High Temperature Coatings

High Temperature Coatings

Second Edition

Sudhangshu Bose

Retired Fellow, Pratt & Whitney, East Hartford Connecticut, Retired Professor of Practice Rensselaer Polytechnic Institute, Department of Mechanical Engineering, Troy, New York

Table of Contents

Cover image

Title page

Copyright

Dedication

About the Author

Preface to the Second Edition

Preface to the First Edition

Chapter 1. Introduction

1.1. High-Temperature Environment

Chapter 2. Fundamental Concepts

2.1. Thermodynamic Concepts

2.2. Concept of Kinetics

2.3. Crystal Structure

2.4. Equilibrium Phases

2.5. Mechanical Behavior

Chapter 3. Substrate Alloys

3.1. Temperature Capability of Metals, Alloys, Intermetallics, Ceramics, and Composites

3.2. Strengthening Mechanisms

3.3. Titanium Alloys

3.4. Steels

3.5. Nickel–Iron Alloys

3.6. Nickel and Cobalt Base Superalloys

3.7. Ceramics, Refractory Intermetallics, and Composites

3.8. Need for Coatings

Chapter 4. Oxidation

4.1. Oxidation Process

4.2. Oxidation Testing and Evaluation

4.3. Oxidation of Alloys

4.4. Roles of Specific Alloying Constituents

4.5. Oxidation in the Presence of Water Vapor

4.6. Oxidation of Polycrystalline Versus Single-Crystal Alloys

4.7. Oxidation of Intermetallic γTiAl

Chapter 5. High-Temperature Corrosion

5.1. Hot Corrosion Processes

5.2. Hot Corrosion of Metals and Alloys

5.3. Role of Specific Alloying Elements in Hot Corrosion of Ni- and Co-Based Alloys and Coatings

5.4. Influence of Other Contaminants

5.5. Hot Corrosion of Thermal Barrier Coatings

5.6. Hot Corrosion-Like Degradation

Chapter 6. Oxidation- and Corrosion-Resistant Coatings

6.1. Requirements for Metallic Coatings

6.2. Coating Processes

6.3. Diffusion Coatings

6.4. Overlay Coatings

6.5. Overlay Coatings by Spray and Arc Processes

6.6. Overlay Coatings by Physical Vapor Deposition

6.7. Relative Oxidation and Corrosion Resistance of Coatings

6.8. Modeling of Oxidation and Corrosion Life

6.9. Interaction of Erosion–Oxidation and Erosion–Corrosion

Chapter 7. Thermal Barrier Coatings (TBCs)

7.1. Temperature Reduction by Thermal Barrier Coatings

7.2. Materials Requirement for Thermal Barrier Coatings

7.3. Partially Stabilized Zirconia

7.4. Plasma-Sprayed Thermal Barrier Coatings

7.5. Electron Beam Physical Vapor Deposited Thermal Barrier Coatings

7.6. Environmental Barrier Coatings

Chapter 8. Nondestructive Inspection (NDI) of Coatings

8.1. Nondestructive Inspection Techniques

Chapter 9. Coatings Repair

9.1. Limits to Coatings Repair

9.2. The Repair Process

9.3. Recoating and Material Restoration

Chapter 10. Field and Simulated Field Experience

10.1. Gas Turbine Engine Application

10.2. Other Applications

10.3. New Field Observations on Gas Turbine Engine Hot Section Parts

Appendix

Author Index

Subject Index

Copyright

Butterworth-Heinemann is an imprint of Elsevier

The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom

50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

Copyright © 2018 Elsevier Inc. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library

ISBN: 978-0-12-804622-7

For information on all Butterworth-Heinemann publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Matthew Deans

Acquisition Editor: Christina Gifford

Editorial Project Manager: Ana Claudia Garcia

Production Project Manager: Paul Prasad Chandramohan

Designer:Alan Studholme

Typeset by TNQ Books and Journals

Dedication

This book is lovingly dedicated to our two grandchildren, Colin and Samuel as an inspiration to love the enchanting world of learning.

