CHARACTERIZATION OF 10MOL% Sc2O3-1MOL% CeO2-ZrO2 CERAMICS AS ELECTROLYTE MATERIAL FOR LOWER TEMPERATURE SOLID OXIDE FUEL

CELLS

by

Devendra Ray

A thesis submitted to the graduate faculty in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE

Department: Mechanical & Chemical Engineering Major: Mechanical Engineering Major Professor: Dr. Jag Sankar

North Carolina A&T State University Greensboro, North Carolina 2007

DEDICATION

First and foremost, I would like to thank my Lord Shiva for giving me the strength and passion to arrive at this point and for putting the right people in my life at the right time to help guide me. I dedicate this thesis to my parents, Ramkailash Ray, father, and late mother, Ramshakhi Devi Ray, for their love, encouragement and the many sacrifices they made that have enabled me to arrive at this point of my life. I would also like to dedicate this thesis to my wife, Sima Ray. Finally, I would like to thank all my family and friends who have encouraged and supported me to reach this milestone in my life.

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BIOGRAPHICAL SKETCH

Devendra Ray was born in Nepal and immigrated to the United States of America (USA) on September 7, 2004. In 2002, he graduated from Kathmandu University, Nepal with an undergraduate degree in Mechanical Engineering. He is a candidate for the Master of Science degree in Mechanical Engineering at North Carolina Agricultural and Technical State University. He has performed research on solid oxide fuel cells (SOFC) electrolyte materials.

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ACKNOWLEDGEMENTS

I would like to begin by thanking my major advisor, Dr. Jag Sankar, and senior research scientist/co-advisor, Dr. Sergey Yarmolenko, for their consistent guidance and support over the past two years. I significantly benefited from their knowledge and valuable experience in the field of material science and its characterization. I would also like to thank all my friends and the staff of the Center for Advanced Materials and Smart Structures (CAMSS). I would also like to express my thanks to Dr. Z. Xu and Dr. M. T. Saad for their suggestions. I am very grateful to my family for their support, sacrifice, and encouragement in assisting me to achieve this goal.

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TABLE OF CONTENTS
LIST OF FIGURES ........................................................................................................... ix LIST OF TABLES............................................................................................................ xii ABSTRACT..................................................................................................................... xiii CHAPTER 1. INTRODUCTION ........................................................................................1 1.1 Research Objective ..................................................................................................2 CHAPTER 2. LITERATURE REVIEW .............................................................................3 2.1 Background .............................................................................................................3 2.2 Function of Fuel Cells.............................................................................................3 2.3 History of Fuel Cells...............................................................................................4 2.4 Types of Fuel Cells .................................................................................................5 2.5 Basic Components of SOFC ...................................................................................7 2.5.1 Electrolyte ......................................................................................................8 2.5.2 Electrolyte for Solid Oxide Fuel Cells...........................................................8 2.6 Introduction of Zirconia........................................................................................10 2.6.1 Crystallographic Structure ...........................................................................10 2.6.2 Application of Scandia Stabilized Zirconia (ScSZ).....................................12 2.6.3 Different Electrolyte Materials ....................................................................14 CHAPTER 3. EXPERIMENTAL METHODS AND CHARACTERIZATION ..............18 3.1 Materials ...............................................................................................................18 3.2 Fabrication of Ceramic .........................................................................................18

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3.2.1 Powder Compaction.....................................................................................18 3.2.2 Sintering.......................................................................................................19 3.3 Sample Preparation ...............................................................................................20 3.4 Study of Mechanical Properties ............................................................................22 3.4.1 Density and Porosity Analysis .....................................................................22 3.4.2 Indentation Techniques for Hardness and Fracture Toughness Analysis....24 3.4.2.1 Nanoindentation..................................................................................24 3.4.2.2 Microindentation.................................................................................31 3.5 Microstructure Characterization ...........................................................................36 3.6 XRD Measurements..............................................................................................43 3.6.1 Coefficient of Thermal Expansion (CTE)....................................................44 3.6.1.1 Temperature Calibration .....................................................................48 CHAPTER 4. RESULTS AND DISCUSSION.................................................................50 4.1 Charaterization of Praxair and DKKK Powders...................................................50 4.1.1 Theoretical Densities and Actual Composition ...........................................50 4.1.2 XRD of Powders ..........................................................................................54 4.2 Sintering Behavior of Powders .............................................................................57 4.2.1 Density Measurements of ScCeSZ and its Porosity ....................................58 4.2.2 Microstructure and Grain Size .....................................................................63 4.3 Phases and Stability of DKKK and Praxair Ceramics ..........................................67 4.3.1 Phase Analysis in DKKK-based Samples ...................................................68 4.3.2 Phase Transition in J1600 Sample ...............................................................69

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4.4 Coefficients of Thermal Expansion (CTE) ...........................................................71 4.5 Hardness and Fracture Toughness ........................................................................78 4.5.1 Microindenatation of Etched and Non-Etched Samples..............................78 4.5.2 Nanoindentation...........................................................................................87 CHAPTER 5. CONCLUSION AND FUTURE WORK ...................................................89 5.1 Conclusion .............................................................................................................89 5.2 Future Work ...........................................................................................................90 REFERENCES ..................................................................................................................91

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LIST OF FIGURES

FIGURE

PAGE

2.1 Schematic representation of fuel cell...........................................................................4 2.2 Phase diagram of Sc2O3-ZrO2 system .......................................................................11 3.1 Illustration of changes in the surface morphology after polishing on diamond paper with grits 3µm, 1 µm, and 0.5µm (from left to right) ......................................21 3.2 A schematic representation of the indentation process showing various parameters involved in the analysis ...........................................................................26 3.3 Nanoindentation load-displacement relationship.......................................................27 3.4 Typical images collected at 500x on optical microscope for hardness study ............33 3.5 (a) Schematic figure having crack and indent length; (b) Image collected at 1000x on optical microscope (Indentation load is 200g)..................................................35 3.6 Typical SEM images for grain size study ..................................................................38 3.7 Typical AFM working principle ................................................................................39 3.8 (a) Typical AFM images for grain size study; (b) Grain size and cavitations measurements............................................................................................................42 3.9 Temperature dependent shifting of XRD peaks positions ........................................45

3.10 Constant, linear and quadratic fitting with temperature vs. log (LT) (P1600powder) .....................................................................................................................47 3.11 Instrumentally set temperature vs. residuals (P1600-powder)..................................48 3.12 Polynomial fitting of calibrated temperature vs. instrumentally set temperature ...............................................................................................................49 4.1 SEM micrographs of powders (a-Praxair, USA) and (b-DKKK, Japan)...................53

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4.2 XRD pattern at different temperatures.......................................................................54 4.3 XRD pattern of as-received Praxair powder..............................................................55 4.4 XRD pattern of as-received DKKK powder..............................................................56 4.5 Fracture surfaces of samples P1600-(a) and J1600-(b)..............................................59 4.6 Grain structure of samples produced from Praxair powder sintered at temperatures 1500ºC (left) and 1600ºC (right) ..........................................................60 4.7 Grain structure of samples produced from DKKK powder sintered at temperatures 1400ºC (left), 1500ºC (middle) and 1600ºC (right) ...................................................60 4.8 SEM images of polished and low angle ion-milled surface of sample P1600 (a) and thermally etched surfaces of samples P1600 (b) and J1600(c).................................61 4.9 The dependence of density on sintering temperatures...............................................62 4.10 Porosity level vs. sintering temperature....................................................................62 4.11 SEM images of DKKK samples from left to right sinter correspondingly 1200-1600°C.............................................................................................................64 4.12 SEM images of Praxair samples from left to right sinter correspondingly 1500-1600°C.............................................................................................................64 4.13 Grain size vs. sintering temperatures ........................................................................65 4.14 SEM images collected after 1hr ion milling at 30 deg (left - J1600 right - P1600, right - P1600) ............................................................................................................66 4.15 SEM images collected after ion milling (left-J1600 milled at 9-deg for 18hrs, right - P1600 milled at 5 deg for 20hrs)....................................................................67 4.16 SEM images of P1600 collected after ion milled at 5 deg for 20hrs (right high porous area, left - less porous) ..........................................................................67 4.17 Phase content in the sample DKKK-1200 at different temperatures from XRD (Retvield multiphase analysis) ........................................................................69 4.18 Changes in XRD pattern of powdered sample J1600 heated from 300 to 500°C with step 10°C...........................................................................................................70

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4.19 Phase transition in DKKK ceramic sintered at 1600°C............................................70 4.20 Instrumentally set temperature vs. residuals (Praxair powder).................................74 4.21 Constant, linear and quadratic fitting with temperature vs. log (LT) (Praxair powder) .....................................................................................................................74 4.22 Instrumentally set temperature vs. residual(DKKK powder) ...................................75 4.23 Constant, linear and quadratic fitting with temperature vs. log (LT) (DKKK powder) .......................................................................................................75 4.24 Instrumentally set temperature vs. residuals (J1500 Powder) ..................................76 4.25 Constant, linear and quadratic fitting with temperature vs. log (LT) (J1500 Powder) .....................................................................................................................76 4.26 Instrumentally set temperature vs. residuals (J1500 ceramic) ..................................77 4.27 Constant, linear and quadratic fitting with temperature vs. log (LT) (J1500 ceramic).....................................................................................................................77 4.28 Hardness vs. sintering temperature plot for etched and non-etched sample.............78 4.29 Variation in fracture toughness value with temperature ...........................................79 4.30 (a) Effect of sintering temperature on microhardness and fracture toughness at the load 1000g; (b) Micrograph of typical Vickers indents and cracks at different loads (thermally etched J1600) ..................................................................81 4.31 ISE analysis using power law (a) and Nix-Gao (b) models......................................86 4.32 Nanoindentation Young’s modulus results...............................................................88 4.33 Nanoindentation hardness results .............................................................................88

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LIST OF TABLES

TABLE

PAGE

2.1 Description of major fuel cell types.............................................................................6 2.2 Commercially available types of electrolyte materials..............................................14 3.1 Name of sample based on powder and sintering temperature ...................................19 3.2 Calculation of actual temperature from set temperature ...........................................49 4.1 Theoretical density from the actual composition of DKKK powder.........................51 4.2 Theoretical density from the actual composition of Praxair powder.........................52 4.3 Powder characterization.............................................................................................53 4.4 Density and porosity of sintered samples ..................................................................58 4.5 Grain size and in-grain cavities at different sintering temperatures ..........................65 4.6 Coefficients of thermal expansion for Praxair and DKKK samples in ceramic and powder forms ......................................................................................................73 4.7 Hardness (H) and fracture toughness (K1C) values at different sintering temperatures and loads for non-etched samples .......................................................82 4.8 Hardness (H) and fracture toughness (K1C) values at different sintering temperatures and loads for thermally etched samples ...............................................83 4.9 Comparison of hardness (H) and fracture toughness (K1C) of non-etched and etched samples. .................................................................................................84 4.10 ISE parameters for Praxair and DKKK-based samples ............................................86 4.11 Nanoindentation values……….................................................................................87

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ABSTRACT

Ray, Devendra. CHARACTERIZATION OF 10MOL% Sc2O3-1MOL% CeO2-ZrO2 CERAMICS AS ELECTROLYTE MATERIAL FOR LOWER TEMPERATURE SOLID OXIDE FUEL CELLS (Major Professor: Dr. Jag Sankar), North Carolina Agricultural and Technical State University. Material properties such as hardness, fracture toughness, densities and coefficients of thermal expansion are very important parameters for stability and reliability of solid oxide fuel cell (SOFC) operation. Ceria doped Sc2O3-CeO2- ZrO2 ceramics are also very promising materials as electrolyte in solid oxide fuel cells (SOFC) due to their high oxygen conductivity in the 800-1000°C temperature range. In this experimental work, sintering behavior of two commercial powders with the nominal composition 10mol% Sc2O3-1mol% CeO2-ZrO2 which were produced by Praxair surface technologies, USA and DKKK, Japan was studied. Ceramics were made by sintering uniaxially pressed pallets at temperature range 1100-1600°C in air. Hardness and fracture toughness of ceramics sintered at different temperatures were studied by microindentation method. The density measurement was done using Archimedes’ principle. Porosity level in ceramics was estimated using actual and theoretical densities calculated using lattice parameter a=5.09 Ǻ of FCC unit cell obtained from XRD data and actual composition of powder. Hardness of most dense ceramics reaches 15GPa and fracture toughness is in the range of 1.8-2.5MPa×m 0.5. These results are in good agreement. Hardness of ceramics depends on indentation depth due to indentation size effect (ISE). Indentation size effect parameters were analyzed using Power law model.

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CTEs were studied. These results can be further used for the optimal design of SOFC layered structures as well as for determination of their reliability and durability under operational conditions.

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CHAPTER 1 INTRODUCTION

It is well known that production and distribution of energy affects all sectors of the global economy. The increasing industrialization of the world requires sustainable, highly efficient energy production. Without major technological advancement, energy production will impact the quality of human life on Earth. Dependency on fossil fuel will not help to maintain the global economy in the long term due to the growing consumption and limitation of fossil fuel. For this reason, the application of fuel cell technologies may be one of the most important technological advancements of the future. A fuel cell operating as a sort of continuously replenished battery provides an alternative whereby electrical energy can be made available with smaller losses. Electrical energy is derived from the reduction/oxidation reaction of a fuel such as hydrogen and an oxidant such as oxygen. If the fuel is clean, the effluents are in principle only water, heat and CO2. Fuel cell plants can be modular in design, and the energy production can be adjusted to meet the actual demand, which is a convenient feature for a power source in a technological society [1]. The efficiency of a fuel cell is dictated by factors regarding the kinetics and driving forces of electrochemical reactions. An electrolyte has a very important role which is to achieve optimum efficiency. Only a few materials have survived as practical solid oxide fuel cell (SOFC) electrolytes because many electrical, chemical, and mechanical properties are required of a successful electrolyte. These factors can be 1

improved through the introduction of superior electrolyte materials and enhanced processing techniques [2].

