reduce the thermal conductivity of the TBC [13], [14].
Other important characteristics of a TBC than having a low thermal conductivity

are, excellent thermal cyclic durability and thermal shock resistance, phase stability
at higher temperatures for longer exposure, and low cost (this is a relative factor
and it is not as big driver as the performance). Depending on the application, a
balance between these properties is needed. For example, aero engine turbines
operate at peak power for shorter periods during take-off and landing, hence
experience relatively frequent thermal-cycling and in some cases (e.g. military
aircrafts) also a severe thermal shock, whereas industrial gas turbines (IGTs) run
typically for longer duration at constant temperature and hence experience
significantly less frequent thermal-cycling and negligible thermal shock. This
would require for instance, an excellent thermal shock resistance along with
optimum balance between other properties for TBCs used on military aero-
turbine engines.
6
BACKGROUND
2.1 Thermal Barrier Coating (TBC)

TBC is a multilayer coating system and there are three primary constituents in a
system as shown in Figure 2: (1) a metallic bond coat (BC) typically 150 µm to
300 µm thick [15]; (2) a thermally grown oxide (TGO) which grows from 0 µm
to 10 µm (or even higher) between the TC and the BC [16], [17] during the in
service life; and (3) the ceramic top coat (TC) of typically 300 µm to 1 mm [18],
which acts as a main thermal insulation layer. The BC and the TC layers can be
deposited using various coating technologies. The important thing to note here is
that the TGO is a layer which is generated due to the oxidation of the BC during
the in service life of the TBC. The different layers are described further in the
following subsections.
Figure 2: Schematic of TBC system showing each layer, its material and applications
2.1.1 Bond Coat (BC)
The BC is the first layer that is deposited on the Ni-based superalloy substrate.
The purpose of this coating is to protect the substrate from oxidation and high
temperature corrosion and to provide the necessary bonding of the ceramic to
the substrate material. Also, it helps in reducing the mismatch in coefficients of
thermal expansion (CTE) between the TC and the substrate.
The BC can be divided into two categories, diffusion (Pt-modified Aluminides)

and overlay (MCrAlX-type) coatings [19]. Overlay coatings are typically used in
thermal sprayed TBCs (TBCs can also be deposited by other techniques than
7
thermal spray, such as physical vapor deposition etc.). In overlay coatings, M is
commonly Ni, Co, Fe or a combination of these and X is an oxygen-active
element, for example Y, Si, Ta, Hf or a combination of these [20]. Usually a
mixture of Nickel and Cobalt based coatings are used.
2.1.2 Thermally grown oxide (TGO)
The second layer in a TBC system is the TGO layer (see Figure 2). When a
TBC is under operating conditions (during the in-service life), a TGO layer is
formed between the TC and the BC at the metal – ceramic interface [16], [21].
This layer is formed due to the oxidation of the BC. The porous ceramic TC
allows oxygen to diffuse to the metallic BC, which results in the oxidation of
the BC. Even if the ceramic TCs were fully dense, the high ionic diffusivity of
oxygen in the ZrO2-based ceramic TC renders it ‘oxygen transparent’ [22],
that’s why oxidation still is an issue.
The TGO plays an important role in TBCs performance. Failure in TBCs is
initiated, in or near the TGO, mostly at the TGO–BC and TGO-TC interface
[23]–[25]. The growth of a TGO layer causes stresses during in service in the
TBC, due to the difference in CTEs of different layers in the TBC. These
stresses will initiate cracks or cause crack growth in the TBC, which finally
causes failure of the TBC due to spallation of the TC. Thus, controlling the
growth of this oxide is a critical issue to increase the lifetime of the TBC.
It should be noted that several oxides are formed due to the oxidation of the BC,
which typically are Cobalt, Chrome, Aluminium alloys, such as Chromia ((Cr,
Al)2O3), Spinel (Ni(Cr, Al)2O4), Nickel oxide (NiO), Silica, and Alumina [23].
Chromia, Spinel and Nickel oxides are usually referred together as CSN in the
literature.
2.1.3 Top Coat (TC)
The last layer is the ceramic TC (see Figure 2). The main purpose of this layer is
to provide the thermal insulation to the substrate.
The choice of a material for the TC layer is determined by some basic

requirements such as: high melting point, no phase transformation between room
temperature and the operating temperature, low thermal conductivity, chemical
inertness, high thermal expansion coefficient, good mechanical properties and
good adherence to the metallic BC [10], [26]. Over the years of development of
TBCs, YSZ has become the most widely used commercial material because of its
superior thermal and functional performance compared to other ceramics [1], [2].
It has been shown [8] that by stabilising zirconia with 3-4 mol. % or 6-8 wt. % of
8
BACKGROUND
yttria, a superior coating can be created; 3-4 mol.% YSZ was shown to have high
thermal expansion coefficient, low thermal conductivity ((2.25 𝑊 𝑚−1𝐾 −1) in bulk
form), good mechanical properties and good phase stability up to 1200 ᵒC [27],
[28]. Other ceramics which can be used as TC materials are mullite, Al2O3, TiO2,
CeO2+YSZ, pyrochlores, perovskites, etc. [28].
Zirconia (ZrO2) has three allotropic crystal structures, i.e. monoclinic, tetragonal
and cubic. The monoclinic phase is stable below 1197 ᵒC but transforms to
tetragonal above this temperature; the tetragonal phase is stable between 1197 ᵒC
and 2300 ᵒC; above 2300 ᵒC tetragonal transforms to cubic, which then is stable
up to 2700 ᵒC, the melting point of zirconia [29]. This phase transformation is
illustrated below:
1197 ᵒ𝐶 2300 ᵒ𝐶 2700 ᵒ𝐶
𝑀𝑜𝑛𝑜𝑐𝑙𝑖𝑛𝑖𝑐 𝑡𝑒𝑡𝑟𝑎𝑔𝑜𝑛𝑎𝑙 𝑐𝑢𝑏𝑖𝑐 𝑙𝑖𝑞𝑢𝑖𝑑
↔ ↔ ↔
As the structural phases have different volumes, transformations from one to

another are detrimental for the performance of a TBC as it induces cracks due to
the corresponding volume change and thus promotes failure of the TC [29]. The
largest volume change is from tetragonal to monoclinic (4.5% volume expansion)
and moreover it happens at temperatures which are in the range of the in-service
temperature of a gas turbine. Thus, an external stabilizer e.g. yttria (Y2O3), ceria
(Ce2O3), magnesium oxide (MgO), calcium oxide (CaO) is added to stabilize a
desired phase in the material.
Figure 3 explains the effect of yttria content on the stability of the phases present
within the YSZ. The addition of yttria in zirconia is critical and it is important to
have the content of Y2O3 approximately between 3-4 mol.% in order to obtain a
non-transformable tetragonal (T’) phase (in Figure 3, it is shown as 6-11 mol. %
since it is 0.5 (Y2O3)), which is very resistant to the transformation. Below 3-4
mol. % Y2O3 content a transformable tetragonal (T) phase is formed, which may
undergo phase transformation as explained above.
As it can be seen from the phase diagram (see Figure 3), at higher temperatures,
even the metastable non-transformable tetragonal (T’) phase, undergoes a phase
separation by diffusion, when aged at temperatures greater than 1200 °C. This
can allow the tetragonal to monoclinic (T → M) transformation upon cooling.
This transformation, as explained earlier, induces cracks, which then may lead to
the failure of the coating. Hence, YSZ becomes an ideal material for applications
only up to operating temperature less than 1200 °C [7]. Addition of higher
contents of yttria could completely stabilize the high temperature phases, but the
mechanical properties (toughness, erosion resistance) are also altered, so that the
in-service requirements and lifetime are negatively affected [2], [29].
9
Figure 3: Phase diagram of zirconia showing the influence of yttria content at
respective temperatures on different phases (tetragonal (T), cubic (F) and monoclinic
(M)) of zirconia [29]
2.2 Thermal spraying of a TBC

Thermal spray [18] is a technique used to deposit a coating on various structures;
in which metallic or non-metallic coating feedstock material, in the form of rod,
powder, wire, suspension or solution, is fed into a spray ‘gun’ by a controlled feed
system. This feedstock material is heated by electrical (plasma or arc) or chemical
(combustion flame) means and then accelerated by the hot gas/plasma plume
10
BACKGROUND
towards the substrate. Accelerated feedstock material then impinges the substrate
in the form of molten or semi-molten state droplets, which upon impact form a
pancake shaped so called ‘splats’ and adheres to the substrate by rapid
solidification and quenching.
This coating technology, which is a branch of surface engineering is considered

as one of the production technology methods. This method can be used not only
for repairing, rebuilding, and retrofitting machine components but also for
restoring original dimensions or applying protective metal layers to various
infrastructures, such as bridges, turbines etc. [18], [30].
A major advantage of thermal spraying is that it can be used to produce a coating

without a significant heat transfer to the substrate. This avoids thermal distortion
and possible damage to the substrate. The major disadvantage of thermal spraying
is that it is a ‘line of sight’ process, which makes complex geometry components
difficult to spray. Plasma spray physical vapor deposition is another process by
which shadowed areas can also be coated [31].
For spraying a TBC, several thermal spraying techniques are available. The BC is
usually sprayed by plasma spraying or high velocity oxy-fuel (HVOF) and more
recently by high velocity air-fuel (HVAF) spraying [32].
BC needs to be dense (negligible porosity) to serve its purpose in the TBC, that
is to minimize the oxygen penetration to the substrate and also to avoid internal
oxidation. Due to the high jet velocity involved in the HVAF process (typically
over 1000 m/s), a very dense coating can be produced [33].
Feedstock material in HVAF is mostly in the form of powder, and is injected

axially into the flame at the nozzle exit. The feedstock material is then partially or
fully melted and accelerated towards the substrate. With a very high impact the
particles then form a splat. Subsequent splat deposition over each other at high
velocity lead to the dense coating formation [33].
The TC is usually sprayed by plasma spraying since this process inherently has
enough thermal energy to enable melting of the ceramic powder during the short-
dwell time typical of thermal spray processes. EBPVD process is also
commercially used for TC deposition as it can produce strain tolerant TCs. In the
following subsections, deposition of the TC and BC layers using various thermal
spray processes and feedstock materials used in this study are described.
11
2.2.1 High velocity oxy fuel spraying (HVOF)
HVOF spraying is one of the variant of conventional flame spraying where a

warm flame is produced due to the combustion process which acts as a heat
source to melt the powder feedstock. In this process a mixture of fuel gases
(typically Hydrogen, Propane and Propylene) and Oxygen are introduced into the
combustion chamber along with the powder feedstock. The combustion process
produces high temperature and pressure in the chamber which in combination
with the specifically designed long convergent-divergent nozzle (through which
these gases are accelerated) produces a supersonic jet resulting in high particle
speed. The feedstock powder particles can fully or partially melt (depending on
the fuel/Oxygen) mixture in the chamber as well as during the flight through the
nozzle.
The advantages with this process, due to its reasonable process temperature and
very high particle velocity on impact, are very dense and adherent coatings [34].
The process is suitable for spraying metallic, cermet as well as ceramic coatings
for various applications. This makes it more suitable technique for spraying
especially the BCs [23] but also TCs [35] in TBCs.
2.2.2 High velocity air fuel spraying (HVAF)
Another variant and more recent addition to the flame spraying techniques is
HVAF spraying. Unlike HVOF, a mixture of compressed air and fuel gas is used
in the combustion process which makes HAVF process relatively colder than
HVOF [36]. Hence, HVAF is more suitable for spraying metallic powders
especially those which are sensitive to high temperature oxidation such as metallic
BCs in TBCs.
Advantage with this process over HVOF is the extremely high particle speed
resulting in coatings with negligible porosity and good adhesion strength. In
addition, the low heat input to the feedstock allows good control of oxide content
in some materials which are sensitive to oxidation at high temperature [33], [36].
The low heat input also ensures minimal in-situ particle oxidation and reduced
phase transformation or elemental depletion/decomposition of in-flight particles
due to the lower in-flight particle temperature [37]. Moreover, higher impact
velocity in HVAF can also produce relatively smoother coating surfaces which is
considered to be beneficial, especially for the production of BCs in case of SPS
TBCs to enhance their strain tolerance by increasing the column density (number
of columns per unit length) [38]. In this study, HVAF was used to deposit BCs
because of its capability to produce extremely dense, smooth, oxidation resistant
and adhesive coatings.
12
BACKGROUND
2.2.3 Atmospheric Plasma spraying (APS)
Plasma spraying is the conventional technique to deposit TBCs (both TCs as well
as BCs) where plasma is used as a heat source to melt the feedstock material. If
the process is carried out in inert/controlled atmosphere then it is referred as low
pressure plasma spray (LPPS) or vacuum plasma spray (VPS) process. If the
process is carried out in a normal atmosphere then it is called as atmospheric
plasma spray (APS) which is discussed in more detail in this section. Due to the
high temperature in the plasma, which can exceed 20000 °C [30], and thus the
high thermal energy, the plasma plume can easily melt any type of feedstock
material.
Figure 4: Schematic of conventional powder atmospheric plasma spraying process
The basic principle of this technique consist of melting a consumable (most often
powder of size 10 µm to 100 µm [39]) and projecting it as droplets of molten or
semi molten particles onto the substrate as can be seen in Figure 4. The modern
plasma spraying process uses a direct current electric arc, to generate a stream of
high temperature ionized plasma from one or a mixture of inert gases (Ar, He,
H2, N2), which act as the spraying heat source. The coating material, in powder
form, is conveyed by a carrier gas (typically Argon) stream into the plasma plume,
where it is heated and propelled with a typical particle velocity of 200-300 m/s
towards the substrate [30]. The accelerated droplet of molten or semi molten
particles strike the substrate and under its impact to the substrate forms a splat.
Subsequent deposition of splats over each other leads to the formation of a
coating, see Figure 5. The generated splat can be in a size range of few tens to
few hundreds of micrometre in diameter and few micrometre thick [39],
depending on the spraying conditions or particle size used during spraying.
13
The formed splats, shrink and solidify upon impact, and can form a void or pore
in between the splats. Additionally, a splat may also have gases trapped in it, which
can also lead to the formation of a pore within the splat when the splat is solidified
upon cooling.
To generate a desired coating microstructure by plasma spraying, several process

parameters need to be controlled, which are explained through the schematic
shown in Figure 5. This figure can be generalized for almost all types of plasma
spraying techniques with certain changes depending on the specification of the
technique. In general, these process parameters can be categorized as: injector and
feedstock parameters, spray gun parameters, robot fixture parameters, substrate
and plasma plume parameters. The desired microstructure that forms during
powder spraying is controlled by the complete history of powder material used;
from production, to in-flight conditions to final impact on the substrate leading
to the formation of splats.
The size of the powder particles is very important as it is a major factor

influencing the microstructure of the coating and hence its functional properties
[40], [41]. Many advantages have been found when the coatings were deposited
using fine (submicron and nano-size) powder particles, which are explained below
in detail.
Figure 5: Schematic of plasma spray process characteristics showing the various

process parameters
14
BACKGROUND
2.2.3.1 Fine powder feedstock
Spraying fine powder particles compared to conventional coarse powder particles

result in coatings having fine microstructure. These fine structured coatings are
characterized by their fine (submicron or nano) microstructural features present
in the coating microstructure such as fine pores/cracks, fine grains etc. Any
nanostructured (or nano-crystalline) material is characterized by a microstructural
length or a grain size of 1 nm – 100 nm, whereas submicron structured material
is characterized by 0.1 µm to 0.3 µm of its grain size [42].
Such fine structured coatings have shown to have advantages over conventional
coatings such as lower thermal diffusivity and thermal conductivity at room
temperature [24] as well as at higher temperatures up to 1200 ᵒC [43], [44]. The
sub-micrometric and nanometric microstructural features have been shown to
lower the thermal conductivity [45]. Furthermore, these fine structured coatings
have also been shown to be better in thermal shock resistance, thermal-cyclic
fatigue lifetime and a better CTE match [43], [46].
It is difficult to spray fine solid powder feedstock (20 nm to 5 µm) using a standard
APS equipment. This is because, these fine particles do not have a good flow-
ability and also can’t achieve enough momentum to penetrate the high velocity
plasma stream [47]. Spraying fine powder particles may also be an environmental
issue i.e. a health problem.
For both health reasons as well as to avoid particle agglomeration during storage
and feeding into the spray equipment, a liquid feedstock can be used [48]. The
liquid injection method can increase the momentum of the feedstock particles,
aiding penetration of fine particles into the thermal jet core. Details about liquid
feedstock spraying are provided in the next section.
2.3 Liquid feedstock spraying