About the Author

Dr. Sudhangshu Bose is a retired fellow and manager at Pratt & Whitney, the manufacturer of gas turbine and rocket engines. He has also been professor of practice in mechanical engineering at Rensselaer Polytechnic Institute, Troy, New York and Hartford, CT, United States. He holds a PhD in materials science and engineering from the University of California, Berkeley, having previously obtained BSc (Honors) and MSc in physics from Ranchi University, Ranchi, India. Dr. Bose has taught undergraduate and graduate level courses in physics and conducted research in materials characterization by X-ray diffraction prior to completing the doctoral degree. While at Pratt & Whitney and its sister divisions, Dr. Bose has conducted and managed research, development, and testing of advanced materials and processes including oxidation and corrosion in fuel cells and gas turbine engine, catalysis, high temperature coatings, superalloys, intermetallics, and ceramic matrix composites. He holds over 24 patents. As a professor of practice at Rensselaer, he taught courses and supervised research in the areas of superalloys, high temperature coatings, and conventional and renewable energy technologies. He is currently associated with the Department of Mechanical Engineering and Materials Science at Yale University, New Haven, CT.

Preface to the Second Edition

The first edition of this book was published in 2007. It was gratifying to see the book well received by the academics involved in studying and teaching high temperature coatings and related fields, by practicing professionals in the disciplines of engineering design, manufacturing, materials, durability assessment, as well as by the research community. I was pleased to receive a request from the publisher, Elsevier, to bring out a second edition. The literature of high temperature coatings has grown in leaps and bounds since the publication of the first edition. This growth encompasses all aspects of the field including novel compositions and processing methods involving both physical and chemical process routes, the use of sensors in processing and during use, understanding of the microstructure property relationships, deciphering fundamentals of environmental interactions, repair of coated parts through stripping of old coating followed by refurbishment, newer applications, innovative methods of characterization, predictive modeling of behavior, and enhanced physics-based life prediction methodologies. The new edition has been fully revised, incorporating many of the changes described above, replacing some of the qualitative reasoning with quantitative arguments. Additional illustrations have been incorporated to improve clarity. Many sections and subsections have been added or rewritten to bring the contents more up-to-date. The appendix has new additions. The intent has always been to make the content up-to-date without making it unwieldy.

It is a pleasure to acknowledge help and assistance from many people to make this endeavor possible. Elsevier's editorial team of Christina Gifford (USA), Ana Claudia Garcia (Brazil), and Swapna Praveen (India), and Paul Chandramohan (India) provided professional help in bringing out this edition. Prof. Maury Gell, University of Connecticut, provided encouragement and Dr. Jim Smialek of the NASA Glenn Research Center was very helpful in providing more recent data and his analysis. Finally, my sincere thanks go to the authors and copyright owners for providing permission to use excerpts, data, figures, tables, and artworks.

Sudhangshu Bose,     Manchester, Connecticut, USA

2017

SudhaBose@gmail.com

Preface to the First Edition

The idea of a book on high temperature coatings arose out of a need for teaching material for a semester-long course for engineering students. Additionally, it would provide a resource of reference material for practicing professionals. It took the author several years during his forays into teaching to assemble the material in a balanced and logical format.

High temperature coatings belong to a technologically important, economically lucrative, intellectually fertile, and fast-evolving field. It encompasses a basic understanding of materials, principles of physical metallurgy and ceramics, environmental interactions, processing sciences, and manufacturing techniques. There is a wealth of information available on various aspects of these coatings. However, the information is dispersed in myriads of technical journals, conference proceedings, handbooks, book chapters, published reports from the manufacturers in the industry, and users of coatings, as well as from National Laboratories and other organizations in a host of countries. The author had the fortune to have access to many of these resources in addition to his own continuing experience in the aerospace industry, spanning over a quarter of a century.

