The Pennsylvania State University The Graduate School Department of Physics

A SOLID-STATE HEAT PUMP USING ELECTROCALORIC CERAMIC ELEMENTS

A Dissertation in Physics by Matthew G. Hilt c 2009 Matthew G. Hilt

Submitted in Partial Fulllment of the Requirements for the Degree of

Doctor of Philosophy May 2009

The dissertation of Matthew G. Hilt was reviewed and approved* by the following:

J. D. Maynard Professor of Physics Dissertation Adviser Chair of Committee

G. D. Mahan Professor of Physics

Peter Schier Professor of Physics

Victor Sparrow Professor of Acoustics

Jayanth Banavar Professor of Physics Head of the Department of Physics

*Signatures are on le in the Graduate School.

iii

Abstract

The thermoacoustic cycle is a robust thermodynamic cycle that can be generalized to describe and develop an all-solid-state heat pump using generic caloric elements. Ferroelectric barium strontium titanate (BST) and relaxor lead magnesium niobate lead titanate (PMN-PT) are two candidate materials for the caloric elements using the electrocaloric eect. I developed a procedure to repeatably produce high quality BST and PMN-PT ceramics so that the electrocaloric and dielectric properties could be accurately measured. The measured electrocaloric properties serve as the baseline numbers for calculating the performance of a proposed all-solid-state cooler based on thermoacoustic principles.

iv

Table of Contents

List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chapter 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Refrigeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.1 1.1.2 1.2 Early history . . . . . . . . . . . . . . . . . . . . . . . . . . . Modern Refrigerators . . . . . . . . . . . . . . . . . . . . . .

viii x xii 1 4 5 5 8 9 10 11 13 13 15 20 21 24 27

Thermoacoustics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 Thermoacoustics, quantied . . . . . . . . . . . . . . . . . . .

1.3 1.4

Solid-state refrigeration . . . . . . . . . . . . . . . . . . . . . . . . . Perovskite ferroelectrics . . . . . . . . . . . . . . . . . . . . . . . . . 1.4.1 1.4.2 1.4.3 Ferroelectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . Relaxors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ferroelectric thermodynamics . . . . . . . . . . . . . . . . . .

Chapter 2. General comments about ceramics and their processing . . . . . . . . 2.1 Preparing ceramic-grade powder . . . . . . . . . . . . . . . . . . . . 2.1.1 2.1.2 Mixing the components . . . . . . . . . . . . . . . . . . . . . Calcining the powder . . . . . . . . . . . . . . . . . . . . . . .

v 2.1.3 2.2 Grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 31 31 33 35 38 39 40 41 42 47 48 50 56 61 66 66 67 67 69 72 75

Preparing ceramic samples . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 2.2.2 2.2.3 Binder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pressing ceramic pellets . . . . . . . . . . . . . . . . . . . . . Sintering the pellets . . . . . . . . . . . . . . . . . . . . . . .

2.3

Preparing samples for measurement . . . . . . . . . . . . . . . . . . . 2.3.1 Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.4

Measurements on ceramic wafers . . . . . . . . . . . . . . . . . . . . 2.4.1 2.4.2 Physical property measurement methods . . . . . . . . . . . . Electrical property measurement methods . . . . . . . . . . .

Chapter 3. Electrocaloric eect in barium strontium titanate . . . . . . . . . . . 3.1 3.2 3.3 3.4 Ferroelectric-Paraelectric transition in BST . . . . . . . . . . . . . . Sample preparation protocol . . . . . . . . . . . . . . . . . . . . . . . Electrical properties measurement . . . . . . . . . . . . . . . . . . .

Comparison to other results . . . . . . . . . . . . . . . . . . . . . . .

Chapter 4. PMN-PT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 4.2 Crystal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Relaxor transition in PMN-PT . . . . . . . . . . . . . . . . . . . . . 4.2.1 4.3 4.4 Transition temperature for PMN-PT . . . . . . . . . . . . . .

Single crystal PMN-PT . . . . . . . . . . . . . . . . . . . . . . . . . Ceramic PMN-PT . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.1 XRD of PMN-PT powder . . . . . . . . . . . . . . . . . . . .

vi 4.4.2 4.4.3 4.5 Electrical property measurements on ceramic PMN-PT . . . 76 79 82 90 93 93 94 100 102 105 108 108 109 109 110 111 113 113 113 113 114

Results for (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15 . . . . .

Comparison to other measurements . . . . . . . . . . . . . . . . . . .

Chapter 5. An electrocaloric solid state heat pump . . . . . . . . . . . . . . . . . 5.1 A theoretical model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1.1 5.1.2 5.2 5.3 A quick review of thermoacoustics . . . . . . . . . . . . . . . Generalizing the thermoacoustic cycle . . . . . . . . . . . . .

Description of device . . . . . . . . . . . . . . . . . . . . . . . . . . . Predicted performance using ferroelectric ceramic elements . . . . . .