In liquid feedstock spraying, fine powder particles are mixed with a fluid to form
a liquid (suspension or solution), which then is injected into the plasma/flame
either by atomization or by a liquid stream [49], [50], [50]. In Figure 4, instead of
solid powder particles one can imagine a stream of liquid or atomized (break-up
of liquid stream into smaller droplets) liquid droplets to be injected into the
plasma plume.
Examples of thermal spray processes that use liquid feedstock are SPPS, S-
HVOF, SPS and ASPS [35], [49]–[53], where a liquid in the form of suspension
or solution, instead of direct solid powder, is used as a feedstock material.
15
2.3.1 Suspension and Solution
Figure 6: Schematic of a suspension and a solution precursor droplet
Suspensions are prepared by mixing solute powder particles of size a few microns,
submicron or nano-meter in range in a solvent (water or alcohol (mainly ethanol)).
A serious issue with suspensions is that they settle down with time, which if not
properly re-dispersed before spraying, can influence the coating microstructure
and properties. To overcome this problem, some additional elements can be
added such as dispersant agents, which can prevent agglomeration of the particles
or settling down of the suspension [49]. Proper stirring is required for the
suspensions during the spray in order to minimize the settling problem. Also,
pumping of suspensions from the storage tank to the plasma torch should be
made in a way to generate as stable flow as possible. Any fluctuations may cause
a non-homogenized coating structure.
Solutions are a homogeneous mixture of a solute (precursor material) and a

solvent, and unlike suspensions no solid particles exist in it. In Figure 6, a droplet
of suspension with many fine solid particles and a droplet of homogenized
solution are shown. Typically the solutions are salts of respective ceramic
powders, such as nitrates, chlorides, acetates, iso-prop oxides and other
combinations [49].
16
BACKGROUND
2.3.2 Solution Precursor Plasma Spraying (SPPS)
A recent development in liquid feedstock spraying is the SPPS process, where a

liquid in the form of a salt solution of a respective ceramic powder is injected into
the plasma. The solution is fed into the plasma plume, where, the salt is oxidized
in-flight forming an oxide particle. Under rapid heating, the solution droplet
evaporates and the solid oxide particles in contact with the plasma, are melted and
subsequently deposited onto the substrate [54]. Deposition of fine, melted
particles then leads to a fine structured coating.
An advantage of SPPS over conventional APS technique in case of TBCs is that

it can produce a strain tolerant vertically cracked microstructure with lower
thermal conductivity than APS, due to vertical cracks (cracks normal to the
substrate) and the submicron and nano-sized interconnected porosity [55].
Another advantage of SPPS is that new chemistries can be sprayed that may not
be possible with other techniques due to unavailability of feedstock. However, a
limitation of this technique is currently the deposition efficiency due to the
difficulty in spraying high molarity solutions.
2.3.3 Suspension High Velocity Oxy Fuel (S-HVOF)
Another possibility in liquid feedstock spraying is the high velocity suspension

flame spraying (HVSFS), which is a modification of the conventional HVOF
thermal spraying process. This is also referred as S-HVOF spraying [52]. Here,
the liquid is in the form of a suspension of the respective ceramic powder.
S-HVOF was developed with the aim of spraying submicron or nanoparticles

suspensions with hypersonic speed to deposit thin and very dense coatings.
Suspension injection in this process usually is done axially i.e. in same direction as
the spray direction [35].
The process parameters which can influence the final coating structures in this
process are different from plasma spraying. Examples of important parameters
that can be controlled in order to obtain a desired microstructure are [35]:
 Suspension injection nozzle shape and geometry: In HVSFS, shape and

exit nozzle diameter plays a crucial role as it decides the shape of the
exiting suspension spray jet.
 Combustion fuel type: Different fuels have different burning
characteristics, which can influence the flame temperature and hence the
particle temperature. Combustion fuels such as propane, ethane,
acetylene etc. can be used.
17
 Total gas flow: Gas flow can influence the flame velocity and hence the
particle velocity. Higher total gas flow rate can result in higher particle
velocity.
Due to the high particle velocity involved in this process (typically around 400
m/s to 600 m/s [30]) the coatings are expected to be denser than the conventional
APS and the SPPS coatings.
2.3.4 Suspension Plasma Spraying (SPS)
Another spraying process by which a liquid feedstock can be sprayed is SPS [49],
[50], [56] which is also the process mostly used in this study. Like in S-HVOF,
submicron or nano-sized powder particles are first dispersed in a solvent, typically
water or alcohol, in a certain ratio (typically referred as solid loading) to form a
liquid (in this case a suspension). This suspension then is injected into the plasma.
The suspension is then undergoes atomization to form very fine suspension
droplets, where each suspension droplet consists of extremely fine solid powder
particles individually or in agglomerated form. The liquid from the droplet
evaporates quickly and the fine powder particles can undergo sintering, partially
or fully melting and may form agglomerates. Then, they get deposited with an
impact on the substrate to form a fine structured coating [49].
The major drive for SPS in case of TBCs comes from the possibility to develop
coatings with a unique strain tolerant columnar microstructure similar to EBPVD.
SPS coatings have shown to have a similar columnar structure as of EBPVD, but
with a lower thermal conductivity [57]. Columnar coatings with a lower thermal
conductivity are demanding in gas turbine industry due to their inherent strain
tolerant nature, which enhances the lifetime of the coating.
Even though, SPS has shown a great interest of research for producing TBCs for
gas turbine applications, the complexity involved in the process as such makes it
a very difficult process. This process can be described by understanding the
detailed process characteristics, which are explained in detail in the next chapter.
18
3 Process characteristics of SPS
Similar to the conventional plasma spray process, coating microstructure and thus
coating properties in SPS depend on various process parameters. In fact, in this
case the process becomes even more complex due to the chemistry of the
suspension and very fine powder particles involved. All process parameters
schematically shown in Figure 5 are also important in SPS. However, some extra
parameters, which are also important in this process and can have significant
influence on the coating microstructure and properties, are discussed below.
3.1 Type of solvent

As explained in section 2.3.1, suspensions can either be water based, alcohol
(mainly ethanol) based or a mixture of water and alcohol based. Both water and
alcohol have some advantages over each other, but also have limitations. The
water based suspension is cheaper and easy to transport/handle than the ethanol
based suspension which requires more safety control. But, the heat required to
vaporize ethanol is one-third of that of water, which leads to higher usage of
power needed during spraying in case of water based suspensions [58]. Also, it
was found that the deposition efficiency and the ratio of the coating mass to the
powder mass sprayed towards the substrate doubled, when switching from a
water-based YSZ suspension to an ethanol-based YSZ suspension [59].
Properties such as viscosity and surface tension of the suspension are also
important and depend on the type of solvent used, which can play crucial role in
SPS coating formation, as further discussed in 3.5 and 3.6. Water based
suspensions has higher surface tension than ethanol based suspensions, due to
the higher surface tension of water than ethanol [49], [60]. However, viscosity of
the suspension is not significantly altered by changing the solvent but by changing
the solid load (amount of powder in suspension) and solute particle size [49], [60],
[61].
3.2 Initial size of the solute powder particles

In conventional solid powder feedstock APS coatings, the scale of microstructural
features present in a coating microstructure directly depends upon the initial
powder particle size. However, unlike APS, initial powder particle size of the
respective solute ceramic powder in a suspension may not necessarily be directly
reflected on the microstructure and the microstructural features in SPS TCs [62].
19
Initial powder particle size is usually denoted as the median size or D50, which is
the median diameter of a powder particle in a certain particle size distribution and
it signifies that half of the particles lies below this size. As discussed earlier, typical
fine powder particles used in SPS are shielded by the solvent fluid around them,
which forms a suspension droplet as shown in Figure 6. Unlike in APS, upon
injection in the plasma plume, it is this droplet which is in direct contact with the
plasma and not the powder particles. This droplet consisting several of those fine
powder particles undergoes a thermal treatment in the plasma, which is discussed
in the section 3.5. Due to this thermal treatment the initial powder particle size
may indirectly influence the microstructure, which is also discussed in section 3.5
(in-flight conditions).
3.3 Solid load in the suspension

Solid load is defined as the relative amount of solute suspended or mixed with the
solvent (water, alcohol or mixture). Typically solid load in suspensions are
measured in units of weight percent. For example 25 wt. % solid load refers to 25
grams of solute and 75 grams of solvent in 100 grams of suspension.
Theoretically, higher the solid load in the suspension more the potential
deposition rate of the SPS process [63] which is of course a major industrial drive.
However, there are several challenges associated with the high solid load content
in the suspension. For instance, the stability of the suspension (suspensions with
higher solid loading may settle down quickly than lower solid loading); clogging
of the gun injector/nozzle; sufficient power/energy required for proper melting
(more power is needed to properly melt the highly loaded suspensions than low
solid load suspension); but more importantly the challenge in droplet formation
or atomization (discussed in more details in section 3.5) which is necessary for
column formation in the columnar structured TBCs. All these challenges can lead
to an undesired coating microstructure which must be countered in order to use
highly solid loaded suspensions in SPS process.
3.4 Injection of suspension

Proper injection of a suspension is as important as other process parameters
discussed so far to obtain the desired coating microstructure. This is because in
SPS, droplet formation has a great influence in the coating formation which will
be discussed in section 3.6.
Injection of the suspension can be influenced by following two factors:
1. Injector type and injector size
20
PROCESS CHARACTERISTICS OF SPS
a. Mechanical injectors
b. Atomizing injectors
2. Injection type
a. Radial injection
b. Axial injection
Injectors can be of two types, either a mechanical injector or an atomizing

injector. In a mechanical injector, which is also called a stream injector, a stream
of suspension is injected into the plasma plume. In this case, the plasma plume
itself performs the step of stream break-up into small droplets. However, in an
atomizing injector, the suspension stream is first atomized (broke-up) into smaller
droplets and then injected into the plasma plume. Apart from the type of injector,
the size or the opening of the injector (orifice) can also significantly affect the
droplet formation. Narrow orifice can shear the suspension stream more
rigorously augmenting in fine droplet formation and can also provide higher
droplet exit velocity into the plasma plume.
The liquid feedstock can be injected into the plasma plume either by radial
injection or axial injection which are explained below.
3.4.1 Axial injection versus radial injection
The term ‘radial injection’ means injecting the feedstock material perpendicular
to the plasma flow. ‘Axial injection’ means injecting the feedstock material in the
same direction as the flow of plasma. This is illustrated schematically in Figure 7.
If the liquid feedstock material is injected radially, it may have a strong effect on
the thermal treatment and the trajectory of the droplets during the in-flight.
Different droplet sizes result in different momentum of the droplets when they
enter the plasma stream and hence their trajectories will be different. For example,
very small droplets may not penetrate the plasma at all or pass only through the
periphery. Optimum sized droplets may enter the core of the plasma and get fully
treated. However, larger droplets may completely pass through the plasma
resulting on the substrates as un-molten particles (overspray) due to insufficient
thermal treatment. Entering different zones of the plasma plume as well as
different dwell times (the total time, a droplet spends in a plasma plume) lead to
different heat treatment and acceleration of the droplets towards the substrate
which leads to a more heterogeneous microstructure. This is explained
schematically in Figure 7 (a).
21
Figure 7: Schematic of radial injection (a) versus axial injection (b) of liquid feedstock
Axial injection on the other hand can overcome this problem, as there is no issue
of trajectory involved due to the parallel injection of feedstock material to the
spray direction. As can be seen from Figure 7 (b) that, instead of an individual
droplet trajectory, distribution of droplets undergo a uniform treatment during
the in-flight conditions in the plasma. This work mostly explored an axial injection
and hence more emphasize is given on axial injection from hereon.
3.5 Sequence of events in SPS coating formation

Assuming a stable flow of suspension upon injection in the plasma plume,
suspension droplets may undergo various stages before impacting the substrate
(see Figure 8). These are, injection of suspension, atomization of suspension,
vaporization of solvent from the suspension droplet, agglomeration of the fine
solid particles in the suspension droplet, melting of solid particles and finally
impacting the substrate in the form of molten/semi-molten droplets to form fine
splats leading to a coating build-up. The treatment of the suspension droplet
during each stage will depend on the characteristics of the solute particles in the
suspension droplet e.g. particle size (D50) and amount/mass (solid load) etc. as
shown for three different cases i.e. medium particle size (I & II), very fine particle
size (III) and coarse particle size (IV). All these different stages are explained in
great detail below.
22
Figure 8: Schematic of various stages of a suspension droplet (having varied particle

size (D50) i.e. medium (I & II), very fine (III) and coarse (IV)) during the in-flight, from
injection of the suspension to the final deposition on the substrate
Stage 1: Injection
Figure 9: Schematic illustration of an axial injection utilized in this work for axial III
plasma system
23
The first stage is the injection of the suspension. As stated above, in radial
injection the suspension droplets can be treated non-uniformly in the plasma
depending on whether the suspension droplets can enter in the core of the plasma
plume, which is extremely hot, or at the periphery which is colder [64]. However,
there is no such problem in an axial injection as the suspension is injected co-
axially with the plasma plume so that most of the suspension droplets are
introduced into the core of the plasma. The axial injection of suspension as
utilized in this work is schematically shown in Figure 9. An important aspect while
axially injecting the suspension is the position of the injector exit orifice (see
Figure 9) as it can significantly influence the suspension stream breakup which is
the second stage as explained below in more detail.
Stage 2: Atomization
The second stage is the atomization of the suspension, which occurs in two steps
that is primary atomization and secondary atomization. Primary atomization is
mainly caused by the atomizing gas which occurs just after the suspension stream
comes out of the injector exit (see Figure 8 and Figure 9). As explained earlier in
Stage 1, the position of the injector exit can also affect the primary atomization
i.e. the primary atomization effect can be made stronger by retracting the injector
as shown in Figure 9. Secondary atomization occurs due to the plasma drag once
the suspension stream or suspension droplets come in contact with the plasma as
shown in Figure 8. The final droplet size is the combination of both primary as
well as secondary atomization effects. However, in high power axial injection
system such as Mettech III axial gun as used in this work, the primary atomization
effect can be considered not as significant as the secondary atomization effect
which is due to the plasma. This is because unlike in conventional plasma spraying
with radial injection, in an Axial III plasma torch the plasma plume forms very
close to the injector exit, thereby negating the primary atomization effect. With
this assumption i.e. neglecting the primary atomization effect, the focus from now
onwards is mainly on secondary atomization effect.
The following factors can influence the secondary atomization:
1. Plasma drag force