For the users of this book, a rudimentary knowledge of physics and chemistry is assumed. The fundamental concepts, which cover thermodynamic and kinetic principles, as well as phases and phase diagrams, are described in the first two chapters. A basic understanding of structural alloys used in high temperature processes and equipment, notably gas turbine engines, which require high temperature coatings, is introduced in a separate chapter. Environmental interactions including oxidation and high temperature corrosion are discussed in Chapters 4 and 5. Metallic coatings for protection against oxidation and corrosion are covered in Chapter 6 in reasonable detail including processing, characterization, and properties. A number of processes traditionally used in the electronic industry to deposit thin films have been included because of their unique characteristics and slow, but progressive, adaptation to deposit thicker coatings in special cases. Thermal barrier coatings (TBCs) for thermal protection are addressed in Chapter 7. For better flow and ease of understanding, this chapter is physically separated into three sections, starting with an introduction in the beginning, plasma-sprayed TBC in the middle, and electron beam TBC at the end, together with the literature references for the whole chapter. Non-destructive inspection, coatings repair, and coating experience in the field are treated in the last three chapters. Extensive references are given for the readers to consult the original sources.

Obviously, the author benefited immensely from the work of many of the pioneers from the past and the present. One such individual is Dr. Bill Goward. The author is deeply grateful to Dr. Goward for his thoughtful review and constant guidance during the writing of the book. Professor Fred Pettit of the University of Pittsburgh, Professor David Clarke of the University of California, Santa Barbara, Professor Maury Gell of the University of Connecticut, and Dr. Bob Miller of the NASA Glenn Research Center, all of whom are prolific contributors to the knowledge base in the field of high temperature coatings, were very kind to review parts of the manuscript and provide suggestions for improvement. My special appreciation goes to Professor Ernesto Gutierrez-Miravete of Rensselaer, Hartford for his encouragement.

Elsevier's Joel Stein has been of immense help from the very beginning of this project, providing advice, encouragement, and the words of wisdom of a seasoned editor. I owe him my sincere thanks. Special thanks are also due to Shelly Palen of Elsevier for her editorial help and to Julie Ochs for her superb production of the manuscript.

The author has made every effort to correct inaccuracies and acknowledge the original sources including authors and publishers. He regrets any omissions.

My appreciation goes to the following sources and copyright owners for their permission to use excerpts, data, figures, tables, and artworks:

Elsevier, John Wiley & Sons, Inc., Springer, Taylor and Francis, Maney Publishing, Blackwell Publishers, The Minerals, Metals, and Materials Society (TMS), American Society of Materials (ASM) International, The American Ceramic Society, American Society of Mechanical Engineers (ASME) International, American Institute of Physics, Science and Technology Letters, Annual Reviews, National Association of Corrosion Engineers (NACE), The Electrochemical Society, Praxair Technologies, Sulzer-Metco, Professor Jogender Singh (Pennsylvania State University), Drs. Jim Smialek and Bob Miller, both of the NASA Glenn Research Center, Dr. Thomas Strangman of Honeywell, Department of Energy, United States Air Force, and the National Aeronautics and Space Administration.

Finally, I am thankful to Pratt & Whitney for permission to use examples from its collection of coatings, coated engine hardware, publications, and the photo of a turbine blade, which appears on the cover of this book.

Sudhangshu Bose,     Manchester, Connecticut, USA

2007

Chapter 1

Introduction

Abstract

This chapter presents the parameters and conditions that collectively describe the high temperature environment existing in many industrial processes and machines. Some of these processes and machines are highlighted.