Chapter 6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Appendix A. Protocol for preparing ceramics . . . . . . . . . . . . . . . . . . . . A.1 BST Protocol, July 2007 . . . . . . . . . . . . . . . . . . . . . . . . . A.2 PMN-PT Protocol, July 2008 . . . . . . . . . . . . . . . . . . . . . . A.2.1 Stage I: MgNb2 O6 preparation . . . . . . . . . . . . . . . . . A.2.2 Stage II: 0.92PMN- 0.08PT preparation . . . . . . . . . . . . A.2.3 Stage III: Pressing 1/2 ceramic disks . . . . . . . . . . . . . Appendix B. Perkin Elmer 4400 Operators Reference . . . . . . . . . . . . . . . B.1 Start up procedure: . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.1.1 Start up from shutdown: . . . . . . . . . . . . . . . . . . . . . B.1.2 Start up from overnight: . . . . . . . . . . . . . . . . . . . . . B.2 Automatically controlled operating procedures: . . . . . . . . . . . .

vii B.3 Sputtering Procedures: . . . . . . . . . . . . . . . . . . . . . . . . . . B.3.1 DC Sputter Deposition: . . . . . . . . . . . . . . . . . . . . . B.3.2 RF Sputter Deposition: . . . . . . . . . . . . . . . . . . . . . B.3.3 RF Sputter etching: . . . . . . . . . . . . . . . . . . . . . . . B.4 Shutdown procedures: . . . . . . . . . . . . . . . . . . . . . . . . . . B.4.1 Overnight: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.4.2 Longterm shutdown: . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 115 115 116 117 117 117 118

viii

List of Tables

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

Compositional analysis of PMN-PT crystal . . . . . . . . . . . . . . . . Furnace instructions for cleaning crucibles . . . . . . . . . . . . . . . . . Powder to make 50 gm Ba0.67 Sr0.33 TiO3 . . . . . . . . . . . . . . . . . Powder to make 50 gm MgNb2 O6 . . . . . . . . . . . . . . . . . . . . . . . . .

22 23 25 25 25 29 29 29 33 36 37 39 51 56 70 74

Powder to make 50 gm (PbMg1/3 Nb2/3 O3 )0.92 (PbTiO3 )0.08

Furnace instructions for calcining BST . . . . . . . . . . . . . . . . . . . Furnace instructions for calcining magnesium niobate . . . . . . . . . . . Furnace instructions for calcining PMN-PT . . . . . . . . . . . . . . . . Furnace instructions for binder burnout . . . . . . . . . . . . . . . . . .

2.10 Furnace instructions for sintering BST . . . . . . . . . . . . . . . . . . . 2.11 Furnace instructions for sintering PMN-PT . . . . . . . . . . . . . . . . 2.12 Furnace instructions for annealing PMN-PT ceramics 3.1 3.2 4.1 4.2 5.1 . . . . . . . . . .

Expected and observed XRD angular peaks in BST . . . . . . . . . . . . Corresponding grain sizes of dierent sintering conditions . . . . . . . . Eect of crystal orientation on the electrocaloric eect in PMN-PT . . . Compositional analysis of PMN-PT crystal . . . . . . . . . . . . . . . . Cooling power at a given temperature span (lift) of a thermoacoustic-like device operating at 30 Hz . . . . . . . . . . . . . . . . . . . . . . . . . .

99 102

5.2

SSHP performance using 1.0 K caloric elements . . . . . . . . . . . . . .

ix 5.3 SSHP performance using BST and PMN-PT ceramic elements . . . . . 103

List of Figures

1.1 1.2 1.3 1.4 2.1 2.2 2.3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.1 4.2 4.3

The vapor compression cycle[1] . . . . . . . . . . . . . . . . . . . . . . . The thermoacoustic cycle along a solid-uid interface . . . . . . . . . . . Perovskite crystal structure[27] . . . . . . . . . . . . . . . . . . . . . . . Ferroelectric and relaxor polarization . . . . . . . . . . . . . . . . . . . . Die used to press ceramic pellets . . . . . . . . . . . . . . . . . . . . . . Setup to measure the electrocaloric properties of BST . . . . . . . . . . Schematic of dielectric constant measurement . . . . . . . . . . . . . . . A compilation of measured Curie temperatures in BST systems . . . . . XRD analysis of BST powder . . . . . . . . . . . . . . . . . . . . . . . . Particle size analysis of BST powders . . . . . . . . . . . . . . . . . . . . SEM micrograph showing carbon contamination in BST ceramics . . . . SEM micrographs of fracture cross-sections of BST ceramics . . . . . . . Dielectric constant of BST ceramics with dierent electrodes . . . . . . The dielectric constant of Ba0.67 Sr0.33 TiO3 . . . . . . . . . . . . . . . . Electrocaloric eect in BST at 1 MV/m . . . . . . . . . . . . . . . . . . Electrocaloric eect in BST as a function of temperature and applied eld Phase diagram for PMN-PT mixtures[62] . . . . . . . . . . . . . . . . . Mask for electroding rectangular plates . . . . . . . . . . . . . . . . . . . High temperature electrocaloric measurement setup . . . . . . . . . . . .

6 8 12 14 34 43 44 49 52 54 55 57 59 62 63 64 68 71 73

xi 4.4 4.5 4.6 4.7 Electrocaloric eect in single crystal (PbMg1/3 Nb2/3 O3 )0.8 (PbTiO3 )0.2 XRD of calcined 0.90PMN-0.10PT powder . . . . . . . . . . . . . . . . . XRD of a sintered 0.90PMN-0.10PT ceramic . . . . . . . . . . . . . . . Eect of dierent electrodes on dielectric constant in ceramic 0.85PMN0.15PT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.8 4.9 Eect of dierent electrodes on electric eect in ceramic 0.85PMN-0.15PT Dielectric constant of ceramic (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15 . 80 81 83 84 86 87 91 93 95 101 74 77 78