2. Surface tension of the suspension
3. Viscosity of the suspension
Fazilleau et al. have derived a relation between these parameters and the atomized
suspension droplet size [65], as shown below:
8𝜎
𝐷= (1)
𝐶𝐷 𝜌 𝑢2
24
Where D (m) is the suspension droplet diameter produced due to atomization, 𝜎

(N/m) is the surface tension of the suspension, 𝐶𝐷 (unit less) is the drag
coefficient, whereas 𝜌 (kg/m3) and 𝑢 (m/s) are density and stream velocity of the
plasma respectively.
From the above equation, it can be seen that, to obtain a smaller suspension
droplet, a lower surface tension and a higher plasma drag force, which depends
on plasma density and velocity, is needed. Also, the viscosity of a suspension,
which is not discussed in this equation influences the atomization. Lower viscosity
favours higher atomization of the suspension [60]. More detailed relation between
atomized droplet size and various factors in general for aerodynamic breakup of
a liquid droplet (in this case suspension) by a certain media (in this case plasma)
is given by Wolfe et al. [66] as shown below:
1/3
1 3
136ɳ𝑑 2 𝜎 2
𝐷=( 1 ) (2)
𝑢4 𝜌𝑠2 𝜌𝑝2
where D (m) is the final droplet diameter produced after secondary atomization,
ɳ (Pa.s) is the viscosity of the suspension, d (m) is the initial diameter due to
primary atomization, 𝜎 (N/m) is the surface tension of the suspension, 𝑢 (m/s)
is the stream velocity of the plasma, whereas 𝜌𝑠 (kg/m3) & 𝜌𝑝 (kg/m3) are the
densities of the suspension and plasma respectively. The utility of this relation for
SPS coatings is discussed by Curry et al. [62].
Plasma stream velocity and plasma density (and hence plasma drag force) can be
controlled directly from the plasma gun hardware. Similarly, they can also be
controlled by the plasma gas compositions, flow rate and the arc current. Surface
tension depends on the solvent used. Water has much higher surface tension than
ethanol, which then makes difficult to atomize the suspension. Viscosity, on the
other hand can be modified by altering the suspension solid load and solute
particle size [49], [60]. In general, the initial suspension droplet size (d) depends
on the atomizing gas composition, atomizing gas flow, injector size, injection type
(radial or axial) and also injector retraction distance if it is axial injection.
Stage 3: Evaporation of the solvent
The atomized suspension droplets are rapidly heated up in the plasma plume and
hence the solvent from the droplets vaporizes. Vaporization of the suspension
during the in-flight stage undergoes with thermal energy absorption from the
plasma plume which thus gets cooler. Cooler plasma may result in insufficient
melting of the solid particles. Hence, suspension plasma spraying needs more
25
energy or power during spraying than conventional powder spraying. Also, the
droplets are accelerated concurrently with the vaporization stage.
Stage 4: Agglomeration of the solute particles
The solute particles (initial powder particles of certain D50 mixed with the solvent
as discussed in 3.2) of respective ceramic powder used in the suspension are
usually very fine. After the solvent evaporation, these fine particles have a
tendency to undergo agglomeration or sintering. The extent of agglomeration can
depend upon the size of the particles as can be seen from the Figure 8 in case IV
where there are coarse powder particles the agglomeration stage is not valid.
Whereas in case of extremely fine powder particle size as in case III the
agglomeration can be larger. Anyway, such agglomeration may certainly lose the
original characteristics of fine particles, since they are no more independent fine
particles but agglomerated and often sintered or fused into larger particles. This
is also one of the reason that the initial powder particle size (D50) may not directly
influence the microstructure. However, larger initial particle size (D50) means that
the atomized droplet (containing some agglomerated fine particles) contains
larger solid particles’ mass, which undergoes melting in the next stage.
Stage 5: Melting of the solute particles
Complete vaporization of solvent leads the agglomerated fine solid powder

particles in direct contact with the plasma, thus they are heated up and melted and
from molten/semi-molten droplets. The molten droplets may consists of few of
the initial powder particles of certain D50, which were agglomerated in the
previous stage and which may result in slightly larger solid mass in the molten
droplet than the initial powder particle mass. This then explains, why the fine
microstructural features may not necessarily be a direct result from the fine initial
powder particles in the suspension started with. Instead, it is this molten droplet
(of different size and mass (typically larger and heavier) than the initial powder
particle), which decides the splat size and hence the other microstructural features
in the coating. The degree of heating so as melting depends again on the overall
power level of the spray process and also the plasma gas composition [67]. The
heating of a solid particle/suspension droplet also depends on the spray distance,
usually in SPS the spray distance is kept shorter than the conventional APS. This
is because of the very fine size of the powder particles involved in SPS; which
needs less time to be melted. The small size also means that the particles are
cooled faster, hence a shorter spray distance is necessary. Longer spray distance
in SPS thus can result in re-solidification of the molten droplets before they arrive
at the substrate resulting in round spherical particles in the coating microstructure.
26
Stage 6: Deposition of the molten droplets
In the final stage, the molten or semimolten agglomerated solid particles in the
form of a molten droplets (larger and heavier than the initial powder particle) end
up on the substrates with a heavy impact to generate fine splats (the region is
highlighted in Figure 8 by red dotted lines close to the substrate). The way the
molten droplet impact the substrate is presented in next section 3.6. Subsequent
deposition of these splats then leads to a coating of a certain thickness depending
on the spraying conditions and the application.
3.6 Coating formation in SPS
Figure 10: Schematic showing the shadowing effect on the substrate asperity of
molten droplets with different sizes
Coating build up in suspension plasma sprayed coatings is completely different to

that in conventional APS powder sprayed coatings. Coating formation in SPS is
understood to be related to the generation of very fine suspension droplets due
to the atomization of suspension after injection and resulting fine molten droplets
[68]. The trajectory of the droplets smaller than 5 µm can be affected by plasma
stream in the boundary layer close to the substrate and deposit at shallow angles
on surface asperities leading to shadowing effect [68], which is shown
schematically in Figure 10. This is because of the low momentum of these smaller
droplets, which can be influenced by the drag of the plasma stream in the
boundary layer close to the substrate. This can be seen in Figure 11 where,
27
Berghaus et al. simulated the influence of plasma direction changes on
droplet/particle velocities [68]. Note that Figure 10 and Figure 11 are describing
the region highlighted by red dotted lines close to the substrate in Figure 8.
Figure 11: Schematic showing the effect of plasma flow on a trajectory of the droplets
just before the final impact as a function of droplet momentum, Adopted from
Berghaus et al. [68]
Based on the above concepts VanEvery et al. has proposed three major possible
types of coating microstructures in SPS [69]. If the suspension droplet size after
the fragmentation is extremely small (< 1 µm), the shadowing effect is larger,
which can generate a columnar type structure. Suspension droplets having higher
size (> 1 µm) but still small enough (< 5 µm) to be affected by the plasma flow
can form a structure with some porosity bands within the columns which can be
termed as feathery columnar structure. Such a column formation is also
demonstrated in Figure 12 where it can be clearly seen the columns building-up
pass-by-pass on BC asperities due to the shadowing effect.
Finally, droplets with significantly larger size (> 5 µm) can have a direct impact
on the substrate with a very little influence of a plasma drag. This may result in to
a lamellar (similar to the conventional powder sprayed APS process) or vertically
cracked structure. The mechanism of vertical crack formation in coatings
produced by conventional APS process is known to be due to the cooling and
shrinkage of the deposited splats which result in high tensile stresses and
subsequent intra-splat cracking during cooling [53]. The presence of such cracks
28
can eventually form vertical cracks as the splats overlap subsequently during
coating build-up. Similarly, increased tensile stress level can be relieved in SPS by
forming vertical cracks as observed in this work during coating build-up [53].
Figure 12: Demonstration of column build-up on an as-sprayed bond coat
A detailed description about the microstructure evolution and coating formation

in SPS is thoroughly discussed in Paper F appended at the end of this thesis.
29
4 Characteristics of TBC
The most important characteristics of a TBC are the microstructure, porosity,

thermal conductivity and lifetime under cyclic thermal loads. The significance of
all of them is discussed in detail in this chapter.
4.1 Microstructure
If there is something which can explain most about the final properties and
performance of a thermal spray coating, then it is the coatings’ ‘microstructure’.
Changes in coating microstructure result in changes in coating properties [10],
[11], [70], thus it is important to understand its formation and how various
microstructural features influence the coating performance. In this section a
typical APS microstructure and a SPS coating microstructure are discussed.
4.1.1 Solid powder feedstock APS sprayed coatings
Typical solid feedstock APS coatings’ microstructure have a lamellar structure as

shown in Figure 13. The coating is built-up by subsequent deposition of splats
with sizes in the range of tens to hundreds of micrometer in diameter and few
tens of micrometer in height, which finally form lamellar structured coating. The
lamellar structured coating is heterogeneous and has lot of microstructural
features such as fine pores, globular pores, cracks and delaminations of various
sizes. They are important characteristic of the coating, since they strongly
influence the coating properties.
Delaminations and cracks are formed in the coating due to the insufficient
bonding of splats to the surface and cooling of splats respectively. Fine pores are
formed due to the gas bubbles between splats or gas voids within powder
particles. Globular pores on the other hand, are formed due to low temperature
or velocity parameters resulting in partially molten particles and voids between
particles [18].
All these features contribute to the overall porosity of the coating which influence
the thermal insulation as well as lifetime of the coating. The role of these various
microstructural features on thermal properties will be discussed in the later
sections in detail. Mechanical and functional properties such as coatings’ stiffness,
31
thermal cyclic fatigue as well as thermal shock lifetime etc. are also influenced by
these features and discussed in the later sections as well.
Figure 13: SEM micrograph of a cross-section of a typical APS powder sprayed

lamellar TC microstructure highlighting the important microstructural features
4.1.2 Suspension plasma sprayed coatings
Suspension plasma spray, as explained in Chapter 2, can give a wide variety of

coating microstructures. On a macro-scale these coatings exhibit different
microstructural features such as: vertical cracks, spacing between columns (inter-
columnar spacing (IC)), inter-pass porosity (IP) bands, branching cracks etc.;
whereas at a micro-scale, coatings show features such as fine pores and cracks
(interconnected or unconnected). Based on the microstructure at a macro-scale
these coating structures can be mainly categorized as follows (Figure 14):
1. Vertically cracked structure

2. Highly porous structure
3. Columnar structure
32
CHARACTERISTICS OF TBC
Figure 14: SEM micrographs of a cross-section of the coating, showing the variety of
microstructures of TC which can be produced by suspension plasma spraying.
(Vertically cracked (a), Highly Porous (b) and Columnar (c))
Depending on a specific combination of numerous factors such as feedstock

material, spray technique and spray parameters etc., which are discussed in
Chapter 3, any of the particular structure or a structure similar to these can be
obtained.
As explained above, these coatings also look different at micro-scale, as can be

seen in Figure 15. It can be observed from the figure that the coating also has
features in submicron and nano range. Various possible typically observed
microstructural features in SPS polished and fractured microstructures are
highlighted in Figure 15 and Figure 16 respectively, where they are indicated with
arrows of different colours and notations as follows: columns (C in blue), inter-
columnar spacing (IC in violet), spherical particles (S in orange), well-molten
splats creating dense zones (black), fine cracks (FC in yellow), nano pores (NP in
red), submicron pores (SP in green) and micron pores (MP in white).
33
Figure 15: SEM micrographs of a cross-section of a SPS TC within a column (a) and
near inter-columnar spacing (b) showing various microstructural features: columns (C
in blue), inter-columnar spacing (IC in violet), spherical particles (S in orange), fine
cracks (FC in yellow), nano pores (NP in red), submicron pores (SP in green) and
micron pores (MP in white) [Ganvir et al. Materials and Design, 2017]
34
Figure 16: SEM micrographs of a fractured top-view (a) and its magnified picture
within a column (b) of a SPS TC showing various microstructural features: columns (C
in blue), inter-columnar spacing (IC in violet), spherical particles (S in orange), fine
cracks (FC in yellow), nano pores (NP in red), submicron pores (SP in green), micron
pores (MP in white) and well molten splats (in black) [Ganvir et al. Materials and
Design, 2017]
4.2 Porosity
Porosity is one of the key characteristics of the ceramic TC. In SPS coatings,
several of the above mentioned different microstructural features, both at large
35
scale and small scale, contribute to the total porosity content of the coating. These
pores are nothing but empty voids mostly filled with air at ambient conditions.
Porosity can be open when the pores are interconnected (accessible by a fluid if
injected externally) or closed when they are isolated from each other (non-
accessible by a fluid from outside the coating). The definition of open porosity
and closed porosity may vary depending on the usage of the porosity term in
various applications, but in case of TBCs it is dealt with a fluid accessibility in
pores.
 Open porosity: Vertical cracks, inter-columnar spacing, inter-pass

porosity bands which are typically connected with the vertical cracks or
inter-columnar spacing. Also, in some cases there can be branching
cracks, cracks which originate at the vertical cracks or inter-columnar
spacing and grow parallel to the substrate.
 Closed porosity: Smaller and larger scaled globular pores which are
independently present in the coating, independent clustered pores which
are connected with each other but not with any of the features shown in
the open porosity so that an external fluid cannot reach them. Also, in
some cases, fine cracks which are present in the coating but not
connected with any of the features shown in the open porosity.
Figure 17: Simplified schematic of typical suspension plasma sprayed TC

microstructure, showing all possible features which can be counted in as total porosity
36
All features shown in Figure 17 can significantly affect both the thermal insulation
nature as well as the lifetime of the coating. Vertical cracks or inter-columnar
spacing are through the thickness of the TC. These cracks. if present in large
number (higher vertical crack density in the coating), can increase the overall
thermal conductivity of the coatings [70], [71]. However, branching cracks and
inter-pass porosity bands are perpendicular (or close to perpendicular) to the
direction of heat flow within the coating and hence can act as a significant thermal
barrier within the coating [70], [72]. Other fine features such as cracks and pores
also help in decreasing the overall thermal conductivity of the coating. This is
because of the much lower thermal conductivity of these features (containing air)
compared to the bulk material.
4.3 Thermal conductivity