Keywords

Adiabatic; Erosion; Gamma prime; Superalloys; Temperature gradient

1.1. High-Temperature Environment

A large number of industrial processes and their products operate in very aggressive environments characterized by high temperature, increased temperature gradients, high pressure, large and often fluctuating or cyclic stresses on individual components, and the presence of oxidizing and corroding atmosphere as well as internally created or externally ingested particulate material, which induces erosion and impacts damage. A few representative examples of such processes are shown in Fig. 1.1 (Stroosnijder et al., 1994). Machines and power plants exhibiting the environments described above include aircraft gas turbine engines; steam turbines; industrial gas turbines; hypersonic flight vehicles; rocket combustion chambers; high-temperature fuel cells; systems involving coal conversion process, petroleum refining, and nuclear power plants; waste incineration and solar thermal energy conversion systems; and test facilities. The generation of large amounts of heat, associated high component temperature, and heat flux lie at the heart of all of these processes. At the core of many of the power systems and processes lies a turbine, better known for powering gas and steam turbines. For example, in the turbines in jet engines, fuel is mixed with highly compressed air entering through the compressor and the mixture is ignited. As a result of the combustion process, heat is released, and the expanding air works on the turbine with the blades to rotate it. The turbine in turn, through the connected shaft, forces the compressor to rotate, which compresses the incoming air. The exiting exhaust gas creates thrust for propulsion. The gas temperature in modern gas turbine engines could well exceed 1650°C (3000°F) in the turbine section, with cooled parts reaching temperatures as high as 1200°C (2200°F). The compression systems in modern engines are now designed to run at higher pressure ratios. Being an adiabatic environment even without any source of heat, the last stages of the compressors are running hotter. Fig. 1.4A shows the cross section of a Pratt & Whitney PW4000 gas turbine engine with 100 inch diameter fan. The gaspath temperature and pressure profile of typical high thrust engines are shown in Fig. 1.4B. Similar profiles for Rolls Royce Trent 800 (Cervenka, 2000) are available in the literature. High-temperature coatings have not only become the enabler of many materials and component designs of the gas turbine engine in its aggressive environment, they have also become a test bed to screen and evaluate performance as well as the durability of these coatings. In coal gasifiers, coal reacts with steam at high temperatures to convert it into usable gas, which can be transported by pipelines and fed directly into processing plants. Process temperatures could be as high as 1650°C (3000°F) with component temperatures reaching 1090°C (2000°F). Process temperature is also high in petroleum refining as well as nuclear power generation. In petroleum refining, crude petroleum is catalytically cracked at high temperatures and fractionated into usable petroleum products such as liquid petroleum gas, gasoline, kerosene, diesel, heavy oils, plastics, asphalt, and coke. In nuclear power plants, the heat from controlled fission of fuel elements, such as enriched uranium and thorium, is used to produce steam, which is in turn fed into turbines, the shaft of which is connected to a generator to provide electrical power. A number of coatings have been evaluated for potential application even in nuclear fusion reactors (Matějíček et al., 2013).

Figure 1.1  High-temperature processes with component temperatures and required lives. Based on Stroosnijder, M.F, Mevrel, R., Bennett, M.J, 1994. The interaction of surface engineering and high temperature corrosion protection, Mater. High Temp. 12 (1), pp. 53–66. Reprinted with permission from Science and Technology Letters.

All these processes require materials of construction with high-temperature capability under load to meet performance, durability, weight, cost, and environmental resistance requirements. During operation, the structural materials of individual components degrade. In addition to fatigue and creep damage of structurally loaded components, the materials undergo oxidation, corrosion, and erosive wear. Typical temperatures seen in some of the industrial processes are compared in Fig. 1.2, benchmarked against melting points of some basic structural materials.

Figure 1.2  Typical temperatures for some industrial processes.

Over time, the required design temperature of many of the processes, components, and the machines described above has been going up. The major driving force for the increase in temperature had been the expected benefit in process efficiency. This is elaborated in a subsequent chapter.

The strength ranges of a few potential materials of construction for high-temperature processes as a function of temperature are shown in Fig. 1.3 (Meetham, 1988). Properties of many of these engineering materials such as tensile, creep, and fatigue strength are generally optimized for maximum load-carrying capability, with less emphasis on the environmental resistance. As an example, turbine blades for jet engines are made of precipitation-strengthened nickel base superalloys, the precipitates being the gamma prime phase in a gamma phase matrix.

One of the constituents of the alloys is aluminum, which participates in the formation of strengthening precipitates as well as in providing for oxidation resistance. Although higher aluminum content of the alloys increases high-temperature oxidation resistance, it is kept at a level below 6% to maximize the creep strength. If such bare alloys are exposed to the environment of high-pressure turbine of modern gas turbine engines, they will degrade fast by several of the processes discussed below.

• Oxidation: The alloys do not have adequate levels of such critical elements as Al and Cr to impart oxidation resistance for the life of the parts. Increasing Al, therefore, would apparently be a logical solution to increase the oxidation capability. However, a high Al level will lower the melting point of the alloys and their creep resistance, reducing, in turn, the load-bearing capability, a must-have property of turbine blades and other turbine hardware.