1.1 Research Objective The objective of this research was to further the development of better electrolyte material. This includes the study of mechanical and microstructure properties of two powders received from Praxair surface technology, USA, and DKKK, Japan. Knowledge and understanding of mechanical properties such as hardness (H), fracture toughness (K1c), thermal properties and densities are very important for the design of electrolyte in SOFC. It is equally important to know the microstructure, such as the grain size of two powders at different sintering temperatures, which has an important role in ionic conductivity. Samples were produced at the temperature range 1100-1600°C in air. Specifically, the objectives can be outlined as follows:

To study mechanical properties such as hardness, fracture toughness, and densities of two powders having nominal composition 10mol%Sc2O31mol%CeO2- ZrO2 at all sintering temperatures.

To study the grain size measurements at different sintering temperatures of the material.

• • •

To study the coefficient of thermal expansion. To study phase stability. To study modulus of elasticity.

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CHAPTER 2 LITERATURE REVIEW

2.1 Background This chapter provides a brief review of solid oxide fuel cells (SOFC), what they are and how they work. It also details their history, the types of fuel cells, working principles and materials employed for SOFC production. This research work emphases the scandia stabilized zirconia (ScSZ) electrolyte material which was selected for the study, in particular, its various properties, research and developmental aspects.

2.2 Function of Fuel Cells A fuel cell is a “factory” that takes fuel as input and produces electricity as output. Furthermore, in terms of chemistry, it is an electrochemical device that directly converts chemical energy from a reaction between a fuel and oxidant into electrical energy as long as fuel is supplied. This is the key difference between a fuel cell and a battery. While both rely on electrochemistry, a fuel cell is not consumed when it produces electricity. It is really a factory, a shell, which transforms the chemical energy stored in a fuel into electrical energy. The basic elements of a typical fuel cell, as depicted in Figure 2.1, consists of electrolyte in intimate contact with a porous anode (negative electrode) and porous cathode (positive electrode). The fuel and oxidant gases flow along the surface of the anode and cathode, respectively, and then react electrochemically in the three-phaseboundary region established at the gas-electrolyte electrode interface. A fuel cell can 3

theoretically produce electrical energy for as long as fuel and oxidant are fed to the porous electrodes, but the degradation or malfunction of some of its components limits the practical life span of all fuel cells.

Fuel

Anode Electrolyte Cathode

e-

External load
e-

Direct current Exhaust gases and heat

Oxidant

Figure 2.1: Schematic representation of fuel cell

2.3 History of Fuel Cells The history of the fuel cell dates back to 1839 when Sir William Grove [3] first described its principle and demonstrated a fuel cell at room temperature using a liquid electrolyte. In 1899, Nernst discovered the solid oxide electrolyte when using stabilized zirconia in making filaments for electric glowers. In the middle of the 20th century the development accelerated. Several types of fuel cells were developed in the race for conquering space. In the eighties, focus on pollution and the demand for higher efficiency in the exploitation of fossil resources initiated a new wave of fuel cell development. At present, several types of fuel cells are approaching the consumer market within a limited

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number of years. The primary challenges are cost and durability, to be solved by materials selection and design engineering [2].

2.4 Types of Fuel Cells Currently, there are five major types of fuel cells, differentiated from one another by their electrolyte material [1]: 1. Phosphoric acid fuel cell (PAFC) 2. Polymer electrolyte member fuel cell (PEMFC) 3. Alkaline fuel cell (AFC) 4. Molten carbonate fuel cell (MCFC) 5. Solid oxide fuel cell (SOFC). While all five fuel types are based upon the same underlying electrochemical principles, they operate at different temperature regimens, incorporate different materials, and often differ in their fuel tolerance and performance characteristics, some of which are listed in Table 2.1[1, 2, 3, and 52]. Among these, operation temperature, electrical efficiency and demands for fuel composition are the defining prospects of each type. Polymer electrolyte member fuel cells are well suited to transportation applications because they provide a continuous electrical energy supply from fuel at high levels of efficiency and power density. They also offer the the advantage of minimal maintenance because there are no moving parts in the power generating stacks of the fuel cell system.

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Table 2.1. The description of major fuel cell types SOFC Ceramic H+ 600-1000º Perovskities (ceramic) Ceramic based H2, CH4 , CO Stainless based H2, CH4 >Electric utility >High efficiency >Fuel flexibility >Can use a variety of catalysts >High temperature enhance corrosion and breakdown of cell components 60% >Cathode reaction faster in alkaline electrolyte that leads to high performance >Requires removal of CO2 from fuel and air streams, which is expensive 40% >Military >Space Carbon based H2 Nickel Platinum Platinum Carbon based H2 >Electric utility >Transportation >Can use impure H2 as fuel 650º 60-200º 175-200º H+ Molten carbonate MCFC AFC PAFC PEMFC

Electrolyte1 Liquid KOH (immobilized) OH80º Liquid H3PO4 (immobilized) CO32-

Charge Carrier1

Polymer membrane O2-

Operating temperature1 Catalyst1

Platinum Carbon based H2, Methanol

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Cell components1 Fuel compatibility1 Applications2

Advantages2

>Electric utility >Portable power >Transportation >Solid electrolyte reduces corrosion and management problems >Low temperature >Requires platinum catalyst >Low current and power 40% >Low operating temperature requires expensive catalysts 40%

Disadvantages2

Electrical Efficiency3

>Electric utility >Transportation >Military >High efficiency >Fuel flexibility >Can use a variety of catalysts >Reduces corrosion problems >High temperature accelerates breakdown of cell components 60%

The low temperature fuel cells (AFC, PAFC) also have a potential for propulsion of cars, where a short heating time is needed and the efficiency has to be compared with that of a combustion engine (~20%) given by the limitations of the Carnot cycle. In miniature applications such as cellular phones, laptops and digital cameras, methanol is reformed to hydrogen in the fuel cell itself (reformation reaction). For applications that require higher output, such as cars, methanol can be reformed in a device that is located outside the fuel cell. This reformation can be accomplished through steam reforming or partial oxidation [2]. Recently invented micro fuel cells are smaller, lighter, cleaner, simpler and less expensive than lithium ion batteries [2].

2.5 Basic Components of SOFC There are different types of electrolytes that are commercially available; however, more research and development is needed to characterize and explore new and promising electrolytes for an intermediate temperature (IT) SOFC. The basic components of SOFC are: 1. Cathode 2. Electrolyte 3. Anode 4. Interconnect This thesis focuses on electrolyte material.

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2.5.1 Electrolyte The most effective electrolytes employed in fuel cells have ionic conductivities of around 0.10 Ώ-1cm-1. The search for better electrolytes has led to the development of three major candidate material classes for fuel cells: aqueous, polymer, and ceramic electrolytes. Regardless of the class, however, any fuel cell electrolyte must meet the following typical properties to be a better electrolyte: • • • • • • High ionic conductivity Low electronic conductivity High stability (in both oxidizing and reducing environments) Low fuel crossover Reasonable mechanical strength (if solid) Ease of manufacturability. Except for the high conductivity requirement, the electrolyte stability requirement is often the hardest to fulfill. It is difficult to find an electrolyte that is stable in both the highly reducing environment of the anode and the highly oxidizing environment of the cathode [1, 52]. 2.5.2 Electrolyte for Solid Oxide Fuel Cells The electrolyte is the central part of an SOFC. Within the electrolyte the oxygen ions (O2-), which are reduced on the air electrode side (cathode), are transported and react with, for example, hydrogen to form water on the fuel electrode side (anode). Conversely, electrons (e-) are formed and while moving in the opposite direction, are available for an outside current use. Nowadays, the most frequently used electrolyte

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material is zirconia (ZrO2). Zirconia is at ambient conditions a poor ionic conductor. If ZrO2 is heated up to temperatures above 2000°C, it becomes ionic conducting due to a phase transformation from tetragonal to cubic structure. By adding stabilizing scandia (ScSZ) the cubic structure is stabilized even at ambient conditions. Because of this stabilization zirconia becomes a reasonable ionic conductor at SOFC operating temperatures (750-1000°C) and can be used as electrolyte material. Ionic conduction proceeds through oxygen vacancies due to insertion of a di- or trivalent element (Ca2+, Y3+, Sc3+) instead of the tetravalent Zr4+. The lack of positive charge is balanced by free oxygen lattice sites. Through these free sites oxygen can move through the cubic structure. Besides good ionic conductivity, gas tightness of the electrolyte is the most important characteristic the material should have. If the gas tightness of the electrolyte is insufficient, a reaction between oxygen (cathode side) and hydrogen (anode side) may occur. Gas tightness is ensured by sintering the electrolyte at temperatures of approximately 1400°C. Lower temperatures lead to inadequate gas tightness, but pure yittria-stablized zirconia (YSZ) cannot be sintered to high densities below 1400°C. In contrast to the high sintering temperature, which is necessary for the electrolyte, the cathode tolerates only maximum temperatures of approximately 1200°C. If sintered at higher values, the amount of triple phase boundaries reduces drastically due to enhanced sintering. These two facts are the reason for one area of major research and development on electrolyte materials, namely, is the reduction of the sintering temperature of the electrolyte (goal ≤ 1300°C). Decreasing sintering temperatures can be reached by a)

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using a nanosized starting material or b) the use of sintering additives. Additional research and development is focused on the coating technologies for SOFC electrolytes [4].

2.6 Introduction of Zirconia Zirconia has become one of the most industrially important ceramic materials of the present time. The traditional applications of ZrO2 and ZrO2-containing materials are foundry sands and flours, refractory ceramic, and abrasives. Because of its high oxygen ion conduction and high refractive index, it is also used in a wide range of newer applications which include fuel cells, catalysts, oxygen sensors, and jewelry. Zirconias have also been utilized in many mechanical applications. Along with high strength and toughness, zirconia also possesses good hardness, wear resistance, and thermal shock resistance. These properties have led to the use of zirconia-based components in a number of engineering applications such as automobile engine parts, wire drawing dies and cutting tools. The low thermal conductivity together with relatively high coefficiency of thermal expansion makes zirconia a suitable material for thermal barrier coating on metal components [6]. 2.6.1 Crystallographic Structure At atmospheric pressure, pure zirconia (ZrO2) has three crystalline polymorphs with monoclinic, tetragonal and cubic structures. The monoclinic from is stable up to 1170°C when it transforms to the tetragonal modification which remains stable up to 2370°C; from 237°C to the melting point (2680°C), the cubic form is stable. The reverse

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transformations take place on cooling. The phase transformations are martensitic in nature. The monoclinic and tetragonal conversion is accompanied by a contraction in volume of approximately 5% which can cause mechanical failure evident by cracking in the ceramic. The phase transformation can be avoided and the high temperature cubic phase can be stabilized at low temperature by substituting low-valency cations for the zirconium (see Figure 2.2).

Figure 2.2: Phase diagram of Sc2O3-ZrO2 system Cubic ZrO2 has the fluorite structure with the O2- ions arranged in simple cubic packing and half the interstices in this lattice occupied by Zr4+ ions. The substitution of 11

lower-valency cations leads to O2- ion vacancies. The vacancies that stabilized the structure also lead to high mobility in the oxygen sublattice and to behavior as a high-ion conductor. The elements that stabilized the cubic fluorite structure in zirconia include scandium, lanthanides, yttrium, magnesium, calcium, manganese and indium. Scandium has been found to give a material with a higher conductivity, which is particularly valuable at a lower temperature. Scandia stabilized zirconia (ScSZ) is one of the solutions to the problem of stabilizing the cubic form of zirconia [6]. 2.6.2 Application of Scandia Stabilized Zirconia (ScSZ) Fully stabilized zirconia based ceramic materials have several areas of application such as an electrolyte in solid oxide fuel cells (SOFC), oxygen sensors and structural applications due to their high oxygen conductivity in the 800-1000oC temperature range, electrical and mechanical properties. Scandia stabilized zirconia (ScSZ) ceramics have the highest oxygen conductivity among zirconia based materials [7] and, with the trend in reducing the operation temperature of SOFCs to an intermediate temperature (IT) range of 600-800ºC, ScSZ ceramics are very attractive materials for IT SOFCs and catalytic membrane reactors. Important requirements for these applications are reproducibility of the electrical and mechanical properties, high density and a low level of internal flaws. However, most commercial ZrO2-based powders typically need high sintering temperatures above 1400ºC in order to form dense ceramics. High sintering temperatures create a variety of problems such as temperature induced degradation and shape change of materials, interface reactions between zirconia-based ceramics and other components,