Thermal insulation (defined by thermal conductivity) is an important functionality
of a TC, which drives the overall performance of a TBC on a gas turbine. The
lower the thermal conductivity of a TC, the better the thermal insulation. Hence,
it is important to understand possible modes of heat transfer in a TC and
henceforth to understand how to lower the thermal conductivity of a TBC. Since,
the work was focused on 8YSZ TCs, in brief, different possible modes of heat
transfer in 8YSZ TCs and their thermal conductivity, both for conventional and
suspension plasma sprayed TCs are discussed.
4.3.1 Heat transfer in conventional APS & SPS TCs
Golosnoy et al. [73] explained several possible contributing modes of heat transfer
in conventional APS 8YSZ TCs, which influences the overall thermal
conductivity of the TBC. These are
 conduction through the solid YSZ,

 conduction through the gases in pores,
 radiative heat transfer, and
 some contribution from convection if the segmented cracks are present.
At room temperature and pressure, conductive heat transfer through solid YSZ
is largely predominant followed by conduction through the gases in pores [73].
Radiative heat transfer is significant only at higher temperatures (greater than
1000K) [73]. Convection plays partial role if ceramic TC have thick or wide and
through vertical cracks or segmented cracks [73]. This is because these segmented
cracks can allow the hot gases to pass through the coating easily hence increasing
the overall thermal conductivity of the TBC [70], [71].
37
For bulk 8YSZ, the thermal conductivity at ambient conditions is ~2.25
(𝑊 𝑚−1 𝐾 −1 ), which is due to the phonon conduction [74]. In reality, since the
coating is not fully dense and consists of many microstructural features such as
pores and cracks, the overall thermal conductivity is lower. This is because the
microstructural features interrupt the phonon conduction by scattering at these
microstructural features’ boundaries. Hence, more scattering interfaces are
preferred in the form of microstructural features in TCs to get a lower thermal
conductivity.
It was found that the pore size can have a significant effect on the pore
conductivity [73]. Conduction through a typical gas in a defect such as pores can
be significant, if the defect size is comparable to the mean free path (μ) of the gas
molecules at atmospheric pressure (μ ~ 60 to 100 nm at ambient conditions) [73].
However, the μ is dependent on the temperature and pressure, where higher
pressure can decrease the μ and higher temperature can increase it [74]. Moreover,
the pore conductivity is nearly close to the free gas conductivity, if the pore size
(d) is much larger than the mean free path (d > ~10 μ). If d is less than 1 µm its
conductivity can be significantly below that of a free gas (air) [74]. In general, in
conventional APS TCs the average size of pores is larger than 1 µm. Hence,
typically at high gas pressures, similar to the gas turbine operating conditions, in
conventional APS TCs, gas conduction can play a significant role and can increase
the overall thermal conductivity of the TBC [74]. As explained earlier in this
section, radiation and convection can be neglected in such coatings under certain
conditions.
4.3.1.1 Heat transfer in SPS TCs
Similar to conventional APS TCs, all the modes of heat transfer, which contribute
for thermal conductivity, are also valid for 8YSZ SPS TCs. However, because of
the presence of different microstructural features, these coatings can conduct heat
through both solid YSZ as well as gases in pores compare to APS coatings in a
significantly different manner. As in conventional APS, radiation heat transfer can
be neglected at ambient conditions but conduction through solid YSZ and gases
in pores can have significant different influence on thermal conductivity due to
the different microstructure of these coatings compared to conventional APS
coatings. As presented in the sections 4.1 and 4.2, SPS coatings can have a
microstructure with considerable higher content of very fine (<1 µm) submicron
or nano-sized porosity.
Due to the presence of fine (<1 µm) submicron or nano-sized microstructural

features in these coatings [75], [76], phonon scattering enhances, which then helps
in lowering the overall thermal conductivity [73], [74]. Also, since the pores
38
present in such coatings are in submicron or nano range, conductivity in the gas
within the pores can also be significantly lower than in conventional APS coatings
(see the discussion in the previous section) [73], [74]. However, presence of
segmented cracks or inter-columnar spacing can increase the thermal
conductivity, if they are large or wide enough to allow convection through them
[70], [71], [73], [74].
4.4 Mechanical properties

As shown in the previous section, the presence of various microstructural features
such as pores and cracks are necessary for providing the required thermal
insulation in a TBC. These features can also affect the coatings mechanical
properties such hardness, E-modulus and fracture toughness [77]. E-modulus and
toughness are considered as the two most crucial mechanical properties for TCs
from the design point of view. In fact most of the studies on mechanical
properties of conventional APS TCs were based on evaluating the E-modulus
[78]–[80]. Similarly, in case of SPS TCs, the mechanical properties were mostly
evaluated in terms of coatings’ E-modulus. However, the literature is limited on
SPS in comparison to APS [81]. E-modulus is a measure of coatings’ compliance
or strain tolerance whereas toughness is measure of coatings’ ability to resist crack
formation and propagation. The lower the E-modulus, higher the strain tolerance
and the higher the toughness, higher the crack initiation and propagation
resistance. Hence from a design perspective, a coating with low E-modulus and
high fracture toughness would be preferred.
High porosity is reported to be beneficial for reducing the E-modulus [82],

however the toughness of the coating was found to deteriorate if coating
possesses high porosity [82]. Also, different microstructural features in the
ceramic TC microstructure can affect these properties in a different way. In fact,
E-modulus is found to be more sensitive to the presence of various
microstructural features due to its anisotropic nature [80] since different features
in the ceramic TC microstructures can be present along different directions. For
instance, the presence of delaminations or inter-splat cracks in conventional APS
TC microstructure can lower the E-modulus in the spraying direction whereas the
presence of vertical intra-splat micro cracks can result in lowering the in-plane E-
modulus which is crucial during thermal cycling [80]. In fact, such understating
was the motivation for developing the dense vertically cracked (DVC) APS TCs
to lower the in-plane E-modulus which can improve the thermal cyclic
performance by improving the coatings compliance as it is in the case of EBPVD
columnar TCs [83]. This has further motivated the thermal spray community to
develop DVC or columnar coatings by SPS process [84]. Higher porosity and
39
unmolten zones in SPS TCs than APS was found to lower the E-modulus whereas
the presence of dense zones were found to increase the E-modulus [81], [85].
Similar to the E-modulus, the toughness of the TC can also be reduced due to the
presence of delaminations or horizontal cracks in the APS sprayed conventional
microstructures as the crack propagation along these features can be easier.
Similarly, in SPS sprayed microstructures the presence of branching cracks,
interpass-porosity bands or high porosity etc. can also substantially reduce the
toughness due to easier crack propagation. As reported by Zhou et al., toughness
was identified to be more important mechanical property than E-modulus for
lifetime and has been considered as the crucial thermal cycling life-determining
factor in case of SPS TCs [86].
4.5 Sintering of ceramic TC in TBCs

The exposure of TBCs at high temperatures can lead to significant alterations in
the 8YSZ ceramic TC microstructure due to sintering [87]–[90] of ceramic TC
which can affect TBCs performance significantly [91], [92]. Sintering is a term
most often used in the field of powder metallurgy which is defined as a process
by which a metal/ceramic powder compact (loose powders) is transformed into
dense solids at a temperature lower than the melting point. Loosely bonded
compact powders contain significant porosity which is reduced due to sintering.
Similar to the compact powders, ceramic TCs in the TBCs also contain porosity
in the form of pores, delaminations and cracks, which at higher temperature can
be altered due to sintering. The major driving forces for sintering in general are
the curvature of the pore (surface energy), an externally applied pressure and or
chemical reaction [93]. However, only the first two are reported to be the major
driving forces to cause sintering related changes in 8YSZ ceramic TCs in TBCs
[94], [95].
For conventional APS as well as EBPVD TCs, sintering has been reported to
mainly decrease the porosity due to the closure of pores or healing of cracks (also
referred as densification) [96]–[98]. Mechanism of densification is reported to be
due to the combination of surface and grain boundary diffusion [89].
In addition to densification, coalescence of pores and or widening/opening of

column gaps (also referred as pore coarsening) was also reported in case of
EBPVD TCs [99], [100]. The mechanism of pore coarsening as explained by
Exner et al. in case of several powder compacts during solid state sintering is
caused by localized transport of atoms/molecules due to diffusion and/or bulk
particle rearrangement [101]. Zotov et al. reported that the large pores formed
after annealing in EBPVD TCs are due to the coalescence of initially (in as-
40
produced state) isolated pores or by nucleation and growth during the

recrystallization of the ceramic TC [99]. Widening of column gaps in case of
EBPVD TBCs was reported to be occurring due to the thermal expansion
mismatch between the TC and the substrate (especially when higher thermal
expansion coefficient for substrate than the ceramic TC was noticed) [102].
Another important microstructural change is ‘grain growth’ reported in

conventional APS and EBPVD TCs [98], [99], [103]. Grain growth is the term
that describes the increase in the grain size of a solid which occurs in both dense
and porous polycrystalline solids at higher temperatures [93]. Due to the
conservation of matter, an increase in the average grain size is accompanied by
the disappearance of smaller grains. The driving force for grain growth is the
decrease in free energy that accompanies reduction in the total grain boundary
surface area [93].
These sintering related microstructural changes such as densification, pore

coarsening and grain growth can affect coatings’ thermal and mechanical
properties. For instance it was shown in case of both APS as well as EBPVD TCs
that reduction in porosity due to densification can increase the thermal
conductivity significantly [5], [98], [104], [105]. Similarly, the mechanical
properties such as hardness, E-modulus and fracture toughness were also found
to be increased due to the reduction in the porosity because of densification [77],
[92], [97], [99], [106].
Like conventional APS and EBPVD TCs, SPS sprayed TCs also showed similar
sintering related microstructural changes (densification, pore coarsening and grain
growth) [107] [108]. As a result, both thermal and mechanical properties of SPS
TBCs are also reported to be affected. For instance, as reported by Zhao et al.
and Guignard et al. the hardness and E-modulus were found to increase
significantly as a function of temperature and time respectively [107] [108].
However, the literature is limited when it comes to the understanding of sintering
and the evolution of properties due to sintering related changes in SPS TCs, unlike
for/about conventional APS and EBPVD TCs.
4.6 Lifetime of TBCs

All the gas turbine components protected by TBCs experience severe thermo-
mechanical loading due to the extreme operating conditions. The extent of the
thermo-mechanical load can depend on: 1) the gas turbine application (for
example military aero-engine or land based power generation IGTs or commercial
civilian aero-engines) and 2) the type of component in the gas turbine (for
example: combustor or turbine blades and vanes or after burner). For instance,
41
land based power generation IGTs are run over a long period of time (long
running cycles) under isothermal conditions without frequent start-up and shut
down of the engines; whereas the civilian aero-engines experience more frequent
thermal cycling due to the frequent start-up and shut-down of an engine during
the take-off and landing; and the situation can be extreme when it comes to the
military aero-engines where the engines can experience most frequent start-up
and shut down (very rigorous thermal cycling with severe thermal shock). The
TBCs applied on the gas turbine components for any of the above mentioned
applications can experience high stress loads which are relaxed by forming new
cracks or propagating the pre-existing ones ultimately leading to the delamination
and failure of the TBC. As mentioned earlier, TBC is a multilayer coating system
containing BC, TC and the in-service grown TGO layer and all the three layers
are considered to be equally important from the failure analysis and lifetime point
of view [16], [17], [92], [109]–[113]. The significance of these layers is discussed
in detail in the following sections.
4.6.1 Lifetime and failure associated with the BC and TGO
The significance of metallic BC during the lifetime of the TBC is considered as

the most influencing factor where the failure in the TBC is typically associated
with BC oxidation [109], [110], [113]. During TBCs’ exposure to high temperature
operating environment, the metallic BC undergoes oxidation. This is because the
8YSZ ceramic material is transparent to oxygen under those conditions. Typically
used BC material as mentioned in section 2.1.1 is MCrAlY alloy where M is Ni,
Co or a mixture of Ni and Co. While MCrAlY allows formation of several oxides
in the BC the most common, primary and stable oxide is alumina [114]. This is
because alumina has the least formation energy among other possible oxides of
constituent metals such as Ni, Co and Cr present in the BC [115]. In fact,
formation of alumina is considered as beneficial for the TBC as it is dense and
acts as a protective oxide layer for further oxygen diffusion and prevents
formation of other detrimental mixed oxides [116] collectively named as CSN
(Chromia, Spinel and Nickel oxide) [117]. The oxides formed at the interface of
the bond coat-ceramic TC due to the oxidation BC are collectively referred as
TGO as mentioned earlier in section 2.1.2.
MCrAlY bond coats in the as-sprayed conditions typically show a two phase
matrix structure which as reported in the literature consists of β-(Ni(Co)Al) (beta
phase) precipitates in a continuous γ-(Co/Ni/Cr) (gamma phase) matrix [17]. Beta
phase is an aluminium rich phase which acts as an aluminium reservoir in the
formation of α-alumina [17], [26]. After exposing these TBCs at high temperature,
the aluminium starts to diffuse towards both the BC –TC interface as well as the
BC-substrate interface consuming the aluminium reservoir (beta phase). After
42
some time the beta phase depleted region close to both the interfaces become
rather clear and this region is referred as ‘depletion zone’. These depletion zones
are formed in the BC due to the incomplete diffusion of the aluminium from the
BC.
After certain time during the lifetime of the TBC, the aluminium level within the
BC is reduced due to its continuous depletion. Thermodynamically stable α-
alumina slowly grows first as a TGO layer and continues to grow to a certain
critical thickness. The α-alumina layer grown on a highly wavy BC profile cracks
on cooling as a result of high local curvatures and thermal expansion mismatch
between BC and TGO (α-alumina). These cracks can now provide an easy ingress
of oxygen to the underlying BC. This may then further continue the α-alumina
formation if there is still some aluminium left, otherwise start forming mixed
oxides of other underlying BC elements which in this case are Ni, Co, Cr etc. It
has been shown that when the aluminium is depleted to below 2.5 wt. % Al in the
BC, no more formation of the protective α-alumina occurs [118].
Formation of other mixed oxides such as Ni/Co/Cr spinels [16], [17], [26] in the
TGO is considered as detrimental for the TBC life due to their faster growth rate
which leads to the rapid local volume change in TGO that generates excessive
stresses [110]. It has been identified as impossible to completely eliminate the
formation of such detrimental spinels [26], [119]. Spinels are reported to have
lower fracture toughness than the alumina which then eases the cracking and
crack propagation through TGO [113].
The major cause of failure in TBCs associated to BC oxidation is related to the

stress state at the BC/TGO/ TC interfaces. These stresses are introduced in the
TBC due to mismatch in CTE (mismatch stress) between different layers (BC-
TGO-TC) and/or due to the growth of a new layer in the form of TGO in
between BC and TC (growth stress) [118], [120]. These stresses are relaxed by
forming cracks close to the BC-TGO-TC interface ultimately delaminating the
ceramic TC and resulting in failure of the TBC.
Conventional plasma sprayed BCs are reported to be very rough (about 11 µm -

12 µm Ra [38]). BC roughness is crucial in a thermally sprayed coating as it
provides mechanical anchoring of the TC layer on the underlying BC. The
roughness however creates a wavy profile with hills and valleys on the BC. The
TGO is typically formed following nearly the BC profile. As reported by Evans
et al. [26] and Schilichting et al. [16], in case of conventional TBCs this wavy
profile creates a different stress distribution along the profile in the TGO. Due to
the wavy profile of the TGO geometry, out-of-plane stresses are produced
resulting in tensile stresses at the hills and compressive stresses at the valleys [121].
These tensile stresses at the hills act as a driving force for the crack propagation
43
through the BC-TGO interface [121]. These cracks are formed because of the
volume change near the TC-BC interface due to the formation of an extra layer
(TGO). As the TGO layer is formed due to BC oxidation in this case, such a crack
formation cannot be easily avoided.
The major influencing factors controlling the lifetime and failure associated with
the BC and TGO are BC chemistry, BC roughness and TGO composition. In
order to minimize the failure associated with BC and TGO and increase the
lifetime of the TBC, BC with sufficiently high aluminium reservoir is necessary.
In addition, smoother bond coats can also minimize the cracking issue at the BC-
TGO interface and hence increase the lifetime of the TBC. In fact the relatively
new techniques such as HVOF and HVAF were reported to produce smoother
BCs than the conventional plasma sprayed BCs (in the range of about 3 µm - 8
µm [122]). Hence selection of both the BC chemistry as well as the BC spraying
technique becomes more important while controlling the lifetime of the TBC.
4.6.2 Lifetime and failure associated with the ceramic TC
Significance of the ceramic TC in controlling lifetime of the TBC is as crucial as