Figure 1.3  Temperature capabilities of classes of materials. From Meetham, G.W, 1988. Requirements for and factors affecting high temperature capability, Mater. Design 9 (5), p. 247. Reprinted with permission from Elsevier.

Figure 1.4  (A) A commercial transport jet engine, Pratt & Whitney's PW4000 with 100 inch fan diameter showing various stages. (B) Gas path pressure and temperature profile of a typical high thrust jet engines. Reprinted with permission from Pratt & Whitney, a division of United Technologies.

• High-temperature corrosion: The Cr content of the majority of the alloys used in the turbine section of the gas turbine engine is below the requirement for corrosion resistance. Again, the reason for lower Cr content is to have other critical elements necessary to meet the structural capability requirement to carry load.

• Heat damage: Two of the consequences of high-temperature exposure are oxidation and corrosion, as explained earlier. Additional damages due to cyclic exposure to high temperature in the presence of fluctuating stresses come about by the process of thermal fatigue. The strengthening of the alloys helps to some degree in developing resistance to fatigue cracking. The overall protection against heat damage requires surface treatment of the alloys. For oxidation and corrosion, surface treatment by coatings is the only choice. The coatings provide barriers between the alloys and the outer environment. These coatings can be tailored to meet requirements for environmental resistance, for example, by increased Al and Cr content because they do not need to have load-bearing capability. Chapter 6 addresses oxidation- and corrosion-resistant coatings. An additional avenue to reduce heat damage to the alloys is to lower their temperature without sacrificing the performance of the turbine. This is addressed for hot components by thermally insulating them. A class of coatings called thermal barrier coatings in combination with active cooling accomplishes this function.

Often components undergo environmental damage such as chemical degradation reacting with deposits ingested from the outside. These deposits may infiltrate through chemical reaction into the interiors of the load-carrying walls. In such cases environmental barrier coatings are used to effectively protect the component surfaces from coming in contact with the deposits.

Nondestructive testing of the coating is an essential tool to monitor quality of new coatings and progressive degradation during their use. Understanding this technologically important area is vital.

Repair of coatings is another technologically important area, which also has a large financial component due to the high cost of coatings and coated hardware.

This book addresses, under one roof, most of the aspects of coatings discussed earlier. For better grasp of the subject matter, introductory materials essential to the understanding of the science and technology of coatings are covered in Chapters 2 and 3. Knowledge of how the coatings have fared in the real environment is described in Chapter 10 to tie into the earlier chapters on their processing, structure, and properties.

References

Cervenka M. Google Image. 2000.

Matějíček J, Vilémová M, Mušálek R, Sachr P, Horník J. The influence of interface characteristics on the adhesion/cohesion of plasma sprayed tungsten coatings. Coatings. 2013;3:108–125.

Meetham G.W. Requirements for and factors affecting high temperature capability. Mater. Des. 1988;9(5):244–252.

Stroosnijder M.F, Mevrel R, Bennett M.J. The interaction of surface engineering and high temperature corrosion protection,. Mater. High. Temp. 1994;12(1):53–66.

Chapter 2

Fundamental Concepts

Abstract

This chapter introduces the concept of the crystal structure of materials and the background needed for an understanding of the thermal, thermodynamic, kinetic, and mechanical responses of the materials when exposed to various elements of the high temperature environment.

Keywords

Activation energy; Arrhenius equation; Bernoulli's theorem; CALPHAD; Carnot engine; Closed thermodynamic system; Enthalpy; Fick's law of diffusion; Free energy; Gibbs free energy; Isolated system; Nonequilibrium thermodynamics; Open thermodynamic system; Thermal barrier coatings; Thermo-Calc

Background in the fundamental concepts of thermodynamics, kinetics of reactions, diffusion, crystal structure, phase equilibrium, and phase diagrams of alloys is essential to understand the selection, processing, and behavior of high-temperature coatings. These concepts are discussed briefly in this chapter.