4.10 Electrocaloric eect in ceramic (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15 4.11 Strip chart recording of the electrocaloric eect in PMN-PT . . . . . . . 4.12 Strip chart recording of joule heating in a ceramic sample . . . . . . . . 5.1 5.2 5.3 5.4 A heat switching heat pump . . . . . . . . . . . . . . . . . . . . . . . . . The thermoacoustic cycle . . . . . . . . . . . . . . . . . . . . . . . . . . A generalized Stirling-like heat pump cycle . . . . . . . . . . . . . . . . Proposed design of all solid state heat pump . . . . . . . . . . . . . . . .

xii

Acknowledgments

I would like to thank my advisor and my committee for their guidance and their assistance throughout my graduate research. I would like to thank Omega Piezo Technologies, Inc. for technical support and the use of their facilities while preparing materials. I would like to thank the technicians at the Materials Research Lab for countless hours of discussion and help rening my sample preparation and characterization techniques. Finally, I would like to thank my patient wife for supporting me through the completion of this research.

Chapter 1

Introduction

Perhaps the most inuential technological developments in human history are agriculture, medicine, and the atomic theory of matter. Supplementing all of these great advances, refrigeration has emerged as one of the greatest recent advancements. Refrigerated storage allows for better food preservation and transportation over longer distances, mitigating the eects of seasonal variance in farming conditions. Local droughts and regional crop failures no longer lead to mass starvation and famine. The preservation of medicines and vaccines have led to radical advances in the treatment and even the elimination of many diseases. Study of matter at its coldest temperatures has given us insight in to fundamental interactions of the structure of matter. Despite this progress, problems arising from our implementation of refrigeration are threatening each of these advances. For over one hundred years vapor compression techniques have been the gold standard for the design of refrigeration and air conditioning systems. The most ecient uids to drive these systems were Freon gases or chlorouorocarbons (CFCs). As CFCs entered the atmosphere they catalyzed a reaction with the atmospheric ozone, depleting the natural barrier against ultraviolet (UV) radiation. The rise in UV radiation exposure has led to increased rates of skin cancers, impacting public health[9]. Eventually the world adopted the Montreal Protocol eectively banning CFC use.

2 Though the replacement for CFCs, hydrochlorouorocarbons (HCFCs), do not deplete the ozone, they feed a growing problem: atmospheric global warming. While carbon dioxide is the most publicized contributor to global warming, HCFCs have global warming potential 3000 times that of an equivalent volume of carbon dioxide[14]. New advancements in refrigeration are needed to extend the benet of articial cooling, but also limit, eliminate, or hopefully reverse the disastrous environmental consequences. Liquids and solids are attractive candidate media for new refrigeration techniques, both because their higher mass density allows a higher energy density, and because they avoid the release of harmful gases. The main drawbacks to current alternatives are twofold: energy eciency and scalability. This thesis explores an all-solid-state alternative to existing refrigeration technology with several target goals: 1. Identify an appropriate solid-state caloric eect which could be used in a scalable refrigeration device. 2. Find a specic material which maximizes the magnitude of the solid-state caloric eect. 3. Determine a design for a device incorporating the material so that its caloric property results in a temperature lift and cooling power suitable for a real refrigerator. To acheive target 1, the remainder of this chapter reviews various refrigeration schemes and shows that a property of solids referred to as the electrocaloric eect could be used for refrigeration. For target 2, a search of the literature indicated that there were some electrocaloric materials which could be used to make a real, practical refrigerator. Specically, materials literature implied or reported extremely large values of the

3 electrocaloric eect in both barium strontium titanate, Bax Sr1x TiO3 , (BST) and lead magnesium niobate-lead titanate, (PbMg1/3 Nb2/3 O3 ) (PbTiO3 )1x , (PMN-PT). At x this point it was believed that one could simply locate a company capable of making these materials and order a quantity suitable for research. With considerable suprise, it was discovered that no such company is currently in existance worldwide; a company proposed to use its best eort to make the desired material but fell considerably short. The results are documented in Chapter 2. A search to collect the necessary information for fabricating these materials in house was undertaken; this proved to be far more dicult than it should have been. Many papers omitted what turned out to be critical steps or reported procedures that were at odds with every other protocol in the eld. At least one thesis presumably containing detailed steps was not made available even after both a direct, informal request and a formal request through the library of the granting institution. Despite the diculties, excellent materials, which were in many aspects superior to those found in the materials literature, were made in house. Contrary to what seems to be the apparent practice in the eld of materials research, the full details, as well as general concepts of the materials processing are provided in Chapter 2 and in Appendix A. It was with further dismay that the values of the electrocaloric eect measured in the high quality materials of this thesis were somewhat smaller than values claimed in some of the materials literature. This seems to be another feature of materials literature: papers which report unbelievable results should, in fact, not be believed. The reputation of the research lab preparing the material must be known before any result reported in the

4 materials literature can be accepted. Another problem with some results in the literature may have been poor practices used to measure and report the material properties. In this thesis, the methods used to characterize the materials followed the high standards of condensed matter and low temperature physics, and are reported in full detail in latter part of Chapter 2. Furthermore, the raw data are presented unmodied, and any calculations based on the data are fully explained. Data from measurements on BST samples are presented in Chapter 3 and data from PMN-PT samples are presented in Chapter 4. Concerning target 3, a device based on the thermoacoustic eect [discussed below] was designed. However, setbacks encountered from having to reproduce and verify the materials literature precluded the construction of an actual device. A rst principles theory of operation was developed to predict the performance of the device and an analysis of using BST and PMN-PT as caloric elements in such a device is presented in Chapter 5. To properly introduce a conceptually new heat pump, one must have a background on refrigeration techniques and the relevant thermodynamics of the electrocaloric eect, and this is presented next.