BC and TGO layers. Most common failure mode observed in the conventional
APS as well as EBPVD TBCs is cracking in the ceramic TC close to the TGO-
TC interface [113]. Such crack formations in the TC are also associated with the
TGO formation. The crack initiates at the region where the curvature of the BC
roughness profile changes from concave to convex as reported in case of
conventional TBCs [123]. The interfacial fracture toughness of the TC/spinels
interface is lower than that of the TC/α- Al2O3 interface which can increase the
possibility of fracture between the TC and TGO [113]. Such failure can be
minimized by increasing the fracture toughness of the TC at the TGO-TC
interface. This was achieved by several researchers by adding a thin dense YSZ
layer close to the TGO-TC interface [124], [125].
In several cases where TBC experiences a severe thermal gradient or thermal

shock (for example in case of military aero-engine) the significance of ceramic TC
becomes even more crucial in the failure of TBC. Failure associated with severe
thermal gradients through the ceramic TC in TBCs is typically analysed by
studying TBCs’ thermal shock behaviour. As reported in the literature, under
thermal shock conditions, TBC experiences a severe thermal gradient across the
ceramic TC layer compared to the isothermal cyclic conditions [126]. Higher
thermal gradient across the ceramic TC layer can affect the BC temperature which
in turn can affect the TGO formation and thermal mismatch stresses in the
ceramic TC near the BC-TC interface affecting the lifetime [127].
44
The thermal gradient is of course dependent on coatings’ thermal conductivity

which in turn depends on TC microstructure and porosity. Higher the thermal
conductivity of the ceramic TC lower the thermal gradient across it, meaning the
BC can experience higher temperature which as reported by Vassen et al. can
result in lower lifetime [128]. In case of conventional APS TBCs, porosity and
various microstructural features of the TC were found to have a significant role
on their thermal shock behaviour. For example, the presence of inhomogeneous
distribution of pre-existing micro cracks and pores were found to deteriorate the
thermal shock life [129]. Whereas the presence of segmented vertical cracks and
nanostructured features were found to improve the thermal shock life [129]–
[131].
As mentioned in section 4.4, the mechanical properties of the ceramic TC are very
much dependent on its microstructure and porosity which in turn can affect the
lifetime. For instance, higher strain tolerance, which is a major characteristic of
the columnar EBPVD as well DVC TCs, can accommodate the strain introduced
in the TC during the frequent thermal cycling in both isothermal as well as thermal
gradient conditions [132], [133]. Such an increased strain tolerance in those types
of TBCs is reported to be beneficial for improving their thermal cyclic lifetime
[131], [133]. In addition to the strain tolerance, the fracture toughness of the
ceramic TC is also widely reported to be one of the crucial factors in determining
the lifetime of the TBC [134], [135]. Higher fracture toughness is needed not only
close to the TC-TGO interface but also throughout the ceramic TC, as cracks can
initiate anywhere in the coating especially under sever thermal gradient conditions.
For conventional TBCs, the influence of fracture toughness on TBCs’ lifetime is
extensively studied where an improvement in the fracture toughness of the
ceramic TC was shown to be beneficial for the lifetime [124], [134], [135].
Similarly, in SPS TBCs an improvement in fracture toughness of the ceramic TC
also showed to enhance the lifetime [86], however unlike in conventional APS
TBCs the literature on SPS TBCs is limited.
45
5 Experimental techniques used to
characterize TBCs
Many characterization techniques are used to investigate TBCs [11], [12], [136]–
[139], however, only those which are within the scope of this work are presented
in this chapter. Figure 18 describes in brief different types of characterization
techniques used in this work.
Figure 18: Different characterization techniques used in this work to study TBCs
5.1 Microstructure evaluation

Microstructure of the TBCs was studied in this work in general using scanning
electron (SEM) and optical microscopy (OM). Phase analysis was performed
using X-ray diffraction (XRD). In case of SPS coatings, due to the fine scaled
features present in the microstructure, a high resolution SEM is necessary to get
a thorough understanding of all the features.
Prior to the microstructure study in a microscope, it is very important to prepare

the samples using proper metallographic techniques. Typically, sample
47
preparation of TBCs involves cutting, mounting in a low viscosity epoxy resin,
grinding and polishing the samples manually or using semi-automated machine.
The standard procedure for conventional TBCs is presented in detail elsewhere
[136]. For SPS TBCs, the samples are first mounted in a low-viscosity epoxy resin
prior to the steps involved in a standard procedure as mentioned above, to avoid
any damage to the coating during cutting. Details can be found in any of the paper
appended in this thesis.
5.2 Porosity measurement

Measuring the porosity in a SPS coating is a big challenge due to the presence of
different length scaled porosities, starting from micrometer-sized vertical
cracks/inter-columnar spacing to submicron and nano-sized pores and cracks.
Hence, porosity analysis was done using three different techniques. Open porosity
measurement was done using water impregnation (also known as Archimedean
porosimetry) and mercury intrusion porosimetry (MIP). Also, image analysis (IA)
was carried out to determine the content of both closed and open porosity in the
coating.
In Archimedean porosimetry, a free standing ceramic coating is immersed in

water and kept there under vacuum for certain time (around 5 minutes) to force
the water into the pores. Both wet (immersed coating) weight and dry (as-sprayed
coating) weight are measured by an electronic weighing machine. Weight
difference of wet and dry coating is then calculated, which gives a measure of the
water residue in the coating and hence the coating porosity. Detailed explanation
of the experimental procedure can be found in the appended Papers A and Paper
B.
Unlike water as in Archimedean porosimetry technique, mercury is intruded into

the coating in MIP. Similar to water impregnation, a free standing ceramic coating
is kept under vacuum in a capillary tube and the mercury is forced by using an
external pressure, which can then fill the coating pores. MIP is based on the
premise that a non-wetting liquid (one having a contact angle greater than 90°)
will only intrude capillaries under pressure [140]. A detailed explanation of the
MIP technique and the equipment is provided in Paper C and Paper H. The pore
size distribution is determined from the volume intruded at each pressure
increment; whereas the total porosity content is determined from the total volume
intruded.
The conventional way of analysing porosity of TBCs is using IA on a determined

number of SEM micrographs of coatings’ cross-section. The analysis involves
converting a SEM greyscale image into a binary image (black and white) using any
48
EXPERIMENTAL TECHNIQUES USED TO CHARACTERIZE TBCS
image analysis software (ImageJ, Aphelion etc.) with proper thresholding for
determining the boundary between bulk and porosity. Finally, the fraction of
white (pores) portion relative to the black (bulk material) portion of the binary
image of a given SEM greyscale micrograph gives a porosity content in that
particular image. Average of the porosity of all the images then gives the net
porosity content of the coating.
Since SPS sprayed coatings showed porosity at varied length scale (micron,
submicron, and nano pores); two or three different magnifications were utilized
for analysis, e.g low (x500 or x1000), high (x 7000 or x10000) and sometimes even
very high (x15000) in this work. These multi magnifications were selected such
that low magnification should capture features like inter-columnar spacing, big
vertical cracks, and micron-sized pores, whereas high and very high should
capture features like submicron and nano-sized pores. While capturing the higher
magnification micrographs, it was made sure that these micrographs should not
contain any big features (which were already captured at lower resolution) in order
to avoid repetition. Such a repetition was avoided by using a count mask in a
software (i.e. the software will consider porosity under certain pore size range
only). This technique is explained in detail in Paper C & Paper H. The image
analysis technique adopted for this work is time-consuming but can provide an
estimate of all types of pores (connected, non-connected, vertical cracks,
branching cracks etc.) present in the coating. This is not possible using techniques
like Archimedean porosimetry or MIP which can only measure open porosity.
However, image analysis is still sensitive for sample preparation and may
introduce errors while measuring fine pores. For this reason a combined porosity
measurement technique that is coarse porosity measurement by image analysis
and fine porosity measurement by MIP was adapted in this study. More details
about such a procedure can be found in Paper H.
5.3 Evaluation of thermal conductivity

Thermal conductivity is an indicator of the amount of heat flow through a
material (in this case a ceramic TC). The most common method to evaluate the
thermal conductivity of a TC in TBC is to derive it from its diffusivity which can
be measured experimentally. Thermal conductivity is calculated using the
following equation:
𝜆 = 𝛼 𝜌 𝐶𝑝 (3)
where 𝛼 (𝑚2 𝑠 −1) is the thermal diffusivity, 𝐶𝑝 (𝐽 𝑘𝑔−1 𝐾 −1) is the specific heat
capacity, 𝜌 ( 𝑘𝑔 𝑚−3) is the coating density and 𝜆 (𝑊 𝑚−1 𝐾 −1 ) is the thermal
conductivity.
49
The most widely used experimental technique for thermal diffusivity
measurement of a TC is the laser flash analysis (LFA) technique [141]–[143].
Several types of LFA equipment are available today so that thermal diffusivity can
be measured either at room temperature or higher temperatures (up to 1500 ᵒC)
as well as in ambient atmosphere and controlled atmosphere (Argon). The
schematic of a typical laser flash equipment during the LFA experiment is shown
in Figure 19.
During the laser flash experiment a laser pulse is fired at the rear face of the TBC
sample (at the substrate). The heat pulse travels through the TBC sample and the
resulting temperature increase at the surface of the ceramic TC is measured with
an InSb infrared detector at a high sampling rate. The thermal diffusivity is
calculated using the following equation [144]:
𝛼 = 0.1388𝐿2 /𝑡(0.5) (4)
Where 𝛼 (𝑚2 𝑠 −1 ) is a thermal diffusivity, 𝐿 (𝑚) is the thickness of the sample and
𝑡(0.5) (𝑠) is the time taken for the rear face temperature of the TC to reach half of
its maximum rise. Detailed information about the origin and usage of equation 4
for diffusivity measurement in TBC can be found elsewhere [144]. An average of
five laser shots is made for each measurement when the sample is at a steady state
condition.
As zirconia is transparent to the laser wavelength used for measurements, the

samples need to be coated with a layer of graphite or gold to prevent the laser
pulse from traveling through the ceramic TC layer and allow energy from laser
light to absorb [145]. The wavelength used in this work was 1064 nm (LFA 427,
Netzsch Gerätebau GmbH, Germany), which is transparent to zirconia, hence,
the samples were coated prior the diffusivity measurements.
Thickness measurement in this work was performed by optical microscopy by

taking around 200 measurements all across the coating cross-section. Thickness
for each layer in a multilayerd TBC system (𝐿 in the equation 4) is an important
factor for the accuracy of the results in a LFA experiment. It can be seen from
the equation 4 that thickness has a square dependence on the thermal diffusivity.
An error of 20 % in the total thickness (𝐿) of the TBC can give almost 50% change
in thermal conductivity [144]. It is important to realize that SPS deposited ceramic
TCs show significant variation in the coating thickness due to their rough nature
because of the presence of columnar features.
The specific heat capacity can be measured using differential scanning calorimetry
(DSC). For this work, the specific heat capacity measurement was not performed,
50
instead the values from existing databases on the same material (8YSZ) for
specific heat capacity were used [15], [25], [25].
Figure 19: Schematic of the laser flash analysis equipment, note that the sample is
placed in a specimen holder with a substrate facing the laser beam
5.4 Evaluation of mechanical properties

Hardness, Young’s modulus (E-modulus) and fracture toughness are the key
mechanical properties of TCs in TBCs as mentioned in section 4.4. Several
measurement techniques are employed in literature for measuring these properties
of ceramic TCs in the TBC. For instance, E-modulus is reported to be measured
by three or four-point bending [146], [147], indentation method [79] etc. Similarly,
for fracture toughness measurement, several techniques such as double torsion
method [82], double cantilever bending [148], indentation method [149] etc. are
reported. Despite several techniques can be used there are no standardised
techniques available for TBC characterization. Moreover, it has been shown that
the absolute values are highly dependent on the techniques used to evaluate them
and the results could vary even if the test specimens are identical between
different techniques [150]. Hence, these properties, especially E-modulus (and
hence toughness), need to be considered as an engineering value (used for design
purpose) for quantifying and ranking of TBCs rather than a fundamental
property. Indentation method was used in this work to measure the three
51
mechanical properties and hence only indentation method is explained in detail
below.
Indentation method was employed in this work to measure hardness, E-modulus

and also fracture toughness. Instrumented micro-indentation method was
employed to measure hardness and E-modulus. The instrumented hardness (HIT)
(convertible into Vickers Hardness HV) and instrumented E-modulus (EIT)
(obtained from the unloading slope) values were determined by the commercial
WIN-HCU® software (Helmut Fischer GmbH) using equations (5) and (6):
𝑃𝑚𝑎𝑥 𝑃𝑚𝑎𝑥
𝐻𝐼𝑇 = =
𝐴𝑝 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 × ℎ𝑐 2 (5)
1 − 𝜈2
𝐸𝐼𝑇 =
𝑑ℎ
2√𝐴𝑃 ( )
𝑑𝑃 𝑃𝑚𝑎𝑥 1 − 𝜈𝑖2 (6)
{( )−( )}
√𝜋 𝐸𝑖
where 𝑃𝑚𝑎𝑥 (N) is the maximum applied indentation load which was 1 N; 𝐴𝑝 (mm2)
is the projected (cross-sectional) area of contact between the indenter and the test
specimen determined from the force-displacement curve and a knowledge of the
area function of the indenter; ℎ𝑐 (mm) is the contact depth; 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 is constant
for a given indenter, here 24.5; 𝜈 is the Poisson’s ratio for 8YSZ, which was
considered to be 0.25 [151]; 𝜈𝑖 and 𝐸𝑖 are the Poisson’s ratio and E-modulus of
the indenter, here for diamond 0.07 and 1140 GPa, respectively. A total of 25
indents were made on as-sprayed, polished cross-sections with a maximum load
of 1 N (being equivalent to HV0.1) yielding average values of both hardness and
E-modulus.
Cracks were generated for fracture toughness measurements using Vickers

indentation technique. Cross-section polished TBCs were indented at a maximum
load of 9.807 N (HV1) in the ceramic TC using a Vickers indenter for 13 seconds.
The chosen load was identified as the optimum one for such coatings to produce
Palmqvist type cracks without significantly damaging the coating. The following
equation was used to calculate the fracture toughness, as the cracking pattern was
identified as Palmqvist cracks (0.25≤l/a≤ 2.5) type in these coatings [152]:
2 1
𝐸 5 1 𝑎 2
𝐾𝐼𝐶 = 0.018 ( ) 𝐻𝐼𝑇 𝑎2 ( ) (7)
𝐻𝐼𝑇 𝑙
Here 𝐾𝐼𝐶 is the mode I indentation fracture toughness (MPa.m1/2), E is the elastic
modulus (MPa) of the coating determined from 𝐸𝐼𝑇 (𝐸 = 𝐸𝐼𝑇 ∗ (1 − 𝜈 2 )), a is the
indentation half-diagonal length (m) and l is the crack length (m).
52
Detailed procedure adapted for measuring the mechanical properties using the
above mentioned indentation methods can also be found in Paper H.
5.5 Evaluation of sintering behaviour