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excessive grain growth as well as energy production costs. Lower processing temperatures can limit grain growth to nanocrystalline size which has beneficial effect on the improvement of electrical properties of solid electrolytes [8] due to specific grain boundary conductivity. Recent studies of nanocrystalline scandia stabilized zirconia thin films prepared by sol-gel using a polymer precursor solution showed that the electrical transport of this material can also be enhanced [9]. Therefore the reduction of the sintering temperature towards an SOFC’s operating temperature can improve mechanical and electrical properties and make possible co-firing zirconia-based electrolytes with other SOFC components and significantly lower production costs. Properties such as hardness, fracture toughness and coefficients of thermal expansion (CTEs) are very important parameters for stability and reliability of SOFC operation. Extensive research has shown that a phase transition from cubic to rhombohedral structure of 11mol%Sc2O3-89%ZrO2 occurs when the temperature decreases below 600°C [10, 11]. This phase transformation prevents the direct use of this ceramic in SOFC applications. The aging process of scandia doped zirconia is also accompanied by the formation of a less conductive rhombohedral phase resulting in degradation of ionic conductivity of Sc2O3-ZrO2 electrolytes [12, 13]. Usually the cubic phase can be stabilized over a wide temperature range by substitution of 1 mol% of scandia by another stabilizer such as Yb2O3 [13], Y2O3 [10], Bi2O3 [14], Al2O3 [15], and so on. The addition of a low amount of other oxides usually does not greatly deteriorate the sintering activity and other properties of the resulting powder. It was reported recently that replacement of 1mol% Sc2O3 by CeO2 stabilized cubic phase led to only 50ºC increase in sintering

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temperature [14]. Also it was found recently that scandia-ceria doped zirconia ceramics have a very high ionic conductivity (0.151 S/cm at 800oC) [16]. In this experimental work the study of sintering behavior of two commercially available powders with a nominal composition of 10mol%Sc2O3-1mol%CeO2-ZrO2 (ScCeSZ) that can be used to fabricate dense and stable ceramic electrolytes was carried out. The crystal structure, the morphology and phase transitions of powders and ceramics were also investigated. Mechanical properties, such as hardness and fracture toughness, of the Sc2O3-CeO2-ZrO2 ceramics were reported. These results can be further used for the optimal design of SOFC layered structures as well as for determination of their reliability and durability under operational conditions. 2.6.3 Different Electrolyte Materials Table 2.2 briefly describes all types of commercially available SOFC electrolyte materials currently available in different forms for developing solid oxide fuel (SOFC) [18].

Table 2.2. Commercially available types of electrolyte materials No Name Form 1 Scandia Nano Powder Stabilized Zirconia (10 mole %) Nanopowder Description Scandia Stabilized Zirconia (Sc2O3)0.10(ZrO2)0.90 Nanoscale powder for use as sintering aid, catalyst support, and as a component for mixed conducting anodes and cathodes to enhance catalytic activity Surface area: >100 m2/g Particle size: softly agglomerated

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Table 2.2. (Continued) No Name Form Description 2 Gadolinium Nanopowder Gadolinium Doped Ceria Gd0.10 Ce0.90 O2- Nanoscale Doped Ceria powder for use as sintering aid, catalyst support, and (10% Gd) as a component for mixed conducting anodes and Nanopowder cathodes to enhance catalytic activity. Surface area: >100 m2/g Primary crystallite size: 5-10 nanometers Secondary particle size: softly aggolomerated 3 Gadolinium Doped Ceria (10% Gd) Aqueous Suspension Suspension Gadolinium Doped Ceria (10% Gd) aqueous suspension specially formulated suspension for colloidal deposition and spray coating methods. Suspension is stable for an extended period of time. Surface area: >20-40 m2/g (estimated) Particle size: 50-80 nm Solids loading: 10-15 volume % Gadolinium Doped Ceria Gd0.10 Ce0.90 O2- Powder suitable for tape casting, ink manufacture, pellet pressing and other non-aqueous manufacturing processes. Surface area: >5-8 m2/g Particle Size: d50-0.5 microns

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Gadolinium Doped Ceria (10% Gd) Ceramic Powder

Ceramic Grade Powder

5

Gadolinium Nanopowder Gadolinium Doped Ceria Gd0.20 Ce0.80 O2- Nanoscale Doped Ceria powder for use as sintering aid, catalyst support, and (20% Gd) as a component for mixed conducting anodes and Nanopowder cathodes to enhance catalytic activity. Surface area:>100m2/g Primary crystallite size: 5-10 nanometers Secondary particle size: softly agglomerated Gadolinium Doped Ceria (20% Gd) Ceramic Powder Ceramic Grade Powder Gadolinium Doped Ceria Gd0.20 Ce0.80 O2- Powder suitable for tape casting, ink manufacture, pellet pressing and other non-aqueous manufacturing processes. Surface area: >5-8 m2/g Particle Size: d50-0.5 microns

6

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Table 2.2. (Continued) No Name Form Description 7 Samarium Nanopowder Samarium Doped Ceria Sm0.15 Ce0.85 O2- Nanoscale Doped Ceria powder for use as sintering aid, catalyst support, (15% Sm) and as a component for mixed conducting anodes Nanopowder and cathodes to enhance catalytic activity. Surface area: >100 m2/g Particle size: softly agglomerated 8 Samarium Ceramic Doped Ceria Grade (15% Sm) Powder Ceramic Powder YttriaStabilized Zirconia 3 mole% Ceramic Powder YSZ 8 mole% Engineered Coating Ceramic Grade Powder Samarium Doped Ceria Sm0.15 Ce0.85 O2- Powder suitable for tape casting, ink manufacture, pellet pressing and other non- aqueous manufacturing processes. Surface area: >5-8 m2/g Particle Size: d50-0.5 microns Ytrria Stabilized Zirconia (Y2O3)0.03 (ZrO2)0.97 Partially stabilized zirconia powder suitable for pellet pressing, injection molding and aqueous manufacturing processes. Can be calcined for use in non-aqueous applications. Surface area: >13-19 m2/g Particle Size: d50-0.5 microns Yttria Stabilized Zirconia (8% Yttria) Aqueous suspension for colloidal deposition, dip coating and spray coating methods. Has engineered particle sizes to match shrinkage to typical anode materials. Can be engineered to match the shrinkage of cathode supports. Suspension is stable for an extended period of time. Surface area: Engineered Particle Size: Engineered Solid loading: 10-15 volume %

9

10

Suspension

11

YttriaNanopowder Ytrria Stabilized Zirconia (Y2O3)0.08 (ZrO2)0.92 Stabilized Nanoscale powder for use as sintering aid, catalyst Zirconia 8 support, and as a component for mixed conducting mole% anodes and cathodes to enhance catalytic activity. Nanopowder Surface area: >100 m2/g Particle size: softly agglomerated

16

Table 2.2. (Continued) No Name 12 YttriaStabilized Zirconia 8 mole% Aqueous Suspens Form Suspension Description Yttria Stabilized Zirconia (8% Yttria) Aqueous Suspension specially formulated suspension for colloidal deposition and spray coating methods. Suspension is stable for an extended period of time. Surface area: 20-40 m2/g (estimated) Particle Size: 50-80 nm Solid loading: 10-15 volume % Yttria Stabilized Zirconia (Y2O3)0.08 (ZrO2)0.92 Full stabilized powder suitable for tape casting, ink manufacture, pellet pressing and other non-aqueous manufacturing processes. Surface area: 4-8 m2/g Particle Size: d50-0.5 microns

13

YttriaStabilized Zirconia 8 mole% Ceramic Powder

Ceramic Grade Powder

17

CHAPTER 3 EXPERIMENTAL METHODS AND CHARACTERIZATION

3.1 Materials Two different powders with nominal composition 10mol%Sc2O3-1mol%CeO2ZrO2 were studied in this research work: • • Praxair Surface Technology, Specialty Ceramics, USA Daiichi Kigenso Kagaku Kogyo Co., Ltd , Japan (DKKK, Japan)

3.2. Fabrication of Ceramic 3.2.1 Powder Compaction Powder compaction was performed using the uniaxial pressing method. Uniaxial pressing involves the compaction of powder into a rigid die by applying pressure in a single axial direction through a rigid punch or piston. The presses were hydraulic and needed manual operation. A 31mm steel die was used for the preparation of all samples. The setup consisted of a steel die, a steel punch and two plugs. The powder was poured in between the two plugs. The steel punch was placed on top of the second plug, and the pressure was applied. The applied force was 15000N. The calculation is as follows:

Pr essure, P =

Applied Force( F ) Area( A)

∏d2 Area, A = = 1.1697 in2 4

18

Applies Force, F = 15000N = 3372.134 lb
Pr essure, P = 3372.134 1.1697

= 2882.92 Psi
3.2.2 Sintering

Sintering converts a compacted powder into a denser structure of crystallites joined to one another by grain boundaries. Grain boundaries vary in thickness from about 100µm to over 1µm. Samples were numbered based on the company name for all different temperatures as listed in Table 3.1. They may consist of crystalline or vitreous second phases, or may simply be a disordered form of the major phase because of the differing lattice orientations in neighboring grains. They impart strength to the body,

Table 3.1. Name of sample based on powder and sintering temperature No of Samples Sintering Temperature (°C) 1100 1200 1300 1400 1500 1600 1100 1200 1300 1400 1500 1600 Name (J-Japan, PPraxair) J1100 J1200 J1300 J1400 J1500 J1600 P1100 P1200 P1300 P1400 P1500 P1600

1 2 3 4 5 6 7 8 9 10 11 12

19

typically in the range 70-350 MPa (cross-breaking). Grain boundaries are generally not as dense as the crystals [6]. The sintering process of two uniaxially pressed powders was performed in a high quality, high temperature Micropyretics Heaters International (MHI) furnace. The sintering temperature was from 1100-1600°C in air. The sintering time was 2 hours and heating and cooling rates were 10°/minutes.

3.3 Sample Preparation

Sample preparation is one of the most important steps during the various experimental testing of ceramic materials. This process involves several steps to produce a smooth surface for analysis. The main objective is to obtain an absolutely flat, highly polished, and clean sample. This process was completed basically in two different steps as follows: • • Polishing Etching.

Polishing

This is an integral part of most types of testing. The best and the fastest polishing to produce flat and smooth surfaces was performed with the lapping tool typically used for SEM, AFM and TEM sample preparation and polishing by diamond grinding paper with a grain size from 30 µm to 0.5 µm. The following steps were taken during the polishing of the samples: • The ceramic was cut to size using a diamond saw.

20

• •

The sample was mounted on a lapping stage using wax and heat. Diamond paper was placed on a clean wet glass plate and air bubbles were removed from beneath the paper.

The lapping tool with the sample was slid under the self-weight of the lapping tool on 30 micron diamond paper using water for lubrication to obtain a fully flat surface.

The sample was flipped over to begin final polishing on the other side Figure 3.1 represents the polished surface obtained by different grit sized diamond

paper.

Figure 3.1: Illustration of changes in the surface morphology after polishing on diamond paper with grits 3µm, 1 µm, and .5µm (from left to right)

Etching

Etching is performed to make visible the grain boundaries for study of grain size in material and granular microstructure. All samples were polished up to 1 micron on diamond paper and were etched thermally in air for 30 minutes at 1300°C regardless of 21

the sintering temperature. A Thermcraft Incorporated Furnace model#TSL-2-0-6-1SJ7409/1A was used for thermal annealing.

3.4 Study of Mechanical Properties

Mechanical properties like densities, fracture toughness and hardness were experimentally studied for samples made at different sintering temperatures.
3.4.1 Density and Porosity Analysis

Density is the quotient of the mass and volume. The unit is g/cm3 which is basically adopted in lab work. Density determination is frequently performed by Archimedes’ principle which states that every solid body immersed in a fluid apparently loses weight by an amount equal to that of the fluid it displaces. The densities of sintered specimens were determined here by the standard Archimedes’ method in acetone. For each sample 12 readings were taken. The apparatus used for this purpose was Mettler Toledo of Model: AX105 Delta Range(R). The procedures adopted to calculate density were as follows: • A balance with all necessary setup (draft shield elements, bracket, equalizing washer and platform, thermometer) for density measurements was prepared. • • • The balance was initialized to zero. The dry weight of a sample was taken in air. The sample was immersed in acetone and the reading was taken after stabilization of number displayed on a screen of the balance. • For porous samples wet weight was taken.

22

The density ρ was calculated from the two weighings as follows

Density : ρ =
Volume
where, ρ = Density of sample A = Weight of sample

A (ρ 0− ρ L ) + ρ L A−B
A − B ρ o − ρ

:V = α

L

B = Weight of sample in the auxiliary liquid

ρ L = Air density (0.0012 g/cm3)
ρ 0 = Density of the auxiliary liquid

α = Balance correction factor (0.99985), takes air buoyancy of the adjustment
weight into account [19].
Theoretical Density

Theoretical density is based on crystal structure and molar mass of material, the formula used for theoretical density calculation is:

Theoretical Density : ρ =

Atomic Weight ( M * N ) N A * a sin α * b sin β * c sin γ

where, M = Molar mass, N = Atomic Number, NA = Avogadro’s number, a, b, c are lattice parameters, obtained from XRD experiments, Angle α, β, and γ = 90°, The procedures and calculation are detailed in Chapter 4 [20].