1.1

Refrigeration
Any physical mechanism which can displace heat further than it will naturally

diuse can be adapted to form a heat pump or refrigerator. Many thermodynamic eects exist which can repeatedly generate changes in heat. A most fundamental dierence

5 between all forms of heat engine or pump is the manner in which heat is used to do work or the manner in which work is done to move heat.

1.1.1

Early history Early examples of heat engines based o natural work are waterfalls and wind-

mills. Evaporation and condensation do work against gravity, creating a reservoir of water at a higher altitude. As the water ows downhill to a reservoir at a lower gravitational potential, the current is used to drive mechanical wheels. Windmills similarly rely on rotors driven by a uid ow, though the moving gas comes from nonuniformity in atmospheric temperature and pressure. The earliest forms of refrigeration were also based on natural mechanisms. Ancient Egyptians used evaporative cooling systems[12]. Advances in shipping and land transportation lead to a boom in the ice trade during the eighteenth and nineteenth centuries[12]. While ice has been stored under insulation since ancient times, by the eighteenth century it could be transported from colder regions. Ice was sold in large blocks which were placed in chests, creating a reservoir at 0 C. A great boom in refrigeration came at the end of the nineteenth century with the advent of mechanical vapor compression refrigerators.

1.1.2

Modern Refrigerators The refrigerator as it is currently known started with the vapor compression cycle

in the 1850s with ammonia-based refrigerants. In the 1920s, CFC gasses were discovered with very large thermal expansion coecients near room temperature. This expansion

Fig. 1.1. The vapor compression cycle[1]

7 was exploited by compressing the gas in one location and then allowing the gas to expand through a long network of tubes. A schematic of a vapor compression refrigerator is shown in gure 1.1[1]. A mechanical compressor condensed the CFC gas, dumping heat into the environment. The condensed gas was then forced through a long network of coils wherein the gas expanded drawing heat into the gas from the coils. The gas was then returned to the compressor. As the compressor is maintained at room temperature, the free expansion of the gas in the coils cools the coils below room temperature. Though the technology is over 150 years old, vapor compression refrigeration is still the workhorse in most refrigeration applications. CFC gas has been banned by the Montreal Protocol due to the catalyzing eect CFCs have in breaking down atmospheric ozone[9]. A dierent class of gases, HCFCs, had less ideal thermodynamic and transport properties; however, they were good substitutes for CFC gases in vapor compression refrigerators. Unfortunately, because of the relatively low concentration of HCFC gases in the atmosphere, the infrared absorption spectrum of HCFC gases make them 1000 to 3000 times worse than carbon dioxide as green house gases. As HCFCs are emitted, they settle in the upper atmosphere. HCFCs are man-made; they have never been produced naturally. The photoabsorbtion spectrum of HCFCs is dierent than carbon dioxide, with the result that light that had previously passed through the atmosphere is now being absorbed. As the atmosphere is normally 1% carbon dioxide, additional releases of carbon dioxide are only slowly increasing the amount of light absorbed because it is in the same frequency spectrum that has always been absorbed. More nations are focussing on legislation to limit emissions to combat global warming, and more research will be needed in alternate refrigeration cycles based on completely environmentally inert uids

8 or solid state techniques. One technology using environmentally-safe uids as a working medium is thermoacoustics.

1.2

Thermoacoustics
A simple picture of a sound wave is a small pressure oscillation within a uid

about some equilibrium coordinate. Considering the ideal gas law, P V = nRT , if volume were held constant that pressure oscillation would correspond to a temperature oscillation. This is not a useful means of transporting heat, however, because these oscillations happen on a time scale faster than the heat is able to be displaced. Normal sound propagation is therefore adiabatic.

Fig. 1.2. The thermoacoustic cycle along a solid-uid interface

9 If the parcel of gas is placed next to a solid plate, parallel to the displacement of the gas, the gas is able to transfer heat to and from the solid. The gas can expand above the plate, drawing a small amount of heat from the solid. The gas then moves and compresses further down the plate, dumping a small amount of heat into the solid. The gas then returns to its initial position, repeating the cycle. This is the thermoacoustic eect and the cycle is shown in gure 1.2. The displaced heat would naturally travel back down the solid to restore thermal equilibrium. However, the gas displaces more heat per unit time than the solid is able to transport, breaking a symmetry. On either side of the gas parcel is another gas parcel, and each individual temperature oscillation acts as a bucket brigade converting the small local temperature oscillations into a temperature gradient along the length of the solid. Quantitatively, the presence of the uid-solid interface introduces a phase shift between the pressure oscialltion, pa , and the volume oscillation, ua .

1.2.1

Thermoacoustics, quantied Using the approximation that a uid is oscillating parallel to a solid plate in a very

open channel, the cooling power for a thermoacoustic cycle is found by the relation[50]:

1 Q = Tm p pa ua (1 RT ) 2

(1.1)

where is the perimeter of the channel, =

2/ is the thermal penetration depth,

Tm is the average temperature, p is the thermal expansion coecient of the uid, pa is the amplitude of the pressure oscillation, ua is the amplitude of the velocity oscillation

10 and RT is the ratio of established temperature gradient to a characteristic or critical temperature gradient. The acoustic wave equations have been more properly solved including thermal and viscous loss eects and geometries beyond open parallel plates[50, 51]. As devices are being scaled to kilowatt levels of refrigeration power, the thermoacoustic equations are being tested to incorporate non-linear eects such as mass streaming[46]. In addition to switching to inert gases using thermoacoustic refrigerators, research into alternatives to vapor compression refrigeration has focussed on solid-state refrigeration.