In order to assess the sintering behaviour of TBCs isothermal heat treatment in
an inert atmosphere was employed in this work. The reason for using an inert
atmosphere was to avoid any cracking in the ceramic TC associated with the TGO
formation. The oxidation of the BC and hence the TGO formation in an inert
atmosphere can be minimized which can be helpful while studying sintering
related changes in the ceramic TC microstructure. It must be borne in mind that
in reality the operating conditions would not be in an inert atmosphere. However
the purpose in this case was to study independently the TC microstructural
changes due to sintering. This was only possible by using inert atmosphere to
avoid the BC oxidation and TGO formation.
Thin square plate TBC samples were first water jet cut into ϕ10 mm coupons and
subjected to isothermal heat treatment. Samples were placed into a furnace at
room temperature, and heated to a temperature of 1100 ᵒC in about 4 hour. Prior
to adding the samples, the furnace was evacuated and flushed with
Argon/Hydrogen mixture with a flow rate of 200 L/hour. The heat treatment
was done for 1, 3, 10 and 200 hours. Finally, all the samples were cooled down to
room temperature in about 4 hours and removed from the furnace for further
characterization.
5.6 Evaluation of thermal cyclic fatigue (TCF)

lifetime
Lifetime assessment of TBCs is all time challenging, since it is hard to provide the
realistic conditions as it is in-service on real components. However, accelerated
and simplified tests are used to estimate the lifetime for comparative purposes [2],
[132].
In TCF testing, samples are heated in a furnace (in air and normal atmospheric
conditions) up to 1100 °C for a period of 1 hour followed by rapid cooling, using
compressed air to approximately 100 °C within 10 minutes. This heating and
cooling is termed as one cycle. After each cycle, a visual record of the samples’
surface is made and samples are repeatedly cycled in this fashion until failure. This
allows crack evolution to be observed and cycles to failure to be estimated. The
criterion for failure in TCF testing is when the TCs show more than 20%
spallation of the whole coating surface. A more extensive description of this
technique is provided in Paper A, Paper B and Paper G.
53
5.7 Evaluation of thermal-shock (TS) lifetime
In order to replicate the rapid heating and cooling experienced by the TBCs
during civil or military jet engine operation, thermal shock (TS) tests are
employed. Mostly such a thermal shock testing is done in a so called burner rig
and the testing is called burner rig testing [153].
In burner rig testing, samples are heated to a set TC surface temperature (in this
study it was about 1300 °C) using combustion burners for a set duration (in this
study it was 75 seconds) and then forced cooled by compressed air to a set TC
surface temperature (about 600 °C in this study) in a set duration (75 seconds in
this study). Prior to the start of the cycling, the samples are preheated by hot air
guns from the back side (from the substrate side) to a set substrate surface
temperature (about 700 °C in this study) and maintained at that temperature
throughout the cycling. This allows the TCs in TBC samples to experience a
severe temperature gradient during each cycle as it is the case in reality. Hence,
burner rig tests can be considered as the most relevant test to assess the failure
and thermal shock behaviour of ceramic TCs simulating the conditions close to
the real life jet engine operating conditions. However, there are still some
important differences to real life conditions that must be considered. For instance,
the burners are normally run on gas fuel such as propane and does not have the
same characteristics as it is in the case of jet fuels. Also, most of the times the
burner rig tests are performed at atmospheric conditions and subsonic speed
which are also not close to the real life conditions.
More detailed description of the burner rig test to evaluate the thermal shock
behaviour for the TBCs studied in this work is provided in Paper H.
54
6 Microstructure selection and coating
design for TBC applications using SPS
Like all other engineering applications, no single microstructure type and coating
system exists that can be suitable for all the TBC applications. Unlike
conventional APS and EBPVD which are mainly capable of producing porous
lamellar and dense columnar microstructures respectively, SPS has larger process
window giving rise to various types of microstructures as shown in Figure 14 in
section 4.1. In addition, the major advantage of SPS over both APS as well as
EBPVD is that it can produce a porous columnar microstructure combining both
the coating attributes which are provided by the above mentioned conventional
techniques as shown in Figure 20. Despite of this unique advantage of SPS over
APS and EBPVD, the large process window, especially in case of ASPS, makes
the microstructure selection and tailoring process for a given TBC application
more challenging.
Figure 20: Comparison of typical microstructures produced by EBPVD, APS and SPS
i.e. dense columnar, porous lamellar and porous columnar respectively
This chapter provides a general thought process towards microstructure selection

and coating design for different TBC applications in gas turbine industry.
Moreover the chapter also discusses in detail a methodology for microstructure
tailoring and designing an optimized columnar TBC with enhanced durability
sprayed by SPS for both industrial as well as aero gas turbine applications.
6.1 Processing and microstructure

Figure 21 shows various possible routes which can be utilized to produce a
specific type of microstructure as presented in section 4.1. The routes shown in
Figure 21 summarizes the results from an extensive experimental study that was
55
performed with various liquid as well as solid feedstock thermal spray techniques
and discussed in more detail in appended Papers (A, B, C and D).
Solution precursor plasma spraying (investigated in Paper A) and suspension high

velocity oxy fuel spraying (investigated in Paper B) have produced TBCs with
vertically cracked type microstructure. Conventional solid powder feedstock
plasma spraying as expected has resulted in lamellar microstructure (investigated
in Paper A). However, conventional solid powder feedstock plasma spraying in
addition to its typical lamellar structure can also produce vertically cracked
structure under certain spraying conditions, which has been shown elsewhere
[133].
Suspension plasma spraying on the contrary has shown to be able to produce all
three types microstructures, i.e. vertically cracked, highly porous and columnar.
Investigations in Paper A and Paper B provided the first hint of a microstructure
with features resembling like columns while using suspension plasma spraying.
This was further investigated in Paper C and Paper D where axial suspension
plasma spraying (ASPS) was utilized and it was found that it is possible to obtain,
not only different types of columnar microstructures i.e. with different porosity,
but also other types of microstructures as discussed in section 4.1.2 and shown in
Figure 21 below using the same ASPS technique.
Figure 21: Flow chart showing the route of production of a specific type of
microstructure for a TBC application using various feedstocks and spray processes
56
MICROSTRUCTURE SELECTION AND COATING DESIGN FOR TBC
APPLICATIONS USING SPS
6.1.1 Influence of process parameters on TC microstructure
As discussed earlier in Chapter 2 & Chapter 3, the microstructure of coatings

sprayed by both APS as well as SPS can be significantly influenced by several
process parameters. A few of those parameters that can significantly affect the
coating microstructure (and relevant to this work) while deposition by SPS
process are listed in Figure 22. For simplicity, these process parameters can be
grouped as shown in Figure 22 i.e. plasma spray parameters, suspension
parameters, plasma gun hardware related parameters and others such as surface
roughness of bond coat/substrate etc. These parameters and their influence on
coating microstructure in case of SPS are discussed in detail in the appended
papers. For instance, influence of plasma spray parameters (without changing
other parameters) is discussed in Papers (B, C, D, G and H); whereas the influence
of suspension parameters as well as surface roughness (without changing other
parameters) on the microstructure is discussed in detail in Paper F. Influence of
gun hardware (especially for Axial plasma gun) such as nozzle, injector size etc.
was not discussed as it was not in the scope of this work. However, these can also
significantly influence the microstructure and hence need to be investigated in
future.
Figure 22: Flow chart listing major processing parameters that can significantly
influence the microstructure produced by SPS process
57
The parameters mentioned in Figure 22 can be difficult to study individually as
most of them have a strong interdependence among each other. Hence, in case
of SPS, the coating formation (columnar or vertically cracked) as mentioned in
Chapter 3 should be discussed in terms of droplet momentum which is dependent
on most of the parameters mentioned above. Higher droplet momentum can
result in normal deposition giving rise to lamellar and or vertically cracked type
coatings whereas lower momentum can result in shadowing effect giving rise to
columnar structures (see section 3.6).
Figure 23: Simplified flow chart showing the necessary process parameters and their
target in the formation of columnar type microstructures and for vertically cracked type
the target of these process parameters can be considered as vice-versa (note: there
is an interdependence between droplet size and speed, however droplet size can be
considered more significant)
The relationships between various important process parameters and droplet

momentum and hence columnar microstructure type are given in Figure 23 where
it is shown that low droplet size and droplet speed can produce columnar
microstructures. To achieve a vertically cracked type microstructure, it can be
considered as vice-versa i.e. high droplet size and high droplet speed. Again, the
figure here is just a simplified representation of the relative magnitude of different
process parameters needed for forming either columnar or vertically cracked
microstructures using SPS. Also, due to the interdependence of droplet size and
droplet speed, it’s more difficult to assess the individual role of different
parameters as listed in Figure 23. However, the significance of droplet size is
58
considered to be more important than the droplet speed due to the third-power
momentum dependence of droplet size as shown in equation 8 below (see Paper
F for more details).
4 𝐷 3
M𝑜𝑚𝑒𝑛𝑡𝑢𝑚 = ( 𝜋 (( ) )) 𝜌𝑠 𝑣 (8)
3 2
Here, 𝐷 is the droplet size after secondary atomization, 𝜌𝑠 is the suspension

density and 𝑣 is the mean droplet velocity. Hence, while designing columnar
structures using SPS process, it’s important to prioritize the fabrication of finer
droplets. More detailed discussion regarding the influence of process parameters
on microstructure (columnar or vertically cracked) is performed in the appended
Papers (F and H).
6.1.2 Tailoring of porosity in a SPS TC microstructure
As mentioned in Chapter 2, TBCs are extensively used in the gas turbine industry
for various high temperature applications. The performance-based criteria for
ensuring superior performance of TBCs can differ, depending upon the different
environments and exposure conditions experienced by the TBCs. This particular
work has mainly focused on achieving high thermal insulation, high TCF and high
TS life. However, several other criteria such as high CMAS (Calcia-Magnesia-
Alumina-Silica or molten silicate), erosion and corrosion resistance could also be
crucial under certain exposure conditions. For example, as explained in Chapter
2, high TS life is more important along with high thermal insulation for TBCs
deposited on military aircrafts’ aero-engines. Similarly, for TBCs that are
deposited on commercial/military aircrafts’ aero engines which regularly fly
through desert areas will require in addition to high thermal insulation and high
life, high erosion and CMAS resistance. Also, TBCs deposited on IGTs’ engines
which typically encounter corrosive elements such as Sulphur due to their
exposure to low grade fuels, require in addition to high thermal insulation and
high TCF life, a superior high-temperature corrosion resistance.
The performance and durability of TBCs in any of the above-mentioned

environments is intimately related to the porosity and pore structure/size.
Therefore, tailoring of porosity in SPS microstructures to achieve a desired TBC
is very important. The significance of various process parameters on total porosity
content and pore size distribution in different SPS microstructures is very
complex due to their interdependencies among each other. Therefore in practice
and different studies, most of the process parameters are frozen (kept constant)
while only one (or very few) is modified in order to see the effect of that parameter
on coatings’ microstructure and porosity. The discussion on achieving different
59
porosity content and pore size distribution is performed in more detail in all the
appended papers. However, a brief summary of such a porosity tailoring strategy
as discussed in great details in Paper H is provided in this section.
A first step towards tailoring of porosity in such complex SPS microstructures

would be to identify the major microstructural features that can contribute to
coatings’ total porosity. For example, a simplified flow chart of such different
microstructural features typically noticed in SPS coatings studied in this work is
provided in Figure 24. It is very important to identify different features in the
microstructures as they vary vastly in their size and accordingly they can influence
not only the total porosity but also the coating properties and performance.
Figure 24: Summary of major microstructural features present in SPS coatings
The second step of porosity tailoring would be to select the pore classification,
where the total porosity can be smartly distributed in different categories/groups
based on the size or structure of these features. For example, porosity in SPS
coatings in this work (see Paper G & H) is classified based on the size range of
various microstructural features and shown in Figure 25. The figure shows the
classification of porosity based on the equivalent pore size diameter (see equation
9) where porosity is categorized mainly in two major groups which are coarse
porosity (>1 µm), and fine porosity (<1 µm).
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑝𝑜𝑟𝑒 𝑠𝑖𝑧𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 = √(4/𝜋 (𝑎𝑐𝑡𝑢𝑎𝑙 𝑝𝑜𝑟𝑒 𝑎𝑟𝑒𝑎)) (9)
These two major groups are further subcategorized in four different subgroups
i.e. large (>10 µm), micron (10 µm - 1 µm), submicron (1 µm - 100 nm), and nano
(<100 nm)) and are also referred as Class-1, Class-2, Class-3 and Class-4
respectively. Major contribution from different microstructural features towards
60
each pore class is also shown in Figure 25. Such a breakdown of porosity in
different classes for SPS coatings can be very helpful while systematically tailoring
the porosity as per the requirement for various TBC applications.
Figure 25: Flow chart showing the classification of total porosity and the contribution
of various SPS microstructural features present at different length scales in different
pore classes
In the third step, after classification of the porosity in different classes, a target
for each porosity class should be set, for example negligible/low/optimum/high,
based on the desired TBC response. In the fourth step, various sources/origins
for each porosity class should be carefully identified from the different
microstructural features as listed in step 1. For instance, as shown in Figure 26
the main sources of Class-1 porosity as noted in this study are the inter-columnar
spacing and region in the vicinity of the inter-columnar spacing. In the fifth step,
the target for each of these sources should be set in a way so that the desired
target for the respective porosity class can be achieved. For instance, in order to
achieve for example, an optimum Class-1 porosity, either an optimum inter-
columnar spacing and a negligible vicinity of the inter-columnar spacing region
can be targeted or vice-versa. After that, in the sixth step, all the major control
factors (i.e. process parameters such as plasma power, feed rate, suspension
viscosity, solid load etc.) which can significantly influence each of the
source/origin should be listed. For instance, inter-columnar spacing can be
affected by modifying the BC roughness as it can significantly alter the column
density and hence the total number of inter-columnar spacing in the
microstructure. After that, in the seventh step, with the help of systematic
61
experimental design (DOE), a “calibration” study to achieve the desired numbers
for each of these control factors should be performed. After the calibration study,
in the eighth and final step, it should be verified whether or not the desired target
for each porosity class is achieved. If yes, then the tailoring of porosity is finished
but if not then the “calibration” study (i.e. seventh step) should be repeated until
the desired target for each porosity class is achieved.
Figure 26: Origin/source of Class-1 porosity (i.e. inter-columnar spacing & vicinity of
the inter-columnar spacing) shown in case of columnar SPS microstructure [Ganvir et
al. Materials and Design, 2017]
All these eight key steps involved in tailoring of porosity in SPS microstructures
to achieve a desired TBC response are also schematically shown in the form of a
flow chart in Figure 27. A detailed discussion regarding tailoring of porosity as in
case of achieving higher TS life and high thermal insulation which is used as an
example to describe the above mentioned tailoring strategy has been successfully
demonstrated in detail in Paper H. A philosophy similar to that described in Paper
H can also potentially be used to tailor the porosity for all other TBC applications.
62
Figure 27: A flow chart showing systematic steps to be followed for tailoring the
porosity in SPS microstructures
6.2 Effect of SPS TC microstructure on thermal

conductivity
As explained in Chapter 4 and the previous section, the presence of various
microstructural features observed in SPS microstructures can significantly affect
the porosity at different length scale and hence the total porosity. The total
porosity content of the coating has a significant impact on thermal conductivity
as explained in Chapter 4 and shown in Figure 28 (a) (more details can be found
in appended Papers (A, B, C, D and E)). These features and their formation are
mostly governed by the different deposition/spraying conditions which is
investigated in more details in Papers (B, C, D and H).
63
Figure 28: A relationship between the porosity and the thermal conductivity in SPS
TBCs (a) [Ganvir et al. JTST, 2015] and the comparison of total porosity content in
SPS and APS TBCs (b) [Ganvir et al. IJACT, 2015]
The major reason for achieving extremely lower thermal conductivity in SPS TBC
compared to the APS as well as EBPVD TBCs (see Figure 29) is not only the
presence of extremely high total porosity content (see Figure 28 (b)), but also the
presence of various fine features contributing to the relatively higher (about 50%
of total porosity) fine porosity content (i.e. porosity <1 µm) as shown in Figure
31 (a).
Figure 29: Comparison of thermal conductivities of SPS and ASPS TBCs with
conventional APS as well as EBPVD TBCs [Ganvir et al. IJACT, 2015 & Ganvir et al.
JTST, 2015]
64
In addition to these fine features, coarse features such as vertical cracks, inter-
columnar spacing, inter-pass porosity bands etc. also have a significant impact on
the thermal conductivity. Presence of all these features at different length scales
span the porosity over a wide size range in a SPS microstructure and depending
on their distribution the resultant thermal conductivity can vary. This is the reason
why the microstructures produced by SPS (more specifically by ASPS) show
varying thermal conductivity (ranging from as low as 0.30 W/(m.K) to as high as
0.76 W/(m.K) or even higher) as shown in Figure 29.
The individual significance of some of the microstructural features in a typical