23

3.4.2 Indentation Techniques for Hardness and Fracture Toughness Analysis 3.4.2.1 Nanonindentation

Indentation techniques are used as effective means of measuring the hardness of bulk materials. Nanoindentation is a simple method consisting of pressing a material of known mechanical properties such as hardness and elastic modulus into a material whose properties are to be estimated. The material is subjected to load by pressing an indenter through the material and the images of the indent impressions are captured. Hardness of the material is defined as the mean pressure the material can support under load and is calculated as H = P/A, where P is the applied load and A is the projected contact area of the impression. Elastic modulus is a measure of the recovery of the material during unloading and is an indicator of its elastic properties. Conventional indentation techniques involve optical imaging of the indentations for calculation of the contact area. Microindentation testing carried out using Rockwell and Vickers’ hardness tests involve high loads and are applicable for bulk materials. Nanoindentation, a recently developed technique, involves indentation depths in the order of nanometers and loads of few millinewtons. Nanoindentation, also known as depth-sensing indentation, is a relatively new testing technique that involves a significant expansion on the capabilities of conventional hardness testing. Nanoindenters employ high-resolution instrumentation to continuously control and monitor the loads and displacements of an indenter that is driven into and withdrawn from the material being tested [22-28, 29]. Depending on the specifications of the equipment, loads as small as 1 nN and displacements as small as 0.1nm (1 Å) can be

24

measured [30]. The first major contribution in indentation experiments was made by I.N. Sneddon (Sneddon, 1965). Sneddon studied the relationships between the load, displacement and contact area for different indenter geometries and derived with an equation, P = αhm, where P is the indenter load, h is the elastic displacement of the indenter and α and m are constants [31]. Values of the exponent m for some common punch geometries are m=1 for flat cylinders, m=2 for paraboloids of revolution [22]. Nanoindentation technique has various advantages compared to traditional micro indentation techniques. The load-displacement data from nanoindentation contains an enormous amount of information and techniques are developed for characterizing a variety of mechanical properties such as hardness, stiffness and elastic modulus. Methods have also been developed for evaluating the yield stress and strain-hardening characteristics of materials [32-34]. Damping and internal friction characteristics such as storage and loss modulus, activation energy and stress exponent for creep are also being evaluated from the nanoindentation data [35-37]. Fracture toughness is also being estimated from the optical measurements of the cracks that have formed at the corners of indent impressions made with sharp indenters [38-39]. Tabor used hardened spherical indenters to perform indentation tests on metals [21]. Stillwell and Tabor noticed that at least in metals, the impression formed by the spherical indenter is still spherical with a slightly larger radius than the indenter, and the impression formed by a conical indenter is still conical with a large included tip angle. Tabor showed that the shape of the entire unloading curve and the total amount of recovered displacement could be accurately related to the elastic modulus and the size of

25

the impression for both spherical and conical indenters [40]. It is also notable that the diameter of the contact impression on the surface formed by the conical indenter does not recover during unloading and only the depth recovers. The indenter is loaded and unloaded a few times before the load displacement behavior becomes perfectly reversible. The plasticity can be dealt with by taking into account the shape of the perturbed surface in the analysis of the elastic unloading curve. Therefore, the shape of the unloading curve and the recovered displacement characterizes the elastic modulus of the material. Hardness and elastic modulus are the most frequently measured mechanical properties using nanoindentation. A schematic of the indentation process for an axisymmetrical indenter of arbitrary profile is shown in Figure 3.2. As the indenter is pressed into the material, both elastic and plastic deformation processes occur, creating an impression that conforms to the shape of the indenter of some contact depth, hc. The

Figure 3.2: A schematic representation of the indentation process showing various parameters involved in the analysis.

26

radius of the contact circle is a. As the indenter is withdrawn, only the elastic portion of the displacement is recovered and it distinguishes the elastic properties of the material from its plastic properties [30]. Here hs is the displacement of the surface at the perimeter of the contact; h is the total indentation depth; hf is the final depth of the residual hardness impression. Indentation load versus displacement relationship is shown schematically in Figure 3.3.

Figure 3.3: Nanoindentation load-displacement relationship

The critical parameters used in the calculation of hardness and elastic modulus are the peak load (Pmax), the maximum indentation depth (hmax), the residual or final indentation depth after unloading (hf) and the initial unloading stiffness (S = dP/dh). S is also known as the elastic contact stiffness, or simply contact stiffness. Hardness, the mean pressure a material can withstand, is calculated using Equation 1,

H =

P A
27

(1)

where P is the load and A is the projected contact area at that load. The hardness determined by dividing the applied load by the projected contact area under the load should not be confused with the traditional definition of hardness, the load divided by the projected area of contact of the residual hardness impression. These two definitions yield similar values for hardness when the deformation process is mainly dominated by a plastic region and a fully plastic permanent hardness impression is formed. When the contact is predominantly elastic, they exhibit different values for hardness since the residual contact area is very small for a purely elastic contact, which results in infinite hardness based on the traditional hardness definition [30]. This phenomenon plays a crucial role while indenting materials with very sharp indenters at small indentation depths. In these conditions, traditional definition of hardness yields a higher value than that calculated using Equation 2. Elastic modulus of the test material, E, is calculated using the equation, 1 1 − ν 2 1 − ν i2 = + Er E Ei (2)

where Er is the reduced elastic modulus, E and ν are the elastic modulus and Poisson’s ratio of the test material, and Ei and νi are the elastic modulus and Poisson’s ratio of the indenter, respectively, and for a diamond indenter these values are 1141 GPa and 0.07 respectively. Reduced modulus is used to account for the elastic displacements that occur in both the indenter and the sample. Er is related to the contact stiffness by the equation,
Er =

π S 2β A

(3)

28

where S is the contact stiffness, A is the projected contact area and β is a constant that depends on the geometry of the indenter. This equation is derived from elastic contact theory [41-42] and holds good for any indenter that can be described as a body of revolution of smooth function [43]. Though the equation formally applies only to circular contacts, it has been shown that it works well for different geometries provided a different value of β is used [44-45]. For indenters with square cross sections β = 1.012; for triangular cross sections like the Berkovich and cube-corner indenters, β = 1.034. It has been shown recently that yet another correction factor has to be added to the equation [42, 46-49]. The principal difference between conventional hardness testing techniques and the nanoindentation technique is the manner in which the contact area is determined. Instead of imaging of the indent impressions, the contact area is estimated from the indentation load-displacement data. Oliver and Pharr [22] developed a method by fitting the unloading portion of the load-displacement data to the power-law relation
P = A(h − h f ) m

(4)

where A and m are constants determined by a least squares fitting procedure; hf is the final displacement after complete unloading determined from curve fit. The initial unloading slope is found by differentiating the equation and evaluating the derivative at the peak load and displacement. Contact stiffness is obtained by differentiating Equation (4) and evaluating the value at the maximum indentation depth. The contact depth, hc, is estimated using, the expression,

29

hc = h − ε

P S

(5)

where ε is a constant that depends on the indenter geometry. For spherical indenters ε = 0.75, for conical indenters ε = 0.72 and for Berkovich indenters ε = 0.75. Equation (5) does not account for pile-up formed during indentation because it is assumed that the contact is perfectly elastic and only sink-in occurs continuously [30]. The contact area is calculated as a function of the contact depth, hc, and is written as: A (hc) = 24.5 hc2 for a perfect Berkovich indenter. Taking into consideration the tip blunting effects, the modified area function is written as,
1 1 1 1 1 1 1 1 A(hc ) = 24.5hc2 + C1hc + C 2 hc / 2 + C 3 hc / 4 + C 4 hc / 8 + C 5 hc / 16 + C 6 hc / 32 + C 7 hc / 64 + C8 hc / 128

(6)

(7) where C1 through C8 are constants. The area function is determined by making a series of indentations at various depths in a calibration sample of well-known elastic properties. The basic assumption in this process is that the elastic modulus is independent of the indentation depth. It is also imperative that there is no pile-up. Fused silica is the widely accepted calibration sample. The machine compliance is also calculated during the calibration procedure [22]. Correcting for machine compliance, the load-displacement data are reduced and used to obtain the contact stiffness (S) and the contact depths (hc). For fused silica material, E = 72 GPa; ν = 0.17 and for diamond indenter, E = 1141 GPa; ν = 0.07. The contact area, determined using Equation (6), is plotted against contact depth, hc, and is fitted according to a polynomial order. A weighted fitting procedure

30

ensures that data from all depths are given equal importance. The area function coefficients determined from the fit are used in further calculations.
3.4.2.2 Microindentation

The resistance to indentation or deformation of material is known as its hardness. It is one of the most frequently measured properties of a ceramic. There are many hardness scales and methods of measurements to characterize resistance to deformation, densification, and fracture. In fact, many ceramic specifications list minimum hardness requirements. For example, a new ASTM zirconia’s specification for surgical implants, F 1873-98, stipulates that Vickers hardness (HV) shall be no less than 11.8 GPa (1200 kg/ mm2) at a load of 9.8 N (1 kg). Although measuring and interpreting ceramic hardness should be routine, pitfalls, controversies, and surprises abound. The Vickers hardness test was used for hardness and fracture toughness measurements in this research work. In most engineering and characterization applications, approximately 60% of worldwide published ceramic hardness values are Vickers, with loads typically in the range of a few newtons to 9.8 N (1 kg) and occasional data for soft or high-toughness ceramics as high as 98 N (10 kg). Knoop hardness is more frequently used for glass, glass ceramics, and ceramic white wares. About 35% are Knoop with loads from as low as 0.98 N (100 g) to 19.6 N (2 kg). Rockwell hardness are about 5% [21]. For research purposes, Vickers, Knoop, and Berkovich (triangular pyramid) indenters are customary; Rockwell and Brinell indenters are rarely suitable for ceramics research. Measurements were carried out on conventional microhardness machines with Vickers diamond indenters.

31

A LECO Microhardness testing Machine Model: M-400-H1/H2/H3 was used for indentations. The indentions loads were 100, 200, 300, 500, 1000g. At each load 20 indents were created. The following procedures were undertaken for indentations: • A highly polished flat sample was placed on stage at a right location of microhardness testing machine. • The sample was focused and adjusted to create 20 indents at each load from 100, 200, 300, 500, 1000g. • A loaded indentor was lowered against a polished flat surface of the sample for a specific load time of 30 seconds and retracted automatically afterwards. • During loading, the indentor penetrated into the ceramic and, on retracting, left a permanent pyramidal indentation. • A high quality impression image was collected on an Optical Microscope adjusting the indent on the center of the lens to avoid possible errors of focusing on Zeiss Axiovert 10 at magnification 500x (1000, 500g) and 1000x (100, 200, 300g). • Diagonal lengths of the impression were measured by using Image Pro-Plus software for Vickers hardness. • Crack lengths were measured for fracture toughness analysis.

A typical impression is shown in Figure 3.4.

32

Figure 3.4: Typical images collected at 500x on optical microscope for hardness study

The Vickers hardness is calculated by using the following formula
 F  VHN = 1.8544  2  GPa D  where, F = Load in Kg, D = average diagonal length in µm, VH = kg/mm2 (1 kgf/mm2 = 9.81 MPa.) Fracture toughness, K1C, is a measure of a ceramic part’s resistance to fracture starting from a pre-existing crack. It is one of the most important properties of material for virtually all design applications. If the material has a large value of fracture toughness, it will undergo ductile fracture. Brittle fracture is a characteristic of materials with a low fracture toughness value. There are four different types of fracture toughness,

33

KC, K1C, K11C, and K111C. KC is the fracture toughness of the sample, which is in a state plane stress. K1C, K11C, and K111C are the fracture toughness of material under three different modes of fracture, mode I, mode II, mode III, respectively. Ceramic materials have a much lower K1C value than the metals. The low K1C value shows that ceramic materials are very susceptible to cracks and undergo brittle fracture, whereas the metals undergo ductile fracture. Thus for this study, the fracture toughness, K1C is considered. For fracture toughness calculation Young’s modulus was obtained from nanoindentation data 230GPa and 210GPa for DKKK, Japan and Praxair samples respectively. The equations used for fracture toughness calculation is:
K 1C E = 0.016   H
1/ 2

P C 3/ 2

where, E = Young’s modulus (230/210GPa), H = Vickers hardness (GPa), F = Indentation load (mN), C = Crack length (µm). Figure 3.5 shows diagonals and cracks taken for measurements. Young’s modulus was obtained by nanoindentation technique. The Young’s modulus value for the DKKK based ceramic sample sintered at 1600°C was 230GPa. The same value for the Praxair based ceramic sintered at 1600°C was 210GPa. Both values are in good agreement with the literature review of this experimental work.

34

D

C

(a)

.
(b) Figure 3.5: (a) Schematic figure having crack and indent length; (b) Image collected at 1000x on optical microscope (Indentation load is 200g)

35

3.5 Microstructure Characterization

Microstructure observations of the Scandia Stabilized Zirconia (ScSZ) were performed on the thermally etched samples of DKKK, Japan and Praxair materials using a scanning electron microscope (SEM) Model: Hitachi S3000N and atomic force microscope (AFM) respectively. A brief description of both microscopes and the technique adopted for the collection of images follows. Scanning Electron Microscope The SEM uses electrons rather than light to form an image. There are many advantages to using the SEM instead of a light microscope. The SEM has a large depth of field, which allows a large amount of the sample to be in focus at one time. The SEM also produces images of high resolution, which means that closely spaced features can be examined at a high magnification. Preparation of the samples is relatively easy, since most SEMs only require the sample to be conductive. The combination of higher magnification, larger depth of focus, greater resolution, and ease of sample observation makes the SEM one of the most heavily used instruments in materials research today. The scanning electron microscope (SEM) has a very fine “probe” of electrons with energies of up to 40 keV focused at the surface of the specimen in the microscope and scanned across it in a “raster” or pattern of parallel lines. A number of phenomena occur at the surface under electron impact: most important for scanning microscopy is the emission of secondary electrons with energies of a few tens of eV and re-emission or reflection of the high-energy backscattered electrons from the primary beam.