1.3

Solid-state refrigeration
Most existing solid-state coolers are based on one of two physical eects: thermo-

electrics and adiabatic demagnetization of magnetocaloric materials. The basis of the thermoelectric eect is the work of Seebeck, Peltier and Thomson during the mid-1800s. When a junction of dissimilar metals experience a temperature gradient, a small current is generated. This eect is reversible, where the ow of a current through a metal junction warms or cools the junction. Advances in the 1950s led to the discovery of semiconductor-based thermoelectric materials which allowed the creation of coolers capable of operating at temperature spans of over 30 K. Ongoing thermoelectric research is seeking to tailor the physical properties of semiconducting thermoelectric materials with the ultimate goal of achieving larger temperature changes with smaller applied currents in an eort to overcome the Joule heating limits of thermoelectric materials[30]. Magnetocalorics is the interaction of magnetism and heat. On the application of an external magnetic eld, the magnetic domains in a ferromagnetic material orient

11 along the direction of the applied eld, raising the entropy and therefore the temperature in an isolated system. As the magnetic eld is removed, the magnetic dipoles are able to relax and absorb some heat from the materials crystal lattice, lowering the materials temperature. The largest observed eects occur in gadolinium-based composites with 11 to 17 K magnetocaloric temperature changes occurring upon the application and removal of up to 5 T magnetic elds[21, 54, 61, 69]. Cryogenic adiabatic demagnetization refrigerators have been built to continuously maintain a sensor at 4 K, cooled from 10 K[11]. Current magnetocaloric refrigerators need either large superconducting magnets or heavy permanent magnet arrays to generate the large magnetic elds needed to run the devices[21]. Even these devices can only cool over a 20 to 30 K span. A promising alternative to magnetocaloric ferromagnetic materials are electrocaloric ferroelectric materials. Most of the interesting new electrocalorics come from a class of materials known as perovskites.

1.4

Perovskite ferroelectrics
Perovskite refers to both the mineral perovskite CaTiO3 and crystalline material

with cubic structure and the generic unit cell ABO3 . Oxygen atoms form an octahedral cage around the B-site ions while the A-site ions form a simple cubic lattice, as shown in gure 1.3. The atoms in the B-site cages can often be pulled slightly above and below the equilibrium position which give rise to polarizability and ferroelectric and paraelectric properties.

12

Fig. 1.3. Perovskite crystal structure[27]

13 1.4.1 Ferroelectrics Ferroelectricity is analogous to ferromagnetism in magnetic materials. Weak perturbative elds lead to the formation of permanantly polarized electric dipole domains at low temperatures. As the temperature reaches the Curie temperature, the ferroelectric ordering is quickly lost and the electric domains enter a paraelectric phase. In the paraelectric phases, the electric dipoles are highly mobile and align in response to an applied electric eld, but will not maintain a net polarization when the eld is removed.

1.4.2

Relaxors What separates relaxor materials from similar ferroelectric materials is the nature

of the phase transition. As the temperature is lowered below the Curie temperature, ferroelectrics see a sudden rise in permanent polarization that begins to saturate about 10 K below the Curie temperature. This rise manifests itself as a very sharp peak in the dielectric constant, often occurring in the span of 20 K and almost no thermal hysteresis. Relaxors, on the other hand, see a gradual rise in polarization at the Curie temperature followed by a transition to a ferroelectric-like rise in polarization below the Curie temperature. This manifests itself as a very broad peak in the dielectric constant with a strong hysteresis and a dependence on the frequency at which the dielectric constant is measured. These two behaviors are shown in gure 1.4. The data have been scaled to normalize dielectric peak heights, but the temperature data is not scaled. The ferroelectric dielectric constant data have been plotted as the dashed curve towards the left hand side of the graph. The relaxor dielectric constant data are plotted as the solid curve towards the right hand side of the graph. The ferroelectric has a Curie temperature

14

Fig. 1.4. Ferroelectric and relaxor polarization

15 of 21 C. The relaxor has a freezing temperature which occurs around 100 C and a Curie temperature which occurs at 72 C. For both the ferroeletric and the relaxor, the lower curve represents data taken upon heating the sample and the upper curve represents data taken upon cooling the sample. Arrows have been imposed over the data to indicate the curves corresponding to heating and cooling the sample. Both samples were measured at a frequency of 1000 Hz. Relaxors are analogous to a spin glass in magnetic systems. The Curie temperature refers to the temperature at which the onset of permanent polarization begins; the temperature at which the transition to a ferroelectric-like rise in polarization occurs is called the freezing temperature, a term borrowed from spin-glass literature. Another characteristic of relaxors is a frequency dependence of the dielectric constant. In the region of the phase transition, a larger dielectric constant is measured at lower frequencies. Above the transition region, the dielectric constant is independent of frequency. The divergent results typically begin at the Curie temperature and the dielectric constant is largest at the freezing temperature.