2.1. Thermodynamic Concepts

The principles of thermodynamics are used to determine the spontaneity of many chemical and metallurgical phenomena and the direction in which they proceed. A few examples of practical applications of thermodynamics include understanding heat and work flow (nonequilibrium thermodynamics), study of efficiency of heat engines, processes for extraction of metals from ores, formation of alloys, precipitation and grain growth, and degradation of materials in service. To understand these processes, a number of thermodynamic parameters need to be defined and their interrelationships understood. The concepts, discussed next, will be specifically helpful in understanding the principles of ideal gas turbine engines and other power plants and identifying the thermodynamic parameters that affect their efficiencies. The concepts will also help understand the processes of oxidation and corrosion, phase and microstructure changes of high-temperature coatings, and their interactions with substrate alloys.

Thermodynamic Systems

If the content of a volume of space is selected for thermodynamic analysis, it is defined as a thermodynamic system. The volume may contain matter or only energy or both. This system is separated from the surrounding by its surface, which constitutes the system boundary. If matter or energy does not cross the system boundary, i.e., no matter or energy is being exchanged with the surrounding, then the system is called an isolated system. The universe, as we currently know it, is an example of an isolated system because there is nothing beyond it to exchange matter and energy with. If, however, no matter is being exchanged with the surrounding, but energy flows across the boundary as in the case of an inflated gas-filled balloon, which is gaining heat from the surrounding, the system is called a closed thermodynamic system. On the other hand, a system such as a gas turbine engine in which matter in the form of gases and energy in the form of heat and work are flowing in and out across its boundary with the surrounding is called an open system. At any instant of time, the volume inside the system separating it from the surrounding is called control volume. Fig. 2.10A shows a balloon, which is a closed system, while the depiction of the control volume of an open system with entrance and exit for matter and energy is shown in Fig. 2.10B. The systems described above can be understood and analyzed by studying the evolution of their thermodynamic parameters during changes of the system from one state to another. These changes may be cyclic when the various states and steps repeat themselves over time. Some of the relevant thermodynamic parameters are described here.

Enthalpy

Enthalpy H is the measure of the combination of internal energy E and the product of pressure P and volume V of a system. Thus H  =  E  +  PV. For example, if the system consists of an inflated balloon made of a thermally insulating rubber, the internal energy is the energy of the gas molecules inside the balloon, and the pressure is that of the ambient atmosphere. If a small quantity of heat dQ is added to this system, it will increase the internal energy by dE and induce a change in volume dV while the pressure remains constant at P. Thus, dQ  =  dE  +  PdV. For constant pressure, dQ  =  d (E  +  PV), which leads to dQ  =  dH. This relationship indicates that enthalpy is a measure of heat in the system, which is a composite of the thermal (E) and mechanical (PV) work. A change in enthalpy is related to the heat capacity at constant pressure, (dH/dT)p  =  (dQ/dT)p  =  Cp, where dT is the change in temperature. Integration gives

in which H0 is a constant and T is temperature in absolute (K) units. In the case of an open system such as a gas turbine engine, matter and energy entering the gas turbine at any instant of time contribute additional enthalpy H2  =  E2  +  P2V2, while the exiting gas will remove enthalpy equaling H1  =  E1  +  P1V1. Here the parameters H, P, and V with the subscripts 2 and 1 correspond, respectively, to the entering and exiting volumes of gas at the entry and exit locations. Thus, at that instant, there is a change in the enthalpy content of the gas turbine engine, which, for unit mass, works out to be ΔH  =  H2  –  H1.

Work

In mechanics, work is the result of a force moving through a distance. Four classical types of mechanical work take place: when (1) the boundary of the thermodynamic system moves such as in the case of a balloon expanding, (2) a shaft rotates as in a gas turbine engine, (3) an elastic body deforms as in a spring loaded with a force, and (4) a surface with a surface tension changes in area as in soap bubbles blowing.

Isothermal and Adiabatic Systems

Isothermal systems are those that maintain a constant temperature (dT  =  0) by exchanging heat energy with the surrounding. Adiabatic systems, on the other hand, are thermally insulated from the surrounding so that heat energy does not enter or leave the system (dQ  =  0). For an ideal gas (minimal interatomic forces), the pressure P, volume V, and temperature T in degree Kelvin are related through the gas equation PV  =  RT. For 1  g  mol of gas, R is the gas constant. In the case of an adiabatic system, the relationship is given by PVγ  =  constant, where γ is the ratio of the heat capacities, γ  =  Cp/Cv. For gases such as oxygen, nitrogen, and carbon dioxide, the value of γ lies between 1.4 and 1.5.