36

Backscattered Electron Imaging In this particular research backscattered electron imaging was used to collect images for microstructure characterization. The intensity of emission of both secondary and backscattered electrons is very sensitive to the angle at which the electron beam strikes the surface, that is, to topographical features on the specimen. When the electron beam strikes the sample some of the electrons will interact with the nucleus of the atom. The negatively-charged electron will be attracted to the positive nucleus but if the angle is just right instead of being captured by the "gravitational pull" of the nucleus, it will circle the nucleus and come back out of the sample without slowing down. These electrons are called backscattered electrons because they come back out of the sample. Because they are moving so fast, they travel in straight lines. In order to form an image with BSE (backscattered electrons), a detector is placed in their path. When they hit the detector a signal is produced which is used to form the image. Different elements have different size of nuclei. As the size of the atom nucleus increases, the number of BSE increases. Thus, BSE can be used to derive an image that shows the different elements present in a sample. A typical image collected at SEM is shown in Figure 3.6. The magnification of this microscope is the ratio between the dimensions of the final image display and the field scanned on the specimen. Usually, a magnification range of SEM is between 10 to 200000X and the resolution (resolving power) is between 4 to 10 nm (40 - 100 Angstroms).

37

Figure 3.6: Typical SEM images for grain size study

There are several types of SEMs designed for specific purposes ranging from routine morphological and microstructural studies of materials, to high-speed compositional analyses. Atomic Force Microscope The AFM is also called the scanning force microscope (SFM) and was invented in 1986 by Binnig, Quate and Gerber. The AFM utilizes a sharp probe moving over the surface of a sample in a raster scan. The probe is a tip on the end of a cantilever which bends in response to the force between the tip and the sample. Figure 3.7 illustrates the working of the AFM. As the cantilever flexes, the light from the laser is reflected onto the

38

split photo-diode. By measuring the difference signal (A-B), changes in the bending of the cantilever can be measured.

Figure 3.7: AFM working principle

The interaction force between the tip and the sample can be found as the cantilever obeys Hooke's Law for small displacements. The movement of the tip or sample is performed by an extremely precise positioning device made from piezo-electric ceramics, most often in the form of a tube scanner. The scanner is capable of subangstrom resolution in x-, y- and z-directions. The z-axis is conventionally perpendicular to the sample.

39

The AFM operates by measuring attractive or repulsive forces between a tip and the sample. In its repulsive contact mode, the instrument lightly touches a tip at the end of a cantilever to the sample. As a raster-scan drags the tip over the sample, some sort of detection apparatus measures the vertical deflection of the cantilever, which indicates the local sample height. Thus, in contact mode, the AFM measures hard-sphere repulsion forces between the tip and the sample. In non-contact mode, the tip does not touch the sample and the AFM derives topographic images from measurements of attractive forces. AFMs can achieve a resolution of 10 pm, and unlike electron microscopes, can image samples in air and under liquids. Feedback operation The AFM can be operated in two principal modes: • • with feedback control without feedback control. Once the electronic feedback is switched on, then the positioning piezo which is moving the sample or tip up and down can respond to any changes in force which are detected, and alter the tip-sample separation to restore the force to a predetermined value. This mode of operation is known as constant force mode, and usually enables a fairly faithful topographical image to be obtained. When the feedback electronics are switched off, then the microscope is said to be operating in constant height or deflection mode. This is particularly useful for imaging

40

very flat samples at high resolution. The following procedures were considered to obtain high quality images for grain size study of all samples: • The controller and the main computer were turned on and the SPM cockpit software was launched. • The close-contact EZ-Mode was selected and the corresponding configuration file was loaded. • The cantilever close-contact mode operation was installed in the AFM scanner head. • The cantilever tip was aligned so that the laser light was projected from the back of the cantilever onto the photodetector. • The AFM scanner was moved down and the surface was focused to obtain the high quality image. • The tip approach was carried out and a specific area on the sample was selected to obtain better quality images with distinct grain boundaries. • • • The probe was retracted from the sample. The above procedure was repeated with remaining samples. Grain size measurements were performed by the intersect method of Image ProPlus software using Scanning Electron Microscope (SEM) and Atomic Force Microscope (AFM) images (see Figure 3.8).

41

(a)

(b) Figure 3.8: (a) Typical AFM images for grain size study; (b) Grain size and cavitations measurements

42

The measurements were performed, collecting data by moving the red lines from top to bottom at 10 locations in the same images. Almost 20 grain intersects per line were collected (see Figure 3.8 (b)). For each sample, the data were collected from 4/5 images which gave 800-1000 measurements. Cavities density was collected using the threshold method as shown in Figure 8.3 (b).

3.6 XRD Measurements

The X-ray diffraction experiment is mostly performed to characterize crystallographic structure and chemical composition of the materials. In the present work, the XRD experiment was used for phase identification of ceramic sintered at different temperature, and calculation of coefficient of thermal expansion by obtaining lattice parameters. The experiments were performed using the AXS-Bruker D8 Discover diffractometer with Cu Kα X-ray radiation source and Eurlean cradle. Parallel beam optics was used to minimize errors associated with sample displacement and surface roughness. The Anton Paar H-900 high temperature stage mounted on the XYZpositioning stage was used for measurements at temperatures up to 900ºC. The zero point of detector was <0.004º, and sample height was controlled with accuracy of 0.005 mm. Ceramic samples were polished down to 0.5 mm thick tablet form with final grit size 0.05 µm to avoid stress induced effects on XRD data. Powder samples for high temperature measurements were deposited on Si(100) substrate in the slurry form using colloidal silver paste. Silver matrix has been used for

43

temperature calibration. Diffraction patterns were collected at 25ºC and then between 100 and 800ºC in 100ºC intervals for CTE measurements and 10°C for phase transition analysis. The heating rate was 10 ºC/min and the waiting time was 30 minutes before XRD scans at every temperature for temperature stabilization. High temperature XRD scans were performed in the interval 2θ of 28-66º with integration time 5s/point and step 0.01º. The waiting time for temperature stabilization before the XRD scan at each temperature was 30 minutes.
3.6.1 Coefficient of Thermal Expansion (CTE)

When heat is given to a body, it normally expands. The coefficient of thermal expansion is the relative change in a given dimension when the body is heated. Thermal expansion of the crystalline phase means a change in the cell lattice parameters with the temperature variation. Increase of the lattice parameter in the cubic phase with temperature increase leads to shifting of diffraction peaks towards lower angles. An example of this behavior is shown in Figure 3.9 for the P1600 powdered sample. To determine coefficient of thermal expansion (CTE), cell parameters at every temperature were obtained by Retvield refinement of at least 5 peaks in XRD data using Full-Proof Software. The CTE is defined by the following formula:

CTE =

1 dL L dT

where, L is original length, dL is change in length and dT is temperature difference. This demonstrates the linear expansion of solid material. The cubical or volume expansivities

44

of solids are three times the linear expansivity. The unit of linear CTE is /°C or mm/mm/°C.

Figure 3.9: Temperature dependent shifting of XRD peaks positions

The expansivities of the majority of solid materials increase with increasing temperature and can be fitted in three different ways: 1) Model-I:CTE- constant

CTE = b o
By substitution and integration,

45

ln L T = b o * T + const .
2) Model-II: CTE-varying linearly

CTE = b o + b1T
By substitution and integration,

ln L T = b o * T +
3) Model-III: CTE - varying qudratically

b1 T 2

2

+ const .

CTE = b o + b1T + b 2 T
By substitution and integration,

2

ln L T = b o * T +

b1 T 2

2

+

b2 T 3

3

+ const .

For all three models, coefficients bo, b1, b2 were obtained through curve fitting log (LT) by linear, quadratic, and cubic functions respectively. An example of this fitting is presented in Figure 3.10. Analysis of fitting residuals can help to select the appropriate model for CTE (see Figure 3.11). By substituting value of coefficients and given temperature, the CTE was calculated. In the case of the P1600 powdered sample dependence Ln (LT) is not linear and the best fit is achieved by linear and quadratic models. In cases like this, selection between linear and quadratic models is difficult because residuals are similar. Despite the constant and the linear models, the quadratic model is the better fitting (less residuals) model. The accuracy of coefficients of fitting was used for selection of the appropriate model. In the case of the P1600 powdered

46

sample (see Figures 3.9, 3.10, 3.11) for the linear model b0 = (7.14±0.39)×10-6 and b1=(4.61±0.53)×10-9, while for the quadratic model b0= (5.83±2.33)×10-6, b1=(8.47±6.75)×10-9 and b2=-(2.68±4.67)×10-12. It is evident that statistical accuracy of coefficients for the linear model is significantly better than for the quadratic model. Therefore, the best model was decided based on analysis of residuals, overall standard deviations and standard errors of parameters. To compare our data with the known value of CTE of cubic zirconia (10.5×10-6 deg-1), we have used the results of a constant model.

1.636 1.635 1.634 1.633

Constant Linear Qudratic

Ln(LT)

1.632 1.631 1.630 1.629 1.628 300 400 500 600 700 800 900 1000 1100

Temperature (K)

Figure 3.10: Constant, linear and quadratic fitting with temperature vs. log (LT) (P1600-powder)

47

Residuals
0.00015

Constant Linear Quadratic

0.00010

0.00005

Delta

0.00000

-0.00005

-0.00010

-0.00015 300 400 500 600 700 800 900 1000 1100

Temperature, K

Figure 3.11: Instrumentally set temperature vs. residuals (P1600-powder)

3.6.1.1 Temperature Calibration It is known that the coefficient of thermal expansion is temperature dependent parameters. The actual value of temperature is essential for the accurate calculation of coefficient of thermal expansion. Based on literature reviews, the CTE at known temperature of silver was taken as reference value for temperature calibration. By back substitution and polynomial fitting using Microsoft excel and the Origin program, the coefficient of polynomial equation was obtained for known temperature, and for each set temperature the actual temperature was calculated as shown in Figure 3.12 and Table 3.3. 48

1100 1000 900

Actual Temperature (K)

800 700 600 500 400 300 200 200 400 600 800 1000 1200

Set Tem perature (K)

Figure 3.12: Polynomial fitting of calibrated temperature vs. instrumentally set temperature

Table 3.2. Calculation of actual temperature from set temperature Set Temperature(°C) 100 150 200 250 300 350 400 450 500 550 600 650 700 800 Set Temperature(K) 373 423 473 523 573 623 673 723 773 823 873 923 973 1073 Cell Parameters(Å) 4.09107 4.09618 4.10045 4.10481 4.10911 4.11372 4.11819 4.12312 4.12779 4.13246 4.13728 4.14271 4.14754 4.15823 Calibrated Temperature(K) 356.8 420.2 471.9 523.4 573.0 624.9 674.1 727.0 776.0 823.8 872.0 925.1 971.1 1069.6

49

CHAPTER 4 RESULTS AND DISCUSSION

4.1 Characterization of Praxair and DKKK powders

Two different powders with nominal composition 10mol%Sc2O3-1mol%CeO2ZrO2 were studied in this research work: • • Praxair Surface Technology, Specialty Ceramics, USA Daiichi Kigenso Kagaku Kogyo Co., Ltd , Japan (DKKK, Japan)

4.1.1 Theoretical Dnsities and Actual Composition

The actual composition of powders (obtained by Inductively Coupled Plasma Mass Spectroscopy at the University of St. Andrews, UK by J. Irvine and C. Savanie) and theoretical densities were calculated using the lattice parameter obtained by XRD experiments for both powders (see Tables 4.1, 4.2, 4.3): DKKK Powder The actual composition of DKKK powder is 10.07% Sc2O3 + 0.92% HfO2 + 1.03% CeO2 + 1.4% TiO2 + 86.58% ZrO2. Praxair Powder The actual composition of Praxair Powder is 15% Sc2O3 +0.05% HfO2 + 0.4% CeO2 + 2% TiO2 + 82.55%ZrO2

50

Table 4.1. Theoretical density from the actual composition of DKKK powder
# of Sc,Hf, Ce,Ti, Zr Atomic Mass of Oxygen # of Oxygen Atom Mass per Metal Atom Contents of Each Compd. # of Moles Normalization Oxygen Atomic Weight

Compd.

Weight Mass

Sc2O3
0.14603 0.00437 0.00598 0.01752 0.70265 0.87655 0.00683 0.01999 0.80160 0.00499 0.16659

44.96 178.49 140.12 47.9 91.22 1 1 16 2 2 1 16 2 0.4 1 16 2 0.05

44.96

2

16

3

15

0.24989 0.00997 0.01365 0.03998 1.60321

29.960 3.560 3.826 3.830 292.48

HfO2

178.49

CeO2

140.12

TiO2

47.9

ZrO2

91.22

1
1.91670 122.67 456.34

51

6.032*10 5.09*10-8cm
5.74 gm/cm2

16 2 82.55 Total Moles Oxygen Sum Avogadro’s Number Lattice Parameters Theoretical Density

23

Table 4.2. Theoretical density from the actual composition of Praxair powder
# of Sc, Hf, Ce, Ti, Zr Atomic Mass of Oxygen # of Oxygen Atom Mass per Metal Atom Contents of Each Compd. # of Moles Normalization Oxygen Atomic Weight

Compd.