1.4.3

Ferroelectric thermodynamics In any material, there exists an electric susceptibility describing the capacitance

of a parallel-plate capacitor made with that material between the plates. The dielectric constant, is found from the relation:

D Eq

(1.2)
T

16 where D is the electric displacement, Eq is the electric eld[17]. Ferroelectrics exhibit very large dielectric properties near the phase transition. In ferroelectric materials, there is a permanent polarization, Ps , in addition to the electric displacement. In the following discussions on ferroelectrics, polarization P refers to the total contribution, dened as:

P = Ps + Eq = Ps + (1 + ) o Eq

(1.3)

The temperature derivative of polarization is called the pyroelectric coecient, pq , given as: pq = P . T E q (1.4)

Given that the polarization is the charge per unit area, consider polarization changing as a function of time in the material. Expanding the derivative:

dP 1 dq dP dT = = dt A dt dT dt

(1.5)

where A is the area. We call Ipyro = dq/dt the pyroelectric current. We can rearrange this equation, Ipyro = A P dT dT = Apq T E dt dt q (1.6)

to show the dependence of the pyroelectric current on the pyroelectric coecient and a time-dependent temperature. The converse eect of pyroelectricity is the electrocaloric eect.

17 The electrocaloric eect is derived by considering a temperature change resulting from the application of an electric eld at constant entropy. An electrocaloric coecient, q can be dened as follows:

q (Eq ) =

T Eq

=
S

(Eq , T ) (T, S) (T, S) = (Eq , S)) (Eq , S) (Eq , T ) S Eq =

T

=T

1 T
S T E q

T CE

S Eq

(1.7)
T

where CE is the heat capacity at constant electric eld and S is the entropy. Through
q

a Maxwell relation we nd that

S Eq

=
T

P = pq . T E q

(1.8)

To nd an electrocaloric temperature change, TE resulting from the application of an

q

electric eld, Eq , integrate the electrocaloric coecient in equation 1.7,

Eq o Eq 0

TEC =

q dEq =

T p (E )dEq CE q q
q

T CE

Eq 0

pq (Eq )dEq .

(1.9)

It has been suggested[20] that below the ferroelectric transition temperature, the pyroelectric coecient is independent of electric eld. Using this assumption, equation 1.9 simplies to TEC = T p E CE q q
q

(1.10)

and the observed electrocaloric eect should be linear with respect to the applied eld.

18 Well above the critical region the material should be paraelectric and there should be no remnant polarization. The only contribution from the polarization would then be

P =

o Eq

(1.11)

where

is the dielectric constant dened in equation 1.2 and o is the permittivity of

free space. Integrating equation 1.9 using this assumption yields

o T E2. 2 CE T q q

(1.12)

Equation 1.12 implies that the electrocaloric eect should increase as the square of the applied eld above the transition temperature. The polarization would be more properly dened by including the internal contribution of the polarization using the electric displacement Dq dened as

Dq = o Eq +

o Eq .

(1.13)

The dielectric susceptibility, , is dened as

=1+ .

(1.14)

Using to dene the electrocaloric eect in the perovskite ceramics is not necessary, however, because tends to be very large. At the Curie temperature in BST, is typically over 1,000. is 20,000

or larger. Even well outside the critical region

19 Just a fundamental description of the thermodynamics of ferroelectric materials is not enough to produce electrocaloric materials. An extensive study in the process of preparing high-quality ceramic materials was undertaken to produce electrocaloric ceramics capable testing the electrocaloric eect as a refrigeration mechanism. A protocol to prepare two ferroelectric ceramics, barium strontium titanate (BST) and lead magnesium niobate-lead titanate (PMN-PT), was developed. Samples of both BST and PMN-PT were measured to determine the maximum possible electrocaloric eects. Finally, a complete theoretical framework and a design for an electrocaloric refrigerator was developed to evaluate the practicality of using the electrocaloric eect in a solid-state refrigerator.

20

Chapter 2

General comments about ceramics and their processing

To prepare research-grade ceramics, one must pay careful attention to seemingly insignicant details. Often exotic elements with complex reaction mechanisms are combined in a precise order to form a new material. Impurities on the order of 1 part in 1000 can radically alter ceramic properties. Even the materials forming electrodes for measurements of electrical properties can be the dierence between observing a physical eect and observing practically nothing. Through an exhaustive process, a protocol to reproduce high-quality ferroelectric ceramics was established. Protocols for both barium strontium titanate (BST) and lead magnesium niobate-lead titanate (PMN-PT) were developed through this thesis; step-by-step details of both protocols are presented as Appendix A. BST, Bax Sr1x TiO3 , is made in a single calcination process using barium carbonate, BaCO3 , and strontium carbonate, SrCO3 , and titanium dioxide, TiO2 . The decomposition of the carbonates in to metal oxide and carbon dioxide regulates the reaction of the barium oxide, strontium oxide and titanium dioxide so that the powder ends up in the proper crystalline phase. PMN-PT, (PbMg1/3 Nb2/3 O3 ) (PbTiO3 )1x , must be made in a double calx cination process to avoid unwanted crystalline phases. First, magnesium oxide, MgO, and niobium (V) oxide, Nb2 O5 are reacted to form magnesium niobate, MgNb2 O5 . The

21 magnesium niobate (MN) is then mixed with lead oxide, PbO, and titanium dioxide and reacted to form PMN-PT. The preparation of high-quality ceramics begins with preparing high-quality reacted powder.