Entropy

Entropy is a measure of the order or randomness of the elementary units constituting a system such as the molecules or atoms of a gas. For example, if red and white billiard balls are arranged alternately in an array on a tray, the arrangement is highly ordered with low entropy. If the tray is shaken sufficiently, the arrangement will become randomized, with a red ball as likely to have a red neighbor as a white neighbor. In all processes, entropy maximizes. The quantitative aspect of entropy can more easily be understood with the balloon example. If we add heat dQ to the balloon kept at temperature T, the entropy change is given by dS  =  dQ/T  =  Cp dT/T. Integration provides S  =  S0  +  ∫Cp dT/T, in which S0 is a constant.

Free Energy

Free energy or, more appropriately, Gibbs free energy (after the inventor of the concept, J. Willard Gibbs) is a composite thermodynamic concept involving both enthalpy H and entropy S. It is given by G  =  H  −  TS. If a small change occurs in a system kept at constant temperature, the resulting free energy change is given by ΔG  =  ΔH  −  TΔS. The concept of Gibbs' free energy occupies a central place in the thermodynamics of reactions such as in combustion, oxidation, corrosion, electrolysis, and electrochemistry of fuel cells, to name a few. It is a measure of work done in the reactions described above.

A change in free energy determines the direction in which a process such as a chemical reaction proceeds. For example, at constant temperature, a decrease in free energy (ΔG negative) for the reaction 4/3Al  +  O2  =  2/3Al2O3 indicates that the reaction will go from left to right; that is, aluminum will spontaneously oxidize when in contact with oxygen. On the other hand, for the reaction 2FeO  =  2Fe  +  O2, the free energy increases (ΔG is positive), which means that the reaction will not go from left to right. In other words, iron oxide will not decompose spontaneously into elemental iron and oxygen. However, for the reaction 2Fe  +  O2  =  2FeO, at some temperatures, the free energy decreases (ΔG is negative), which indicates that iron will spontaneously oxidize to iron oxide. Thermodynamics does not predict the rate at which the oxidation or, for that matter, any reaction, proceeds. The rates are controlled by the kinetics of the process. Kinetics will be discussed in a later section. Equilibrium is defined as a state of constancy in which changes do not occur over time. For example, in the hypothetical reaction mA  +  nB  =  pC  +  qD, at equilibrium, as many atoms of A and B react to form C and D as the latter two react to reform A and B. In thermodynamic calculations, the absolute values of enthalpy, entropy, and free energy are never known and are seldom required. The calculations are based on changes in these parameters. To assess changes, a standard state is used as a basis relative to which all changes are measured. The standard state is defined as the state in which the pure substance (solid, liquid, or gas) exists at a pressure of 1  atm and temperature of 298°K (25°C). The absolute values of the parameters at standard state are generally indicated with a superscript such as G°.

Laws of Thermodynamics

The principles of thermodynamics are embodied in two universal laws known as the first law of thermodynamics and the second law of thermodynamics. The first law, which basically is the principle of conservation of energy, can be stated for a cyclic process as follows: When a system undergoes a cyclic thermodynamic change, the total heat supplied to the system from the surrounding equals the total work done by the system to the surrounding. The second law of thermodynamics, essentially an explanation of the direction of spontaneous processes, states that the entropy of a system undergoing change increases unless the change is reversible in which case the entropy remains constant.