Weight Mass

Sc2O3
0.2175 0.0002 0.0023 0.0250 0.6699 0.00025 0.00253 0.0273 0.732 0.237

44.96 178.49 140.12 47.9 91.22 0.9150 1 1 1 16 2 0.4 1 16 2 0.05

44.96

2

16

3

15

0.356 0.00052 0.005 0.054 1.464

42.749 0.185 1.423 5.241 267.14

HfO2

178.49

52

CeO2

140.12

TiO2 ZrO2

47.9 91.22

1 1.881 6.032*10 5.09*10-8cm
5.49gm/cm2
23

120.39
437.13

16 2 2 16 2 82.55 Total Moles Oxygen Sum Avogadro’s Number Lattice Parameters Theoretical Density

Table 4.3. Powder characterization Powder Name Actual Compositions Lattice Parameter(Å) Theorectical Density(g/cm3)

Praxair powder

DKKK powder

15% Sc2O3 +0.05% HfO2 + 0.4% CeO2 + 2% TiO2 + 82.55%ZrO2 10.07% Sc2O3 + 0.92% HfO2 + 1.03% CeO2 + 1.4% TiO2 + 86.58% ZrO2

5.09203

5.49

5.09119

5.74

It was found that the DKKK powder has a composition close to the nominal composition while the Praxair powder has an excessive amount of Sc2O3 and a lower amount of CeO2. The HfO2 is considerably less in the Praxair than in the DKKK and there is no big difference in composition of TiO2 in both powders. The c-phases at room temperature has almost identical lattice parameters as shown in Table 4.3. The result shows that the DKKK powder has a composition close to the nominal while the Praxair powder has an excessive amount of Sc2O3 and a lower amount of CeO2. From Figure 4.1,

Figure 4.1: SEM micrographs of powders (a-Praxair, USA) and (b-DKKK, Japan)

53

it is very clear that Praxair powder consists of relatively large 1-2 µm pre-sintered agglomerates of smaller ~300 nm particles and DKKK powder has significantly higher surface area due to relatively uniform nanograins with size 60-100 nm.
4.1.2 XRD of Powders

The XRD study of as-received powders was performed at different temperature ranges RT-600°C as shown in Figure 4.2. It was found that both powders had a mixture of rhombohedra phase (β-phase) and cubic phases (c-phase) at room temperature.

XRD of DKKK as-received powder at different temperatures
I I Cubic Phase (space group Fm-3m) O Rhombohedral Phase (space group R-3) X Silver (space group Fm-3m) as a reference for HT measurements

I

I

X

X

I I

600°C
O OI O I X X I OO X X I OO O

500°C

O O

O I

I OO

I O O O

RT

30

35

40

45

50

55

60

2Theta (degree)
Figure 4.2: XRD pattern at different temperatures

54

The result showed that with the increase of temperature the rhombohedra phase disappeared in the XRD pattern and only remained in a cubic phase at temperatures higher than 500°C. All samples sintered at temperatures higher than 1200°C existed in cubic phase at room temperature. XRD of Praxair The following XRD patterns were obtained for the as-received Praxair powder (see Figure 4.3).

R e tv ie ld r e fin e m e n t o f a s -re c e iv e d P r a x a ir p o w d e r
5000
M u lt i- p h a s e a n a ly s is r e s u lt s :
Ag 8 .5 7 (0 .1 4 )% C u b ic 8 1 .3 7 (0 .6 2 )% R h o m b o h e d r a l 1 0 .0 7 (0 .2 5 )%

4000

C /R h = 8 .0 8

Intensity (counts)

3000

2000
4 9 .5 5 0 .0 5 0 .5 5 1 .0 5 1 .5 5 2 .0

1000

2 T h e ta (d e g r e e )

0

S ilv e r C u b ic R h o m b o h e d ra l

30

40

50

60

70

80

90

100

110

120

2 T h e ta (d e g r e e )

Figure 4.3: XRD pattern of as-received Praxair powder

The XRD pattern showed that at room temperature, the powder has both rhombohedra and cubic phases. The cubic to rhombohedral phase ratio for Praxair powder is larger than for DKKK powder. The whole pattern was successfully fitted by three known phases: cubic ScSZ, rhombohedral phase (b-phase) of ScSZ and FCC silver 55

(used as internal standard). This powder has small amounts (~12%) of secondary bphase. The insert above shows details of multi-phase fitting used in the Retvield refinement procedure: small amounts of secondary phase can be traced but quantitative analysis cannot be done correctly. The cubic phase had lattice parameter a=b=c=5.09203(7) Å and the corresponding theoretical density is 5.49 g/cm3 based on the exact content of powder. The apparent crystallite size of c-phase is 68.1 nm, which supports SEM observation: big powder particles consist of agglomerates of smaller grains. XRD of DKKK powder The following XRD patterns were obtained for the as-received DKKK powder (see Figure 4.4).

R e tvie ld re fin e m e n t o f a s -re c e ive d D K K K p o w d e r
10000
M u lt i- p h a s e a n a ly s is r e s u lt s :
Ag 4 .2 4 (0 .0 2 ) % C u b ic 7 5 .6 2 (0 .4 3 ) % R h o m b o h e d ra l 2 0 .1 4 (0 .3 4 ) %

8000

C /R h = 3 .7 5

Intensity (counts)

6000

2 9 .0

2 9 .5

3 0 .0

3 0 .5

3 1 .0

3 1 .5

2 T h e ta (d e g re e )

4000

2000

0

S ilv e r C u b ic R h o m b o h e d ra l

30

40

50

60

2 T h e ta (d e g r e e )

Figure 4.4: XRD pattern of as-received DKKK powder

56

DKKK has also both rhombohedral and cubic phases at room temperature. A phase transition was found at a temperature higher than 500°C and cubic phases recorded at 600°C. Whole patterns can be successfully fitted by three known phases: cubic ScSZ, rhombohedral phase (b-phase) of ScSZ and FCC silver. This powder has also significant amounts (~21%) of secondary β-phase. The insert above shows details of multi-phase fitting used in the Retvield refinement procedure: the amount of secondary phase can be quantitatively analysed. The cubic phase has a lattice parameter a=b=c=5.09119(7) Å and its corresponding theoretical density is 5.74 g/cm3, based on the exact content of powder. The apparent crystallite size of the c-phase is 36.8 nm, which is in good agreement with SEM data. The grain size of DKKK powder is two times smaller than the Praxair powder which can lead to lower sintering temperature.

4.2 Sintering Behavior of Powders

The sintering behaviors of powders were studied by density measurement and microstructure of powder. It was found that the DKKK powder had significantly higher sintering activity and required ~200ºC less sintering temperature than the Praxair powder. The difference in the sintering activity of powders was a result of differences in the powder morphology, chemical composition and levels of impurities present in the DKKK and Praxair powder. It was also observed that the agglomeration had a significant influence in sinteribility of behavior of as-received DKKK and Praxair powder.

57

4.2.1 Density Measurements of ScCeSZ and its Porosity

The density of sintered specimens was determined by the Archimedes’ method. The sintering temperature and density data of ScCeSZ are listed in Table 4.4.

Table 4.4. Density and porosity of sintered samples Sample Sintering Temp(ºC) 1100 1200 1300 1400 1500 1600 1100 1200 1300 1400 1500 1600 Density (g/cm3) 3.31 4.96 5.38 5.52 5.55 5.57 2.72 3.11 3.70 4.57 5.11 5.27 Standard Dev .056 .036 .008 .011 .026 .007 .044 .095 .086 .070 .041 .007 Porosity (%) 42.3% 13.5% Standard Dev 1.0% 0.6%

J1100 J1200 J1300 J1400 J1500 J1600 P1100 P1200 P1300 P1400 P1500 P1600

50.2% 43.2% 32.4% 16.4% 6.6% 3.7%

0.8% 1.7% 1.6% 1.3% 0.7% 0.1%

The results show that the porosity level in ceramics sintered from Praxair and DKKK powders has significant sinteribility difference. It was found that the DKKK powder was significantly more active in the sintering process and required ~200ºC lower sintering temperature to produce ceramics of the same level of porosity as in samples sintered from Praxair powder (Figure 4.1). Amounts of porosity had been calculated using theoretical densities 5.49 and 5.74 g/cm3 of ScCeZrO2 ceramics Praxair and DKKK powder respectively which were estimated using XRD data and the actual chemical composition of the powders. Density data showed that for ceramics produced from

58

DKKK powder, density increases rapidly from 1100 to 1400ºC and at higher temperatures become constant (Table 4.4). Similarly, in the same temperature range, grain size in DKKK ceramics increases significantly from 200 nm to 3 µm and stabilizes at higher temperatures. Even at 1200°C samples produced from DKKK powder are dense enough for polishing, grain size measurements and microhardness testing while samples sintered from Praxair powder at 1400°C are still porous for microindentation. Analysis of grain size with increase of sintering temperature allowed for the conclusion that DKKK powder produces dense ceramics at temperatures higher than 1400ºC while Praxair powder is still not fully sintered at 1600ºC. This conclusion was supported by analysis of fracture surfaces. Figure 4.5 shows typical fracture surfaces of the samples sintered at 1600ºC from Praxair powders and DKKK powder. It is evident that DKKK powder created almost

Figure 4.5: Fracture surfaces of samples P1600-(a) and J1600-(b)

59

fully dense ceramic while the sample produced from the Praxair powder had noticeable amounts of porosity. It should be noticed that thermal etching effects on polished surfaces of samples produced from Praxair powders and DKKK are different (see Figures 4.6-4.8).

Figure 4.6: Grain structure of samples produced from Praxair powder sintered at temperatures 1500ºC (left) and 1600ºC (right)

Figure 4.7: Grain structure of samples produced from DKKK powder sintered at temperatures 1400ºC (left), 1500ºC (middle) and 1600ºC (right)

60

Figure 4.8: SEM images of polished and low angle ion-milled surface of sample P1600 (a) and thermally etched surfaces of samples P1600 (b) and J1600 (c)

Praxair-based samples unusually exhibit significant increase of in-grain cavities due to thermal etching with sintering temperature while the in-grain cavitations level in DKKK-based samples remain constant. SEM analysis reveals that all Praxair-based samples have significant non-uniformity. Even the densest sample, P1600, has highly dense and very porous areas with well distinguished borders between them (see Figure 4.8(a)). The difference in overall density between samples P1400, P1500 and P1600 (Table 4.4) results predominantly from different ratios between dense and porous areas in the samples. Grain structures in Figure 4.8(b) demonstrate a higher density area of sample P1600 while average porosity of the sample is 4.4%. Contrary to samples (Praxair), DKKK-based samples have high uniformity, and the density of in-grain cavities remains constant for samples J1400, J1500 and J1600 (Table 4.4). One can conclude that DKKK powder produces dense ceramics at temperatures higher than 1400ºC while ceramics produced from Praxair powder are still not fully sintered at 1600ºC (see Figures 4.9-4.10).

61

6.0 5.5 5.0

Density (g/ccm )

4.5 4.0 3.5 3.0 2.5 2.0 1100 1200 1300 1400 1500 1600

Praxair Japan

Temperature (C)

Figure 4.9: The dependence of density on sintering temperatures

45 40 35
Porosity Level (%)

P ra xair (I) D KK K (II)

30 25 20 15 10 5 0 1100 1200 1300 1400 1500
0

P orous

1600

Sintering T em perature ( C )

Figure 4.10: Porosity level vs. sintering temperature

62

The difference in sintering activity of Praxair and DKKK powders is a result of differences in powder morphology, chemical composition and impurities. Praxair powder consists of relatively large 1-2 µm pre-sintered agglomerates of grains while DKKK powder has a significantly higher surface area due to relatively uniform nanograins (see Figure 4.1) which favors lower sintering temperature for DKKK powder. Also Praxair and DKKK powders have a slightly different chemical composition that could have an additional effect on the sintering process.
4.2.2. Microstructure and Grain Size

The microstructure properties were characterized by collecting images at SEM and AFM of sintered ceramics. The high quality images were obtained with distinct grain boundary and grain size measurement was performed as described in Chapter 4 using Image Pro-Plus. It is observed from the experimental data that the sintering temperature has a significant effect on the grain size of the ceramic and its microstructure is shown in Figures 4.11, 4.12, and 4.13. Results of grain size and cavities are listed in Table 4.5.