SPS microstructure is shown in Figure 30.
Figure 30: Schematic of a trade-off between the density of various microstructural

features present in the coating and the thermal conductivity of the coating
It can be seen from the figure that presence of higher fine porosity and interpass
porosity bands or branching cracks give lower thermal conductivity (investigated
in Papers (B and C)), whereas higher number of vertical cracks and inter-columnar
spacing can increase the thermal conductivity (investigated in Paper C). Moreover,
the effect of vertical cracks or inter-columnar spacing can be neglected if the total
porosity content is increased by increasing the fine porosity in the microstructure
(investigated in Paper D). More details about the influence of different
65
microstructural features in SPS TBCs on thermal conductivity can be found in
the appended Papers (B, C, D, E and H).
As explained in earlier sections 4.2 and 4.3, vertical cracks, inter-columnar

spacing, if very large or wide, may ease the passage of hot gases to flow through
them, which can increase the thermal conductivity of the coating. However, inter-
pass porosity bands are almost perpendicular to the direction of heat flow, so they
can help in decreasing the thermal conductivity. Other fine scale pores also help
in reducing the thermal conductivity due to the enhanced phonon scattering
interfaces in the microstructure.
For a TBC application, lower thermal conductivity is needed which then can be
achieved by tailoring the porosity as suggested in section 6.1.
6.3 Sintering behaviour of SPS TCs in TBCs

As presented in section 4.5, sintering is an important issue in TBCs and it can
affect coating properties and hence performance. This becomes even more
complicated in case of SPS coatings due to the varied pore size distribution. For
this reason porosity at different length scale is investigated in a systematic way to
understand their response individually when exposed to high temperature. As
shown in Figure 31, after 200 hours of isothermal heat treatment at 1100 ᵒC the
porosity at different length scale in a typical columnar SPS microstructure changes
in a significantly different manner.
Figure 31: Relative average porosity distribution of different pore classes in a typical
SPS TC microstructure (a) and change of average porosity at different length scale
after 200 hours of heat treatment at 1100 ᵒC (b) [Ganvir et al. Materials and Design,
2017]
66
For instance, Class-1 and Class-4 porosity show a significant increase and decrease
respectively after the heat treatment compared to the as-sprayed porosity
suggesting both pore coarsening and densification occurring in SPS
microstructures. More details regarding this study can be found in Paper H.
All possible sintering related microstructural changes in a typical SPS

microstructure are summarized in Figure 32, which is based on the results
explained in the appended Papers (D, G and H). Moreover, the corresponding
pore classes that are affected by these changes are also listed in Figure 32.
Figure 32: Flow chart highlighting the major sintering related changes that are
typically observed in SPS coatings and corresponding different pore classes affected
by those changes
Figure 32 shows that Class-1 and Class-2 pores are most susceptible to the pore
coarsening, especially Class-1 porosity which increases mainly due to the widening
of inter-columnar spacing during heat treatment, whereas the very fine pores i.e.
Class-4 porosity are more prone to undergo densification. As it can be seen from
Figure 31, unlike Class-1 and Class-4 porosity, the changes in Class-2 and Class-
3 porosity are difficult to assess, i.e. whether the change is increasing or decreasing
or no change. However, in general, based on the results as discussed in appended
Papers (D, E, G and H) it can be said that the Class-3 pores are most stable
showing a very little change after the heat treatment whereas the Class-2 pores
show a mixed behaviour i.e. both increase as well as decrease but mostly increase.
Such a knowledge regarding the individual response of different pore classes at

high temperature can assist in tailoring of porosity. This can ultimately help in
67
designing the optimized SPS coating microstructure for different TBC
applications.
6.4 Designing SPS TBCs for superior TCF

performance
Several factors summarized from the experimental work carried out during this
study (see Paper G) which can help to design an improved TCF performance SPS
TBC are listed in Figure 33. It should be borne in mind that there can be even
more factors; however only those are listed which were studied in this work.
Figure 33: Summary of several important factors needed for designing high TCF
performance columnar SPS TBC [Ganvir et al. Ceramics International, 2017]
Figure 33 suggests that all the three layers i.e. TC, BC and TGO are crucial and
should be considered while designing the SPS TBC for superior TCF
performance. Factors such as surface roughness and chemistry of the BC, the
TGO composition, and the nature of TC microstructure, TC phases and TC
sintering behaviour were identified as to be the most crucial. Figure 33 suggests
that a BC with lower surface roughness and higher beta phase content; a TGO
layer with lower spinels; and a TC having a columnar structure with high column
density and high total porosity with higher submicron/Class-3 pores can result in
a superior TCF performance SPS TBC. Based on such an understanding, a
simplified schematic of a recommended along with a non-recommended SPS
TBC microstructure design for achieving superior TCF performance is proposed
in Figure 34. The detailed analysis of all these factors and the proposed design
can be found in Paper G.
68
Figure 34: Simplified schematic of a design of two different SPS TBCs; (a) not
recommended and (b) recommended for superior TCF performance [Ganvir et al.
Ceramics International, 2017]
6.5 Designing SPS TBCs for superior TS

performance
Similar to TCF, several factors which can help to design an improved thermal
shock (TS) performance SPS TBC are listed in Figure 35.
Figure 35: Summary of important factors needed in tailoring of microstructure and

porosity for designing high thermal shock performance SPS TBC [Ref: Ganvir et al.
Materials and Design, 2017]
69
The figure in this case only lists factors related to the ceramic TC microstructure
whereas the parameters related to the BC and TGO can be selected as suggested
in Figure 33. It should be noted that there could be even more factors influencing
the TS however only those are listed which were studied in this work (as discussed
in Paper H). Figure 35 also outlines the microstructure tailoring methodology to
achieve higher TS lifetime and optimum thermal conductivity in a columnar SPS
TBC as pointed out in Figure 27 in section 6.1.2.
As it can be seen from Figure 35, for improved TS performance with an optimum
thermal conductivity, the desired target for various sources/origins of porosity in
a columnar microstructure to achieve a desired pore class distribution (i.e.
optimum Class-1 and Class-3 porosity and negligible Class-2 and Class-4 porosity)
can be as follows:
 Optimum column density

 Low column gap width
 Optimum inter-columnar spacing
 Negligible pores in the vicinity of the inter-columnar spacing
 Negligible partially unmolten or improper splats
 Negligible inter-pass porosity bands
 Optimum inter-splat porosity
 Negligible spherical particles and
 Negligible intra-splat porosity
Based on such an understanding based design philosophy, a simplified schematic

of the SPS TC microstructure design, capable of achieving high TS lifetime
without significantly compromising the thermal conductivity is proposed in
Figure 36. The proposed microstructure design tends to be like EBPVD, except
the presence of some porosity inside the columns in the form of Class-3 pores.
Of course, more efforts in the SPS process optimization are certainly needed in
order to achieve the proposed columnar SPS TBC design for superior TS
performance.
70
Figure 36: A simplified schematic of the design of SPS sprayed TC microstructure to

achieve higher thermal shock performance [Ref: Ganvir et al. Materials and Design,
2017]
71
7 Conclusions
This research work has explored the relationships between process parameters,
coating microstructure, thermal conductivity, thermal cyclic fatigue and thermal
shock lifetime in suspension plasma sprayed TBCs. The following conclusions are
drawn from this work correspondingly with the research questions stated earlier
in Chapter 1.
The liquid feedstock technology was shown to provide large opportunities in

creating different types of microstructures by varying different spray techniques
and process parameters. Predominantly, three different types of microstructures
were obtained using the various liquid feedstock sprayed techniques. The types
were categorized as highly porous, vertically cracked and columnar. The three
types of microstructures were shown to give significantly different thermal
properties. Axial suspension plasma spraying was shown as a promising technique
to produce various microstructures including all the three types, as well as low
thermal conductivity coatings.
Examples of microstructural features that were observed in the coatings are

columns, inter-columnar spacing, spherical particles, well molten splats (dense
zones), vertical cracks, fine cracks, branching cracks, inter-pass porosity bands
and pores (micron, submicron and nano sized). It was found that all of these
features influence the total porosity content in the coating, which in turn was
shown to have a significant influence on the thermal and mechanical properties
as well as the thermal cyclic and thermal shock lifetime of the coatings.
Porosity was categorized as open porosity, i.e. pores which are accessible to an
external fluid, and closed porosity. Image analysis on SEM micrographs has
shown to be capable of estimating both closed and open porosity and to provide
a fair estimate of the total porosity if two different magnifications are used. Image
analysis seems thus to provide the best estimate of the total porosity compared to
the two other techniques investigated, i.e. water impregnation and MIP, which
only could estimate the open porosity.
However, image analysis has also shown some limitations especially while
measuring the fine porosity. For this reason the combination of two techniques
i.e. image analysis and MIP for measuring coarse (>1 µm) and fine (<1 µm)
porosity respectively was utilized. The results showed excellent correlation
between the total porosity measured in such a way with the coating properties as
well as performance. This has also helped in classifying the porosity based on the
73
equivalent pore size in four different classes that is Class-1 (>10 µm), Class-2 (10
µm – 1 µm), Class-3 (1 µm – 100 nm) and Class-4 (<100 nm). Such classification
of pores has helped in tailoring the porosity in order to optimize coatings’
performance.
It was found that suspension plasma spraying enables an increase of the total
porosity content in the coating compared to solid feedstock plasma spraying.
Higher total porosity content and presence of fine pores and grains seem as the
most probable reason to the significantly reduced thermal conductivity.
Moreover, it was found that suspension plasma spraying enables a highly porous
as well as dense columnar structured coatings which are shown to be promising
candidates to provide higher thermal cyclic lifetime and higher thermal shock
lifetime respectively.
The individual influence of different porosity classes on thermal shock lifetime

was found to be related to their respective stress intensity factors. Class-1 porosity
was found to have the most severe effect on thermal shock lifetime than other
three pore classes due to its significantly higher stress-intensity factor. In terms of
coatings’ thermo-mechanical properties, fracture toughness was found to be the
most prominent thermal shock life determining factor. The thermal shock lifetime
was found to be increased with the increase in fracture toughness.
Overall this work concludes that suspension plasma spraying and specifically axial
suspension plasma spraying is a very promising technique to produce high
performance coatings for gas turbine applications.
74
8 Future work
This work was dedicated towards developing high performance TBCs using SPS.
However, no comparison was done with the industry standard conventional
TBCs produced by APS as well as EBPVD. Hence, as a first step in continuation
of this work can be a systematic comparative study between the best performing
SPS TBC resulted from this work and the industry standard APS and EBPVD
TBCs.
High temperature sintering related changes in the microstructures were

investigated in this work but not in great details. More fundamental investigations
of high temperature sintering related changes in the microstructures such as
densification, pore coarsening and grain growth could be the next step in
extending this work.
Modifying water based suspension properties using several surfactants to reduce

their surface tension without significantly modifying the viscosity can lead to
columnar type coatings, as noticed in this work. However, due to the lack of time
no more experimental trials were conducted. This could be of specific interest
especially for the industry as water based suspensions sprayed columnar coatings
can replace the ethanol based columnar coatings reducing the safety issue
possessed by ethanol handling.
Mechanical properties were measured using indentation technique but more

techniques can be explored in order to strengthen the claims made in this work.
In addition, properties such as erosion and corrosion resistance is also important
characteristics of a TBC, which could also be investigated in future. Moreover,
more fundamental assessment of failure mechanisms associated with the failure
of TBCs studied in this work during thermal cyclic fatigue as well as thermal shock
testing need to be investigated in future.
The work also showed that, axial suspension plasma spraying can obtain
extremely porous as well as dense coatings, which can be utilized for solid oxide
fuel cell applications; where a porous anode and dense electrolyte is needed. In
addition, the possibility to deposit extremely dense coatings can also be explored
for wear applications. Moreover, this work also showed that a very thin and dense
layer can be deposited using ASPS which makes this technique an exciting
possibility in the field of bio-coating application as well. Hence, these can also be
the possible routes to extend this research work in future.
75
9 Summary of appended publications
Paper A- Characterization of thermal barrier coatings produced by various

thermal spray techniques using solid powder, suspension and solution
precursor feedstock material
The paper was a first attempt in the extensive screening study, which was
performed in this thesis work to achieve a microstructure for the TBC application
with a lower thermal conductivity using liquid feedstock. Existing liquid
feedstocks (Suspension and Solution) were chosen, which were sprayed using
plasma spraying along with conventional solid powder feedstock. A comparative
study was performed on SPS, SPPS and APS sprayed TBCs; which were sprayed
using 8YSZ suspension, solution and powder feedstocks respectively. It was
found that a TBC with a microstructure resembling columnar type (inherently
strain tolerant structure) can be produced using SPS, with a much reduced thermal
conductivity, about half of that of the conventional APS TBC. Apart from this, it
was also found that vertically cracked microstructures can be produced using
SPPS. However, both SPS and SPPS coatings had a shorter lifetime than a
conventional APS coating.
Paper B- Comparative study of suspension plasma sprayed and suspension

high velocity oxy-fuel sprayed YSZ thermal barrier coatings
The second paper was a continuation of the first study where suspension was
found to be the most feasible feedstock. Hence, this paper focused on achieving
different microstructures using suspension as a feedstock, and different spraying
techniques. A comparative study was performed on 8YSZ suspension sprayed
TBCs, with S-HVOF and SPS. Suspension was injected axially and radially in S-
HVOF and SPS respectively. It was found that two different types of
microstructures namely, vertically cracked and columnar type resembling
structure can be predominantly achieved using S-HVOF and SPS techniques
respectively. SPS resulted in highly porous coatings with extremely low thermal
conductivity and relatively high thermal cyclic fatigue lifetime; whereas S-HVOF
resulted in comparatively dense coatings with higher thermal conductivity and
lower TCF lifetime. Apart from this, significant influence of initial powder size in
the suspension (D50) was also noticed on coating porosity and its thermal
properties. Reduction in D50 resulted in higher porosity and lower thermal
conductivity in both SPS and S-HVOF coatings.
77
Paper C- Characterization of microstructure and thermal properties of YSZ
coatings obtained by axial suspension plasma spraying (ASPS)
Although both techniques i.e. S-HVOF and SPS, explored in the study presented
in Paper B showed several advantages, they also showed some limitations. S-
HVOF had the limitation of achieving the desired high porosity due to the high
particle velocity involved, and radial injection SPS showed overspray problems
due to the radial injection. In an attempt to overcome these problems, it was
decided to use ASPS. A screening study was performed in order to explore various
possible microstructures which can be obtained by ASPS. It was found that ASPS
can generate predominantly three different types of microstructures which are
highly porous, vertically cracked and columnar type. These types were discussed
in this paper in detail.
A further aim of this study was to investigate the relationships between the
different microstructures and the thermal properties of the obtained coatings. It
was found that ASPS can be a potential technique to produce low thermal
conductivity TBCs, lower than the conventional APS and EBPVD TBCs. All
three different types (highly porous, columnar (feathery columnar) and vertically
cracked) discussed in this paper, showed varied scale porosity in a micron,
submicron and nano-sized scale. Higher porosity, lower column density and
higher inter-porosity bands present in the coating resulted in lower thermal
diffusivity and conductivity. Image analysis was also shown as a promising
technique to estimate the total porosity in the coatings.
Paper D- Influence of microstructure on thermal properties of axial