2.1

Preparing ceramic-grade powder

Many considerations must be taken into account to make high-quality, ceramic-

grade powder. Proper stoichiometry is essential to ensure that there is no batch-to-batch variance in sample properties. Many steps involve transfer of ingredients and exposure to solvents, each of which runs a risk of contaminating the powder. Even uncontrolled environmental factors, such as loss of air conditioning during powder processing can produce unexpected results. Ferroelectric properties, such as the phase transition temperature, depend highly on mixing components in the proper ratio. Table 4.2 shows the full compositional analysis of a PMN-PT single crystal that had a phase transition at an unexpected temperature. The ratio of ions suggest that this is (PbMg1/3 Nb2/3 O3 )0.82 (PbTiO3 )0.18 , however, using this concentration the sample has a magnesium deciency of 22%. Theoretically, the transition temperature should occur at 88 C; the transition in the sample occurred near 141 C. Note, the calculation to nd the composition assumes the number of oxygen molecules in the unit cell and then nds the amounts of other ions present relative to the assumed number of oxygen molecules. Small levels of contaminants can cause other undesirable eects. Some of our early ferroelectric samples exhibited the behavior of a semi-conductor. The resistivity of BST should be greater than 1013 m. When measured under the small bias eld of

22 Ion Pb Mg Nb Ti O Number per unit cell 0.98 0.21 0.57 0.20 3 Expected 1.00 0.27 0.55 0.18 3 Percent dierence 2.1 21.8 3.6 8.3 0

Table 2.1. Compositional analysis of PMN-PT crystal

a digital multimeter, the sample resistivity was 109 m or greater. Under an electric eld of 0.2 MV/m the resistivity dropped to 104 m. Further analysis showed these samples were contaminated with < 0.5% mol of calcium. The calcium contamination was eventually traced to crucibles that had been washed in State College water, a richer source of calcium than milk. To avoid contamination, all tools, crucibles, storage containers and mixing vessels that contact powder should be cleaned with the following procedure: wash the item in reagent grade acetone (with a purity greater than 99.5%) then dry the item with helium gas. Any component that will go inside a furnace, such as a crucible, should be cleaned as follows: heat the item to 1200 C in a furnace and let it set for 6 hours at that temperature. This procedure will help burn o any contaminants that may have become bound to the surface of the object. Any object used in the making of lead-free powders must only be used to make lead-free powders. If a furnace has ever been used in the production of lead-based powders, it must be assumed to be contaminated with lead and can be used for only the production of lead-based powders. Also, any tool, crucible, storage container or other item used in the making of a lead-based powder must be used only in the making of other lead-based powders.

23 All powders and ceramics were prepared in a Sentro-Tech model ST-1600 furnace with a programmable interface. To clean crucibles the program in table 2.2 should be used. The C0X instructions are temperature set points in C and the T0X instructions are times in minutes. The programming logic is: temperature, time to next temperature, repeat. A time instruction of -121 is the furnaces code to shutdown.

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 200 1400 200 1400 200 0 -121

Table 2.2. Furnace instructions for cleaning crucibles

In addition to a clean working environment, high-quality ingredients are needed to produce high-quality powder. All metal-oxide powders used to create the ceramic powders should be reagent grade or better. All solvents throughout the process also need to be reagent grade or better. No water should ever be allowed to contact powder of any kind. Even the water vapor in a humidity-controlled air conditioned environment can degrade BST ceramics. If a BST ceramic wafer is left exposed to air for six months, the skin of the pellet will change from a light brown color to a dark brown color, and then

24 eventually turn purple. All powders should be stored in sealed containers. Ceramics without electrodes should be stored in a desiccator. With close attention to cleanliness, purity and environmental control, the process to make ceramic samples begins with the mixing of constituent metal oxide powders.

2.1.1

Mixing the components Given all of the attention that must be paid to consistently produce powder with

similar properties, the mixing of the constituent metal oxide powders is perhaps the riskiest step in the procedure. To minimize the risk of contaminating the powder, all constituent metal oxide precursors should be massed onto a fresh waxed massing paper using a balance sensitive to a tenth of a milligram. The powders required to make BST are listed in table 2.3. The total amount adds up to more than 50 grams because the recipe yields 50 grams of reacted powder and 10.1 grams of carbon dioxide is given o as exhaust. Since PMN-PT is made in two stages, the mixture amounts for making magnesium niobate are presented separately in table 2.4 for the mixture amounts for 0.92PMN-0.08PT in table 2.5. The MN numbers are slightly larger than 50 grams because the calculation is performed for mixing in a ratio of 1 mol of MgO to 2 mol of Nb2 O5 . It was previously found that in addition to a two-stage reaction the addition of 2% mol of MgO to the stoichiometric ratio almost prevents unwanted pyrochlore phases of PMN-PT from forming[48, 49]. A 1 l Nalgene bottle should be prepared with a layer of duct tape wrapped twice around both the top and bottom of the wide part of the bottle. This will aid in giving the bottle better traction as the powder mixes. After the powders are massed they are