J1200°C Grain size: 0.34µ

J1300°C Gain size: 0.80 63

J1400°C Grain Size: 2.71

(a)

J1500°C Grain size: 3.61µ
(b)

J1600°C Grain Size: 3.81µ

Figure 4.11: SEM images of DKKK samples from left to right sinter correspondingly 1200-1600°C

P1500°C Grain size: 2.48µm

P1600°C Grain Size: 4.42µm

Figure 4.12: SEM images of Praxair samples from left to right sinter correspondingly 1500-1600°C

64

10 6.0 5.5 5.0 8 4.5 4.0

0

2

4

6

8

10 10

DKKK, Japan Praxair, USA

8

Grain size (µ)

6 3.5 3.0 2.5 4 2.0 1.5 1.0 2 0.5 0.0 0 -0.5 0 1100 2 1200 1300 4 1400 6 1500 8 1600

6

4

2

0 10

Sintering Temperature (ºC)

Figure 4.13: Grain size vs. sintering temperatures

Table 4.5: Grain size and in-grain cavities at different sintering temperatures Sample Sintering Temp (ºC) 1100 1200 1300 1400 1500 1600 1100 1200 1300 1400 1500 1600 Grain size (Stdev) µm 0.23 (0.10) 0.34 (0.15) 0.80 (0.41) 2.71 (1.36) 3.61 (1.89) 3.81(1.95) 2.48 (1.27) 4.82 (2.36) Cavities (Stdev) µm 1.0 (0.4) 1.15 (0.3) 0.94(0.08) 0.68 (0.18) 1.14 (0.23)

J1100 J1200 J1300 J1400 J1500 J1600 P1100 P1200 P1300 P1400 P1500 P1600

65

The ceramic sintered at higher temperature has a large grain size while ceramic sintered at low temperature has a smaller size. The comparative study of grain size of ceramics J1600 and P1600 showed that the P1600 has a larger grain size. While Praxair sintered at 1500ºC has significant difference in grain size (Table 4.5) in comparison to the Japan powder (DKKK). It was found that below 1500ºC, ceramics from Praxair powders is not fully sintered; on the other hand, pallets of Japan (DKKK) powders are fully sintered even at 1400ºC. The grain size versus the sintering temperature plot reveals that the Japan powder can produce the same dense ceramic even at 200 lower temperatures than the Praxair powder (see Figure 4.11). The Praxair powder cannot produce fully dense material even at 1600°C (see Table 4.4). This result was also supported by the images collected after ion milling (see Figures 4.14, 4.15, 4.16).

Figure 4.14: SEM images collected after 1hr ion milling at 30 deg (left-J1600, rightP1600)

66

Figure 4.15: SEM images collected after ion milling (left-J1600 milled at 9-deg for 18hrs, right-P1600 milled at 5 deg for 20hrs)

Figure 4.16: SEM images of P1600 collected after ion milled at 5 deg for 20hrs (right-high porous area, left-less porous)

4.3. Phases and Stability of DKKK and Praxair Ceramics

Phase identification is very important in characterization of materials properties. Transition of phase has a greater impact on the different mechanical, thermal, and microstructure properties of materials. The stability of phase is crucial in the case of

67

SOFC electrolyte design. This is because of the significantly higher ionic conductivity of the cubic phase as compared to the rhombohedral phase. To analyze the DKKK and Praxair materials, several XRD experiments were performed. The cubic and rhombohedral phases were identified along with their phase stability temperature and phase transition temperature.
4.3.1 Phase Analysis in DKKK-based Samples

Ceramics sintered from DKKK powder at temperatures below 1300°C consist of two phases at room temperature. Ceramics sintered at temperatures 1300ºC and higher exist in cubic phase at room temperature. Phase transition from rhombohedral to cubic phase occurs at 400-500ºC (see Figure 4.17).

1.0

0.0

0.8

0.2

0.6

0.4

0.4

0.6

0.2

0.8

0.0 100 200 300 400 500 600

1.0 700

Temperature (°C)

(a)

68

Fraction of Rhombohedral Phase

Fraction of Cubic Phase

400°C 440°C 460°C 480°C 500°C 540°C

30

31

50

51

2 Theta (°)

(b) Figure 4.17: Phase content in the sample DKKK-1200 at different temperatures from XRD (Retvield multiphase analysis)

4.3.2 Phase Transition in J1600 Sample

High temperature XRD experiments were performed to study the phase transition behavior of J1600 and P1600 samples (see Figures 4.18-4.19). Silver peaks were used for internal temperature calibration. It was found that the DKKK based samples underwent the slow cubic to rhombohedra phase transformation at temperatures above 300°C. Rhombohedron to cubic phase transformation occurs at a significantly higher rate at 420°C. Results show that all Praxair-based samples exist in c-phase in the temperature range100-850°C.

69

Figure 4.18: Changes in XRD pattern of powdered sample J1600 heated from 300 to 500°C with step 10°C.

Heat Flow (W/g)

-0.010

0.8

-0.015

0.6

-0.020 449.4 °C 3.462 J/g

0.4

-0.025

0.2

1 hr
-0.030 300 350 400 450 500

0.0

Temperature (°C)

Figure 4.19: Phase transition in DKKK ceramic sintered at 1600°C

70

Fraction of Cubic Phase from XRD

-0.005

1.0

The differential scanning calorimetry (DSC) results show that when this material was heated at temperatures higher than 300°C DKKK samples underwent the slow cubic to rhombohedral phase transformation. This process was not registered as a peak in slow DSC scan. As the temperatures increased above 420°C the reverse rhombohedral to cubic phase transformation occurred at significantly faster rate and this endothermic process was registered by the DSC (see Figure 4.19). There was no such phase transition in the Praxair samples and only c-phase was found in the range of RT-850°C. It is my endeavor to study this behavior by running different samples at different heating and cooling rates for further investigation of material properties. Further experiments are under way at the Center for Advanced Materials and Smart Structure (CAMSS).

4.4 Coefficients of Thermal Expansion (CTE)

The CTE calculation was based on the procedure described in Chapter 4. The results obtained for coefficient of thermal expansion of as-received powders Praxair and DKKK ceramic samples P1600 and J1400 and powders produced from them were obtained by high temperature XRD method in the temperature range 100-850ºC. Powders were used in the form of slurry coating on Si (100) substrate with small amounts of silver paint used as a binder for powders and as internal reference material for temperature calibration. Ceramic samples with thickness equal to Si substrate were polished down to 0.5µm grit size and annealed at 850ºC for 20 minutes to release stresses on sample surface.

71

DKKK-based powders have an almost constant CTE in the temperature range 100-850ºC while CTE of all Praxair-based samples and ceramic sample J1400 almost linearly increase with temperature. CTE of ceramics have the highest increase in this range (almost 2 times for the sample P1600 and 1.7 times for J1400). This difference supports assumption of significant internal compressive stresses in ceramics at room temperature. This also can explain formation of crater-like cavities on fracture surfaces at room temperature due to explosive chipping of material in order to release compressive stresses near to the fracture surface. The three models of fittings are listed in Table 4.6, and are recognized by bold, italic and normal fonts. The best fitting for as-received Praxair powder, as-received DKKK powder and J1500-powder and J1500-ceramic is shown in Figures 4.20-4.25. The best fitting model was chosen based on an analysis of residuals, overall standard deviations and standard errors of parameters.

72

Table 4.6. Coefficients of thermal expansion for Praxair and DKKK samples in ceramic and powder forms Form CTE×106 (deg-1) SD×106 # of Temp.

Sample

Praxair as-received Powder Ceramic Powder Powder Ceramic Powder Powder

Powder

9 8 18 7 8 9 8 13

P1600

P1600

DKKK as-received

73

J1400

J1400

J1500

J1600

10.02±0.21 (6.51±0.24) + (5.16±0.35)×10-3T (7.43±1.19) + (2.25±3.69)×10-3T + (2.12±2.68)×10-6T2 10.45±0.19 (7.14±0.39) + (4.61±0.53)×10-3T (5.83±2.33) + (8.47±6.75)×10-3T - (2.68±4.67)×10-6T2 10.51±0.23 (4.85±0.43) + (8.27±0.62)×10-3T (5.24±2.05) + (7.05±6.37)×10-3T + (0.89±4.62)×10-6T2 9.74±0.16 (7.61±0.91) + (3.17±1.35)×10-3T (4.32±6.06) + (13.4±18.7)×10-3T - (7.6±13.8)×10-6T2 10.35±0.20 (7.67±1.13) + (3.80±1.60)×10-3T (11.8±6.8) - (8.7±20.3)×10-3T + (8.9±14.4)×10-6T2 10.60±0.29 (5.68±0.36) + (7.36±0.53)×10-3T (7.37±1.75) + (1.92±5.52)×10-3T + (4.04±4.09)×10-6T2 10.56±0.23 (4.89±1.51) + (7.27±1.92)×10-3T (22.8±10.2) - (39.8±26.8)×10-3T + (30.2±17.1)×10-6T2 10.45±0.20 (8.49±2.29) + (2.47±2.87)×10-3T (24.0±19.0) - (37.6±48.8)×10-3T + (25.2±30.6)×10-6T2 155.1 27.1 28.0 118.4 32.5 35.0 244.3 69.9 72.2 89.2 60.0 66.0 124.6 92.6 99.0 212.8 39.9 40.0 115.1 64.2 53.9 121.6 123.0 125.0

Note: Bold – best fit, Italic – acceptable fit, Normal – poor fit.

Praxair as received powder The following figures represent the best fitting model for the Praxair as received powder (see Figures 4.20-4.21).

10 0.00025 0.00020 8 0.00015 0.00010 6

Constant Linear Qudratic

Delt

0.00005 4 0.00000 -0.00005 2 -0.00010 -0.00015 0 0 200 300 2 400 500 4 600 700 6800 900 8 1000 1100 10

Temperature, K

Figure 4.20: Instrumentally set temperature vs. residuals (Praxair powder)

1.636

1.634

Constant Linear Q uadratic

1.632
Ln(a)

1.630

1.628 200 400 600
Temperature, K

800

1000

Figure 4.21: Constant, linear and quadratic fitting with temperature vs. log (LT) (Praxair powder)

74

DKKK as received powder The following figures represent the best fitting model for the DKKK as received powder (see Figures 4.22-4.23).

0.00010

Constant Linear Qudratic

0.00005

Delta

0.00000

-0.00005

-0.00010 100 200 300 400 500 600 700

Temperature,K

Figure 4.22: Instrumentally set temperature vs. residuals (DKKK powder)

1.634

Constant Linear Quadratic

1.632

Ln(a)
1.630 1.628 400 600 800 1000

Temperature (K)

Figure 4.23: Constant, linear and quadratic fitting with temperature vs. log (LT) (DKKK powder)

75

J1500 Powder The following figures represent the best fitting model for the J1500 powder (see Figures 4.24-4.25).

0.00020 0.00015 0.00010

Constant Linear Quadratic

Residuals

0.00005 0.00000 -0.00005 -0.00010 -0.00015 -0.00020 300 400 500 600 700 800 900 1000 1100

Temperature (K)

Figure 4.24: Instrumentally set temperature vs. residuals (J1500 Powder)
1.636

1.634

Constant Linear Quadratic

1.632
Ln(a)

1.630

1.628 200 400 600
Temperature, K

800

1000

Figure 4.25: Constant, linear and quadratic fitting with temperature vs. log (LT) (J1500 Powder)

76

J1500 Ceramic The following figures represent the best fitting model for the J1500 ceramic (see Figures 4.26-4.27).

0.0004

0.0003

Ln(a)Calc - Ln(a)

0.0002

Constant Linear Quadratic

0.0001

0.0000

-0.0001

-0.0002 200 300 400 500 600 700 800 900 1000 1100

Temperature (K)

Figure 4.26: Instrumentally set temperature vs. residuals (J1500 ceramic)

1.636

1.634

Constant Linear Quadratic

1.632
Ln(a)

1.630

1.628 200 400 600
Temperature, K

800

1000

Figure 4.27: Constant, linear and quadratic fitting with temperature vs. log (LT) (J1500 ceramic)

77

4.5 Hardness and Fracture Toughness

The hardness and fracture toughness properties were characterized by collecting high quality indent images on Optical Microscope. The measurements were performed as described in Chapter 4 using Image Pro-Plus.
4.5.1 Microindentation of Etched and Non-Etched Samples

Vickers microindentation of mechanically polished surfaces show that hardness increases with increase of density and consequently with increase of sintering temperature. Fracture toughness of ceramics decreases with increase of hardness and/or sintering temperature as shown in Figures 4.28-4.29.

14

13

Non-etched(DKKK) Non-etched(Praxair) Etched(DKKK) Etched(Praxair)

Hardness(GPa)

12

11

10

9

8 1200 1300 1400 1500 1600

Sintering temperature(°C)

Figure 4.28: Hardness vs. sintering temperature plot for etched and non-etched sample

78

3.8 3.6 3.4

Fracture toughness(MPa·m0.5)

3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1200 1300 1400

Non-etched(DKKK) Non-etched(Praxair) Etched(DKKK) Etched(Praxair)

1500

1600

Sintering temperaure(°C)

Figure 4.29: Variation in fracture toughness value with temperature

Hardness of the samples decreases at higher loads. This widely discussed phenomenon, namely, indentation size effect (ISE), is typical for single crystals and metals and is almost absent in fine-grained polycrystals. Most of the mechanisms developed are based on the dislocation nature of the ISE. ISE also can be considered as an artifact of mechanical polishing and measurement errors. We estimated that our mechanical polishing procedure can create damage up to 0.2-0.3 µm in depth (surface nanoroughness range did not exceed 50 nm). To avoid the effect of mechanical polishing we selected loads which create indents at least 1 µm or 3 times deeper than the estimated

79

threshold of damaged surface layer due to polishing. Simple evaluation of ISE can be done by linear log H – log h relationship based on empirical power-law relation H = HI* h-m [50], where h is the depth of indentation, m is power-law exponent of the ISE index, and H1 is constant corresponding to hardness at the depth of 1 µm. Some typical impressions at different loads are shown in Figure 4.30.