This paper continued the study presented in Paper C where the ASPS technique
was explored to achieve various microstructures. This paper focused on
discussing only columnar type microstructures and their influence on thermal
properties. It was shown that the ASPS technique can produce a columnar
structured TBC similar to EBPVD coatings; but with lower thermal conductivity
due to the high amount of fine scaled microstructural features present in the
coating. Higher total porosity content resulted in lower thermal diffusivity and
thermal conductivity. No clear relationship between the column density and the
thermal properties was found. Only the total porosity was shown to have a
significant effect. Higher spray distance and surface speed along with other
process parameters resulted in lower crystallite size, higher total porosity and
higher column density which resulted in lower thermal diffusivity and thermal
conductivity of the coating.
78
SUMMARY OF APPENDED PUBLICATIONS
Paper E- Influence of isothermal heat treatment on porosity and crystallite

size in axial suspension plasma sprayed thermal barrier coatings for gas
turbine applications
During the first half of this work (investigated in Paper A, B, C and D) the thermal
conductivity was found to be affected by the sintering related changes in the
microstructure. Hence, as first step towards the second half of this PhD work, all
the columnar coatings studied in paper D were isothermally heat treated at 1150
ᵒC in an inert atmosphere. The effect of heat treatment on columnar
microstructures was studied in this work. Several sintering related microstructural
changes such as pore densification, crystallite size growth and pore coarsening
were noticed. The effect of these sintering related changes along with the effect
of total porosity on thermal conductivity was also studied. In addition, the two
magnification approach (as suggested in Paper C but not fully used) was
successfully utilized to measure the total porosity.
Total porosity in 8YSZ ASPS sprayed ceramic top coats was found to be not only
decreasing for some coatings as expected in a conventional APS TBCs but also
increasing in some other cases after heat treatment at 1150 ᵒC for 200 h in Argon.
The increase in porosity was attributed to pore coarsening, i.e., of coarser pores
(at about larger than 1 µm^2), more specifically due to the widening of the inter-
columnar spacing and coalescence of pores. It was also found that it is a trade-off
between the three microstructural changes (coarsening, densification and
crystallite size growth) that can decide the overall trend in thermal conductivity
of the respective coating. If the pore coarsening dominated the densification and
crystallite size growth then the overall coating thermal conductivity was observed
to be decreased significantly.
Paper F- Experimental visualization of microstructure evolution during

suspension plasma spraying of thermal barrier coatings
In all the papers related to the SPS coatings during this PhD work, different
coatings were sprayed using varied plasma spray parameters while using the same
suspension (no change in suspension properties). However, this is the only paper
where several coatings were sprayed with different microstructures using different
suspensions but using same plasma spray parameters. This was an attempt to
systematically identify various crucial suspension properties and their role in
coating formation and microstructure evolution in SPS. Six different suspensions
were prepared with different solid load content, solvent types and particle size
distribution. The effect of all these three variables (solid load, solvent type and
particle size distribution) was systematically studied on coating microstructure. All
the ethanol based suspensions were found to produce columnar coatings whereas
water based and mixed (water and ethanol) suspensions were found to produce
79
vertically cracked structures. Such a difference in coating formation was explained
by studying the suspension droplet momentum and the theories available in the
literature. The droplet size was calculated using several suspension properties
measured experimentally along with some simplified assumptions. Similarly, the
droplet speed was also experimentally measured in order to calculate the droplet
momentum. A clear and strong correlation between the droplet momentum and
the coating formation in SPS was shown. Additionally, a systematic progressive
evolution of columnar as well as lamellar/vertically cracked type microstructures
was also successfully shown. Such a progressive microstructure evolution study is
by far the first systematic experimental proof to the much sought after shadowing
effect theory for column formation used and widely accepted in the field of
suspension plasma spraying.
Paper G- Failure analysis of thermally cycled columnar thermal barrier

coatings produced by high- velocity-air fuel and axial-suspension-plasma
spraying: A design perspective
So far (in all the previous Paper A to Paper E) the focus was mainly on
establishing the relationships between coating microstructure and thermal
conductivity in SPS TBCs. In this work, the influence of coating microstructure
on thermal cyclic fatigue lifetime was studied in detail. Eight different TBCs with
four different top coats were sprayed using the same suspension but different
plasma spray parameters on each of the two different bond coats, which were
sprayed using two different BC chemistry with the same high velocity air fuel
spray parameters.
An in-depth experimental investigation was performed to understand the failure

behaviour of columnar TBCs subjected to thermal cyclic fatigue (TCF) test at
1100 ᵒC. The study revealed that the TCF performance was influenced by the TC
microstructure to an extent, but was primarily affected by the severity of thermally
grown oxide (TGO) growth at the bond coat-TC interface. Mixed failure modes
comprising crack propagation through the bond coat-TGO interface, through
TGO and within the TC were identified. Based on the analysis of the experimental
results and thorough discussion a novel design of microstructure for the high TCF
performance columnar TBC was also proposed.
Paper H- Tailoring columnar microstructure of axial suspension plasma

sprayed TBCs for superior thermal shock performance
This work was focused on analysing the thermal shock behaviour of the columnar
SPS TBCs. In fact, this study was an effort towards understanding the basis for
tailoring the columnar microstructures produced by a relatively modern high
power ASPS technique to achieve high thermal shock lifetime for TBCs. Failure
80
SUMMARY OF APPENDED PUBLICATIONS
analysis of columnar TBCs subjected to thermal shock test revealed a strong

correlation between the total porosity and lifetime where the lifetime was found
to be progressively decreasing with the increase in total porosity. Fracture
toughness was found to be the most prominent life-determining factor and have
shown a strong correlation with the lifetime of various ASPS TBCs. The porosity
analysis in this work was done by combining the two techniques namely image
analysis and MIP which were studied in earlier papers. Such a combination of two
different techniques was found to be more beneficial as image analysis was used
to measure only the coarse porosity (due to its sensitivity to measure fine pores)
and MIP was used to measure only the fine pores (as MIP can over predict the
coarse porosity due to the influence of the high surface roughness of SPS TCs).
In addition, a methodology towards tailoring the columnar microstructure by

classifying the porosity in four different classes based on the pore size range was
utilized. The porosity was categorized as Class-1(>10 µm), Class-2(10 µm-1 µm),
Class-3(1 µm-100 nm), and Class-4(<100 nm) and their individual role towards
improving the thermal shock lifetime by improving the toughness was
successfully done. It was found that a tailored ASPS columnar microstructure to
achieve higher thermal shock lifetime without significantly compromising
coatings’ thermal insulation could be a microstructure without Class-4 and Class-
2 porosity, lower Class-1 porosity and optimum Class-3 porosity.
81
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94
APPENDED PUBLICATIONS
Paper A: - Characterization of thermal barrier coatings produced by various

thermal spray techniques using solid powder, suspension and solution
precursor feedstock material
Paper B: - Comparative study of suspension plasma sprayed and

suspension high velocity oxy-fuel sprayed YSZ thermal barrier coatings
Paper C: - Characterization of microstructure and thermal properties of

YSZ coatings obtained by axial suspension plasma spraying (ASPS)
Paper D: - Influence of microstructure on thermal properties of axial

Paper E: - Influence of isothermal heat treatment on porosity and

crystallite size in axial suspension plasma sprayed thermal barrier coatings
for gas turbine applications
95
Paper F: - Experimental visualization of microstructure evolution during
suspension plasma spraying of thermal barrier coatings
Paper G: - Failure analysis of thermally cycled columnar thermal barrier

coatings produced by high-velocity-air fuel and axial-suspension-plasma
spraying: A design perspective
Paper H: - Tailoring columnar microstructure of axial suspension plasma

sprayed TBCs for superior thermal shock performance
96
Tidigare avhandlingar – Produktionsteknik
PEIGANG LI Cold lap formation in Gas Metal Arc Welding of

steel An experimental study of micro-lack of fusion defects,
2013:2.
NICHOLAS CURRY Design of Thermal Barrier Coatings,
2014:3.
JEROEN DE BACKER Feedback Control of Robotic Friction
Stir Welding, 2014:4.
MOHIT KUMAR GUPTA Design of Thermal Barrier Coatings
A modelling approach, 2014:5.
PER LINDSTRÖM Improved CWM platform for modelling
welding procedures and their effects on structural behavior,
2015:6.
ERIK ÅSTRAND A Framework for optimised welding of
fatigue loaded structures Applied to gas metal arc welding of
fillet welds, 2016:7.
EMILE GLORIEUX Multi-Robot Motion Planning Optimisation
for Handling Sheet Metal Parts, 2017:10.
EBRAHIM HARATI Improving fatigue properties of welded
high strength steels, 2017:11.
ANDREAS SEGERSTARK Laser Metal Deposition using
Alloy 718 Powder Influence of Process Parameters on
Material Characteristics, 2017:12.
ANA ESTHER BONILLA HERNÁNDES On Cutting Tool
Resource Management, 2018:16. [Submitted]
SATYAPAL MAHADE Functional Performance of Gadolinium
Zirconate/YSZ Multi-layered Thermal Barrier Coatings,
2018:18. [Submitted]
AMIR PARSIAN Regenerative Chatter Vibrations in
Indexable Drills: Modeling and Simulation, 2018:21.
[Submitted]
ESMAEIL SADEGHIMERESHT High Temperature Corrosion
of Ni-based Coatings, 2018:23. [Submitted].
Design of Suspension Plasma Sprayed
Thermal Barrier Coatings
Thermal barrier coatings (TBCs) are widely used to provide thermal insulation to com-
ponents in both power generation and aero engine gas-turbines. Improvement in perfor-
mance of TBCs will lead to more efficient and durable engines that is why there is a con-
stant need to ﬁnd new TBC solutions. Suspension plasma spraying is a relatively newer
deposition technique and gaining increasing research interest since it has been shown to
be capable of producing TBCs with superior performance.
This work was focused on identifying the relationships between process parameters,
coating microstructure, thermal conductivity and lifetime in suspension plasma sprayed
TBCs. A further objective was to utilize these relationships to enable tailoring of the TBC
microstructure for superior performance compared to state-of-the-art TBC used in in-
dustry today, i.e. atmospheric plasma sprayed TBCs using solid feedstock. A variety of mi-
crostructures, such as highly porous, vertically cracked and columnar, were produced and
investigated. Progressive evolution of the much sought-after columnar microstructure
produced by SPS was experimentally demonstrated. It was shown that there are strong
relationships between microstructure, thermo-mechanical properties and performance
of the coatings. Finally, based on the experimental results, a tailored columnar micro-
structure design for a superior TBC performance is also proposed.
Ashish Ganvir
Ashish comes from a small town ‘Amravati’, Maharashtra, India and received his
bachelor’s degree in materials and metallurgical engineering from Indian Insti-
tute of Technology Kanpur, India in 2013. Before starting his master’s study,
he did an apprenticeship in summer 2013 at International Advanced Research
Centre for Powder Metallurgy and New Materials (ARCI), Hyderabad, India. He
received his master’s degree in manufacturing engineering from University West,
Trollhättan, Sweden in 2014. In 2016, he worked in industry as a visiting researcher at Innovnano mate-
rials, Coimbra, Portugal. He was also a visiting research fellow at the Materials Synthesis and Processing
(IEK-1) research centre of Forschungszentrum Jülich, Germany in summer 2016. His main interests are
in the areas of materials science, surface & coatings engineering, powder metallurgy & defect analysis.
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PhD Thesis

Design of Suspension Plasma

Design of Suspension Plasma

© Ashish Ganvir 2018

Trollhättan, Sweden, 2018

It is with immense gratitude that I acknowledge the financial support provided by

I am grateful to my family: my parents, brother and sisters who have provided me

And finally, to all those individuals/institutions/government agencies back in

Nyckelord: Mikrostruktur; Termiska barriärbeläggningar; Axialmatning;

Titel: Design av suspensionsplasmasprutade termiska värmebarriärbeläggningar

Termiska värmebarriärbeläggningar (TBC) används i stor utsträckning på

Syftet med detta avhandlingsarbete var att undersöka samband mellan

En mängd olika mikrostrukturer, såsom mycket porösa, strukturer med vertikal

Title: Design of Suspension Plasma Sprayed Thermal Barrier Coatings

By using a liquid feedstock in thermal spraying, new types of TBCs can be

A variety of microstructures, such as highly porous, vertically cracked and

Keywords: Microstructure; Thermal Barrier Coatings; Axial Injection; Suspension

2. The second part of this work was primarily dedicated towards

Paper A. Characterization of thermal barrier coatings produced by

Paper B. Comparative study of suspension plasma sprayed and

Paper C. Characterization of microstructure and thermal properties of

Ashish Ganvir has performed all experimental characterization except mercury

Paper E. Influence of isothermal heat treatment on porosity and

Paper F. Experimental visualization of microstructure evolution

Paper G. Failure analysis of thermally cycled columnar thermal barrier

Ashish Ganvir performed all experimental characterization except image analysis

Paper H. Tailoring columnar microstructure of axial suspension

Ashish Ganvir has performed all experimental characterization except mercury

1. A. Ganvir, C. Kumara, M. Gupta, P. Nylen, “Thermal Conductivity in

2. U. Klement, J. Ekberg, A. Ganvir, “EBSD Analysis and Assessment of

3. J. Ekberg, A. Ganvir, U. Klement, S. Creci, L. Nordstierna, “The

5.6 Evaluation of thermal cyclic fatigue (TCF) lifetime .............. 53

APS: Atmospheric Plasma Spraying

ASPS: Axial Suspension Plasma Spraying

BC: Bond Coat

CMAS (Calcia-Magnesia-Alumina-Silica or molten silicate)

CSN: Chromia, Spinel and Nickel oxide

CTE: Coefficient of Thermal Expansion

D50: Median size (diameter) of a particle in a certain particle size distribution.

DSC: Differential Scanning Calorimetry

DVC: Dense Vertically Cracked

EBPVD: Electron Beam Physical Vapor Deposition

FC: Fine cracks

HVAF: High Velocity Air Fuel

HVOF: High Velocity Oxy Fuel

HVSFS: High Velocity Suspension Flame Spraying

IA: Image analysis

IC: Inter-columnar spacing

IGTs: Industrial Gas Turbines

LFA: Laser Flash Analysis

LPPS: Low Pressure Plasma Spray

MIP: Mercury Intrusion Porosimetry

MP: Micron Pores

OM: Optical Microscopy

SEM: Scanning Electron Microscopy

S-HVOF: Suspension-High Velocity Oxy Fuel

SP: Sub-micron Pores

SPPS: Solution Precursor Plasma Spraying

SPS: Suspension Plasma Spraying

TBC: Thermal Barrier Coating

TC: Top Coat

TCF: Thermal Cyclic Fatigue

TGO: Thermally Grown Oxide