Carnot Engine

As discussed in Chapter 1, high-temperature coatings are one of the enablers of heat engines such as gas turbines and steam turbines. The basic principle of these engines can be described thermodynamically without involving the details of the design of hardware, movement of parts, aerodynamics, heat transfer, and the like. The simple thermodynamic engine is called the Carnot Engine, in honor of Nicolas Léonard Sadi Carnot, who proposed the hypothetical concept. In this concept, explained in Fig. 2.11 (Balmer, 2011), the featureless engine receives an amount of heat Qin at temperature TH from a large hot reservoir whose temperature remains unchanged in this transaction. Part of the heat is converted to work Wout by the engine, while the remainder Qout is dumped into a large cold heat sink at temperature TL. Thus, from the first law of thermodynamics, the work output of the engine is Wout  =  Qin  −  Qout  =  QH  −  QL for a heat input to the engine QH and heat release to the sink QL. The efficiency of the engine η is the ratio of the work output divided by the heat input η  =  Wout/QH  =  (QH  −  QL)/QH  =  [1  −  (QH/QL)]. Because the transferred quantities of heat are proportional to the temperature in degree Kelvin, the engine efficiency can be written as η  =  [1  −  (TH/TL)]. This relationship is at the core of the drive over the years in the heat engine community to increase turbine operating temperatures to achieve higher efficiency by increasing TH, the hottest temperature in the engine, assuming that the coldest temperature TL cannot be further reduced. Application of high-temperature coatings on the engine hardware enables the design required increase of the turbine temperature TH without the associated component heat damage.

Steady Flow Energy Equation and Bernoulli's Theorem

One can apply the first law of thermodynamics to the control volume of an open thermodynamic system (Fig. 2.10B). An example of such a system is the gas turbine engine. As shown in the figure, in a time interval dt, an elementary mass dm with a velocity vf is leaving the system through the exit carrying with it per unit mass an amount of enthalpy hf, and potential energy gZf g being acceleration due to gravity. An equal amount of mass dm is flowing during the same time dt into the volume through the entrance, thus maintaining the steady state and adding enthalpy, kinetic energy, and potential energy, all the symbols with the subscript i. In addition, heat dQ is coming into the system as the associated arrow suggests while the system is doing the work dW. Application of the first law of thermodynamics results in the relationship:

Expanding enthalpy h as a sum of internal energy E and expansive work PV, the above equation can be written as

The above equation is called the steady flow energy equation (SFEE). This equation can be applied to open systems such as a gas turbine engine used for thrust generation (Brayton cycle), a steam turbine used for power generation (Rankine cycle), and a few others. A special case can be one in which temperature is constant (ΔE  =  0), no heat flow occurs (dQ  =  0), and there is no shaft work (dW  =  0); the SFEE reduces to

Volume V  =  dm/ρ, for unit mass; therefore, V  =  1/ρ and the above relationship reduces to

The last relationship is the well-known Bernoulli equation. It can be used to easily show how trade-offs occur between pressure and velocity in a gas turbine engine.

Equilibrium Constant

The concept of equilibrium constant is adopted from chemistry and is used in calculations relating to free energy changes. For the reaction 4/3Al  +  O2  =  2/3Al2O3, the equilibrium constant is given by K  =  [Al2O3]²/³/[Al]⁴/³[O2], where [ ] denotes concentration. Note that the concentration is raised to a power equal to the number of molecules (or atoms) participating in the reaction. The free energy change of the reaction at standard state is related to the equilibrium constant through the equation ΔG  =  ΔG°  +  RT ln K, where R is the gas constant, ln is the traditional symbol of the natural logarithm, ΔG is the free energy change in an arbitrary state, and ΔG° is the free energy change involving reactants and products in their standard state. When the reaction is in equilibrium, ΔG  =  0. This gives ΔG°  =  −RT ln K. The convention used in assessing concentration in reactions defines pure materials in either reactants or products as having a concentration of unity. Thus [Al2O3] and [Al] are each unity, resulting in ΔG°  =  −RT ln (1/[O2])  =  RT ln [O2].

Activity Coefficient

In the foregoing discussion, the concentrations [Al2O3] and [Al] each have been taken as unity because they are assumed to be in their standard state as pure solids. However, this assumption is not valid in many instances where Al exists in an alloy or a solution. In such cases, the concept called activity is used instead of concentration. Thus, for a Ni base alloy containing 6% aluminum, knowing that the initial oxidation product is Al2O3, the oxidation reaction needs to be written as 4/3Al (alloyed in Ni)  +  O2  =  2/3Al2O3 with the equilibrium constant K  =  [Al2O3]²/³/[aAl]⁴/³[O2], where aAl is the activity of aluminum in the alloy. Because the product oxide is still pure Al2O3, its concentration (or activity) is unity. The free energy change is now given by ΔG°  =  −RT