Load = 1000g Magnification = 500x H = 12.69GPa K1C = 2.12MPa·m0.5

Load = 500g Magnification = 500x H =12.92GPa K1C = 2.12 MPa·m0.5

Load = 300g Magnification = 500x H = 13.21GPa K1C = 1.79 MPa·m0.5

Load = 200g Magnification = 1000x H = 13.63GPa K1C =1.65 MPa·m0.5 (a)

Load = 100g Magnification = 1000x H = 13.63GPa K1C =1.92 MPa·m0.5

80

12

4

Hardness (GPa)

11 3 10 9 8 7 6 1200 1300 1400 1500 1600 2

Praxair K1C DKKK K1C

1

0

Sintering Temperature (°C)
(b) Figure 4.30: (a) Effect of sintering temperature on microhardness and fracture toughness at the load 1000g and; (b) Micrograph of typical Vickers indents and cracks at different loads (thermally etched J1600)

Tables 4.7-4.8 contain the hardness and fracture toughness values for each load from 1000g-100g. The weighted value for hardness and fracture toughness was also calculated. The results obtained for DKKK based and Praxair-based ceramics are listed in Table 4.7 (for non-etched samples), and Table 4.8 (for thermally etched samples). Table 4.9 contains hardness and fracture toughness values for both etched and non-etched samples.

81

Fracture Toughness (MPa·m

-0.5

13

Praxair Hardness DKKK Hardness

5

)

Table 4.7. Hardness (H) and fracture (K1C) toughness values at different sintering temperatures and loads for nonetched samples 1000g 500g 300g 200g 100g

Sample

Properties

J1200 3.54(0.40) 10.64(0.82) 2.94(0.43) 11.69(0.72) 2.72(0.26) 12.70(0.57) 2.36(0.19) 12.78(0.41) 2.06(0.17) 7.88(1.5) 3.53(0.48) 10.20(1.21) 2.01(0.31) 3.23(0.4) 2.52(0.24) 1.03(0.96) 10.6(0.74) 2.33(0.33) 2.31(0.35) 8.69(1.85) 8.81(1.69) 1.92(0.14) 2.08(0.25) 12.98(0.5) 13.07(0.4) 2.35(0.32) 2.68(0.28) 2.6(0.32) 13.20(0.53) 1.93(0.22) 8.84(1.49) 2.28(0.18) 10.86(0.81) 2.37(0.27) 11.70(1.06) 2.07(0.33) 13.32(0.61) 1.91(0.23) 8.93(2.31) 13.23(0.5) 13.81(0.5) 14.63(0.51) 2.87(0.24) 2.78(0.26) 2.56(0.51) 15.28(1.25) 12.2(0.58) 12.66(0.9) 12.78(1.02) 13.4(1.11) 3.00(0.38) 2.73(0.24) 2.45 10.45(1) 10.91(0.7) 11.09(1) 11.77(1.0) 3.08(0.46) 3.25 3.29(0.23) 11.97(0.9) 2.78(0.24) 12.54(0.6) 2.73(0.13) 13.93(1.03) 2.49(0.16) 13.07(0.48) 1.98(0.08) 8.63(0.43) 2.89(0.6) 10.74(0.69) 2.24(0.17)

H(StDev)

8.89(0.87)

8.59(1.03) 8.59(1.17)

8.98(1.28)

8.77(1.07)

Avg.(H) GPa 8.76(0.17)

Weighted (H) GPa 8.76(0.17)

K1C(StDev)

3.34(0.3) 10.92(0.4) 2.83(.18) 12.35(0.35) 2.77(0.14) 13.70(0.25) 2.46(0.13) 13.03(0.2) 1.97(0.08) 8.57(0.78) 2.55(0.13) 10.74(0.41) 2.24(0.14)

J1300

H(StDev)

K1C(StDev)

J1400

H(StDev)

K1C(StDev)

82

J1500

H(StDev)

K1C(StDev)

J1600

H(StDev)

K1C(StDev)

P1500

H(StDev)

K1C(StDev)

P1600

H(StDev)

K1C(StDev)

Table 4.8. Hardness (H) and fracture toughness (K1C) values at different sintering temperatures and loads for thermally etched samples 1000g 500g 300g 200g 100g

Sample

Property

J1200 11.31(0.87)

9.74(0.88)

10.56(0.97)

J1300

J1400

J1500

83

J1600

P1500

P1600

H(StDev) K1C(StDev) H(StDev) K1C(StDev) H(StDev) K1C(StDev) H(StDev) K1C(StDev) H(StDev) K1C(StDev) H(StDev) K1C(StDev) H(StDev) K1C(StDev) 11.0(0.64) 2.88(0.21) 12.15(0.8) 2.29(0.37) 13.1(0.64) 2.23(0.32) 13.2(0.39) 2.11(0.28) 8.88(1.29) 2.55(0.32) 10.24(0.3) 2.30(0.34) 12.15(0.82) 1.76(0.42) 13.25(0.85) 1.74(0.02) 13.63(0.23) 1.65(0.40) 8.85(0.97) 1.69(0.5) 10.26(0.54) 1.05(0.52)

9.05(1.10) 3.09(0.29) 10.7(0.68) 2.75(0.27) 11.9(0.54) 2.05(0.14) 13.3(0.28) 2.00(0.12) 12.70.41) 1.91(0.21) 8.81(1.58) 2.68(0.53) 10.471.0) 2.11(0.21)

8.55(0.87) 2.70(1.07) 11.07(0.54) 3.08(0.08) 11.94(0.26) 2.02(0.29) 13.09(0.54) 2.02(0.16) 12.92(0.55) 2.12(0.15) 8.44(1.19) 2.81(0.16) 9.93(0.99) 2.18(0.24)

9.94(1.02) 1.86(0.79) 11.91(0.5) 2.50(0.30) 12.2(0.76) 2.16(0.30) 13.6(0.55) 2.02(.19) 13.3(0.45) 1.79(015) 9.49(1.56) 2.29(0.53) 10.99(1.0) 1.70(0.16)

Avg. (GPa) 9.57(0.78) 2.55(0.63) 11.21(0.45) 2.80(0.24) 12.0(0.12) 2.06(0.18) 13.3(0.21) 2.00(018) 13.15(0.3) 1.92(0.20) 8.89(0.38) 2.41(0.44) 10.38(0.4) 1.87(0.51)

Weighted Avg.(GPa) 9.55(0.43) 2.93(0.26) 11.01(0.20) 3.00(0.07) 11.99(0.21) 2.06(0.11) 13.28(0.28) 1.75(0.02) 13.32(0.16) 1.95(0.09) 8.84(0.56) 2.66(0.13) 10.28(0.27) 1.93(0.11)

Table 4.9. Comparison of hardness and fracture toughness of non-etched and etched samples Samples Sintering temperature Non-etched sample H(StDev) GPa K1C (StDev)
(MPa·m0.5)

Etched Samples H(StDev) GPa K1C (StDev)

(MPa·m0.5)

P1500 P1600 J1200 J1300 J1400 J1500 J1600

1500 1600 1200 1300 1400 1500 1600

8.57(0.78) 10.74(0.41) 8.76(0.17) 10.92(0.39) 12.35(0.35) 13.70(0.25) 13.03(0.20)

2.55(0.13) 2.24(0.14) 3.34(0.30) 2.83(0.18) 2.77(0.14) 2.46(0.13) 1.97(0.08)

8.84(0.56) 10.28(0.27) 9.55(0.43) 11.01(0.20) 11.99(0.21) 13.28(0.28) 13.22(0.16)

2.66(0.13) 1.93(0.11) 2.93(0.46) 3.00(0.07) 2.06(0.11) 1.75(0.02) 1.95(0.09)

Indentation size effect in hardness value of materials at different indentation depths was predicted using the empirical power-law as described in Page 80. The results of this analysis are presented in Table 4.5 and in Figure 4.10(a). Most of the samples exhibited relatively weak ISE compared to single crystals of metals and semiconductors (typically m from 0.12 to 0.32). ISE for polycrystals, was found to depend on the grain size. Generally, no ISE is observed if impression covers several grains, and for largegrained polycrystals ISE is significant if impression is localized inside one grain. Nanocrystalline sample J1200 does not exhibit ISE. In the case of other samples, indentation size for most loads are comparable or exceed grain size. We have noticed that at higher loads (500 or 1000 g) hardness values are scattered significantly for samples with large grains. These samples have less porosity. They are dense and are expected to create more regular plastic deformation zones for every indent. This unexpected behavior

84

of large-grained samples can be explained by significant variation of ISE effect from indent to indent due to significant scattering of the volume of stored dislocations under indentation. The Nix and Gao [51] model relates the ISE to geometrically necessary dislocations (GNDs). According to this model, density of GNDs is proportional to the inverse indentation depth. The additional hardening of GNDs is mainly based on total line length of dislocations, necessary to form the permanent geometry of the impression, and on the volume, in which the dislocations are stored. Using strain-gradient plasticity theory, Nix and Gao created a model describing the contribution of GNDs to the hardness (strain gradient effect) properties of material. Based on this model the strain gradient law implies the following relation for the hardness:

H h* = 1+ H0 h
where H is apparent hardness, H0 is characteristic hardness arisen from the statistically

4.1

stored dislocations in the absence of geometrically generated dislocations, h indentation depth, and h* is characteristic length (depth) at which the effect of strain gradient becomes comparable to the effect of strain. From the linear dependences of H2 from the reversed indentation depth (see Figure 4.31), we estimated parameters H0 and h* as listed in Table 4.10. Characteristic hardness of samples strongly depends on sintering temperature and material density. Values of h* indicate that geometrically necessary dislocations are limited by grain size.

85

14 13 12 180 160 140

H (GPa )

11 10 9 8 1 2 3 4 5 6

120 100 80 60 0.2 0.4 0.6
-1

I-1500 I-1600 II-1200 II-1300 II-1400 II-1500 II-1600

Hardness (GPa)

2

2

0.8

Indentation Depth (µm)

1/h (µm )

(a)

(b)

Figure 4.31: ISE analysis using power law (a) and Nix-Gao (b) models

Table 4.10: ISE parameters for Praxair and DKKK-based samples Sample Sintering Temp. (ºC) Power law model m H1 (GPa) Nix-Gao model H0 (GPa) h* (µm)

P1500 P1600 J1200 J1300 J1400 J1500 J1600

1500 1600 1200 1300 1400 1500 1600

0.109 0.116 0.0 0.083 0.109 0.072 0.037

9.64 11.86 8.76 11.81 13.71 13.97 13.44

7.61 9.35 8.76 9.92 11.05 12.25 12.58

0.73 0.71 0.00 0.50 0.61 0.32 0.17

86

4.5.2 Nanoindentation

Nanoindentation tests were performed on the ceramic samples J1600 and P1600 using NanoindenterR XP in a continuous stiffness measurement (CMS) option. A threesided Berkovich indenter was used with a 60nm tip radius and 65.3° included half-angle. The indentation was carried out at a depth of 1000nm for ceramic. Sixteen indents for P1600 and sixty four indents for J1600 samples were created. The data was averaged for each sample and is listed in Table 4.11.

Table 4.11: Nanoindentation values Samples P1600 J1600 Young modulus(GPa) 230 210 Hardness(GPa) 16.5 17.99

It was observed that the hardness and modulus of DKKK ceramic is slightly higher than the Praxair ceramic sintered at 1600°C shown in Figures 4.32-4.33. It was also found that the density of J1600 has a slightly larger density than the P1600. The DKKK samples were fully sintered and had a fewer number of pores and cavities in comparison to the Praxair ceramic (see Figures 4.8-4.11).There was not much difference in hardness and modulus data depending on the number of grains covered by the indentor for both samples.

87

300 280

Praxair, P1600 DKKK , J1600

Young's Modulus (GPa)

260 240 220 200 180 160 0 100 200 300 400 500

Indentation Depth (nm)

Figure 4.32: Nanoindentation Young’s modulus results

24 22

Praxair P1600 DKKK J1600

Hardness (GPa)

20 18 16 14 12 10 0 100 200 300 400 500

Indentation Depth (nm)
Figure 4.33: Nanoindentation hardness results

88

CHAPTER 5 CONCLUSION AND FUTURE WORK

5.1 Conclusion

The following conclusions can be made based on the results of the research work outlined: • Phase and chemical composition, morphology, and grain size of the 10 mol% Sc2O3 – 1 mol% CeO2 - ZrO2 ceramic powders produced by Praxair Specialty Ceramics, USA and by DKKK, Japan has been characterized. • The sinterability of the powders has been studied by sintering at 6 different temperatures (1100ºC -1600ºC). • The sintering rate of the ceramic powder manufactured by DKKK is much higher than the powder manufactured by Praxair. The DKKK powder was able to reach its lowest porosity level at lower temperatures and shorter sintering times than the Praxair powder. • DKKK-based ceramics have phase instability in the region 300-500ºC. Transformation from c- to b-phase at these temperatures is slow process and it is required to use high heating and cooling rates to avoid formation of significant amounts of b-phase. • The ionic conductivity of selected samples is reported to be ~0.088 S/cm for Praxair Ceramics and ~0.156 S/cm for DKKK ceramics at 800ºC.

89

Coefficients of thermal expansion in the range RT-800ºC of both types of ceramics are in the range 10.5 – 10.6×10-6 grad-1 and very close to CTE of cubic zirconia. CTE of DKKK samples have less linear dependency on temperature than Praxair samples.

Young’s modulus and hardness of DKKK samples are higher than Praxair samples.

High temperature fracture toughness measurements confirm that these ceramics are very brittle, especially at elevated temperatures. The highest K1C was 2.5 MPa×m.5 at 300ºC for DKKK ceramics.

5.2 Future Work

The following are recommendations for future work: • Study of mechanical and microstructure properties of J1300 samples by changing the dwell time and heating and cooling rate. • Study of mechanical and microstructure properties of rhombohedral phases of samples J1300-J1600

90

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