25

Component BaCO3 SrCO3 TiO2

Mass (gm) 30.364 11.358 18.436

Table 2.3. Powder to make 50 gm Ba0.67 Sr0.33 TiO3

Component MgO Nb2 O5

Mass (gm) 6.715 43.421

Table 2.4. Powder to make 50 gm MgNb2 O6

Component PbO MgNb2 O6 TiO2

Mass (gm) 34.501 14.549 0.988

Table 2.5. Powder to make 50 gm (PbMg1/3 Nb2/3 O3 )0.92 (PbTiO3 )0.08

26 placed in the prepared bottle. Once a bottle is used for mixing a particular powder, that bottle should be used only for mixing that same powder in all future mixings. For BST, 150 ml of reagent- grade acetone should be added to the powder to form a slurry and approximately 450 ml of yttria-stabilized zirconia spheres should be added to the slurry. For MN and PMN-PT, 75 ml of reagent-grade ethanol should be added to the powder to form a slurry and then approximately 220 ml of yttria-stabilized zirconia spheres should be added to the slurry. In both cases, the level of the spheres should be just below the level of the slurry. More solvent or spheres can be added if needed to get the proper level. Once the proper slurry level is achieved, the bottle should be sealed and placed on a roller mill to mix the slurry. The mill should be set so that the bottle rotates at about 22 rpm. For the 1 l Nalgene bottles, this is a roller speed of approximately 44 rpm. The roller mill has a spring-loaded nylon bolt to maintain a downward force on the bottle to improve traction. Tension should be adjusted so that the bottle rolls smoothly with minimal slipping. At the proper speed, the grinding media should be pulled about one-quarter of the way up the side of the bottle as it rotates. The powder should be mixed for at least 12 hours. Once the mixing has completed, the slurry must be recovered from the bottle and the media and the powder must be dried. The slurry should be poured from the Nalgene bottle through a stainless steel strainer into a large Pyrex mixing bowl. The strainer will separate the zirconia media from the slurry. The Nalgene bottle should be rinsed twice with approximately 25 ml of solvent and the bottle should be drained through the strainer. Additionally, about 50 ml of solvent should be drizzled over the zirconia

27 media in the strainer to wash any remaining powder o the media. It is important to not use too much solvent because this will prolong the drying time, increasing the powders exposure to possible contamination. The media in the strainer should be carefully shaken over the Pyrex bowl to promote the drip drying of the media. The strainer should then be set aside to allow the media to nish drying. To dry the powder, the mixing bowl of slurry should be placed under a 60 W incandescent lamp. As the powder dries, it must be stirred every 15 minutes to prevent the constituent powders from separating as the slurry dries and settles. Once the slurry has dried to a paste-like consistency, stirring frequency can be reduced to once per hour to help complete the drying. Large chunks should be broken up with a stainless steel spatula. Once the powder has nished drying, the dried chunks should be broken up in an agate mortar. The BST and MN powder should be placed in a clean yttria-stabilized zirconia crucible. PMN-PT should be placed in an alumina crucible, that has previously been seasoned with lead-based powder. The powder is now ready for calcination.

2.1.2

Calcining the powder Calcination is the process of heating mixed metal oxide powders to near their

melting points to catalyze a solid state reaction which results in the formation of small crystals of BST, MN, or PMN-PT. The temperatures and duration of calcination is chosen as the ideal conditions under which perovskite structured crystals will form[23, 48, 49]. All calcination was carried out in a Sentro-Tech Model ST-1600 furnace. The BST calcination program is found in table 2.6. The calcination program for MN is found in table 2.7. The calcination program for PMN-PT is found in table 2.8. Calcining for

28 longer times and at higher temperatures can result in the growth of larger crystals which will take signicantly longer to mill. After the powder has been calcined, x-ray diraction (XRD) measurements should be performed on the powder to verify that the reaction has completed and that the powder is not contaminated. According to the Powder Diraction File (PDF-4) maintained by the International Center for Diraction Data (ICDD), BST powder should have an XRD pattern with six strong peaks at angles of 2 equal to 22.399o , 31.866o , 39.312o , 45.733o , 51.486o , and 56.802o . Extraneous peaks in BST data are often the result of unreacted carbonate powders. Good BST powder should also have a white color. According to PDF-4, PMN-PT powder should have one strong central peak at an angle of 2 equal to 32.3o and two smaller peaks at angles of 22.1o and 38.8o . Peaks at angles from 30.2o to 30.5o often accompany powder with a red-yellow salt and pepper color. These peaks are the result of unreacted lead oxide. Good PMN-PT powder should have a faint yellow color. Non-ferroelectric pyrochlore phased material, such as Pb6 MgNb6 O23 can also form during the PMN-PT reaction. This pyrochlore will show up in the XRD spectrum with peaks at 29.2o and 33.9o . Small amounts of pyrochlore in the starting powder often disappear during the sintering process. However, if pyrochlore is present in the powder, XRD should be performed on sintered ceramics to verify that this reaction has completed. The XRD results for BST are presented in Chapter 3 and the results for PMN-PT are presented in Chapter 4. If the calcined powders pass both visual and XRD inspection, they are ready to be ground to a ne size.

29

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 240 1200 360 1200 240 0 -121

Table 2.6. Furnace instructions for calcining BST

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 200 1000 360 1000 200 0 -121

Table 2.7. Furnace instructions for calcining magnesium niobate

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 160 800 600 800 160 0 -121

Table 2.8. Furnace instructions for calcining PMN-PT

30 2.1.3 Grinding As the calcined powder comes out of the furnace, it is typically comprised of polycrystalline granules several microns in size. In order to form a dense ceramic, the reacted powder will need to be packed as tightly together as possible. The ideal packing density is between 55 and 60% of the single crystal density. To accomplish this packing, the powder must be ground to a ne size of 100 nm to 1 m. A distribution of particle sizes can help improve the packing packing density, as will be discussed in section 3.2. The same 1 l Nalgene bottle in which the powder was mixed should be used for grinding. The bottle should be free of unreacted powder and dry. Pour the calcined powder into the bottle and add approximately 150 ml of zirconia spheres to the bottle. Seal the Nalgene bottle and place it in an empty can on the vibratory mill. Secure the bottle in place and grind for 4 hours. After 4 hours, stop the mill and add solvent to the powder: 150 ml of acetone for BST or 75 ml of ethanol for either MN or PMN-PT. The level of the zirconia media should be just below the level of the solvent; add more media to the bottle if needed. Replace the bottle in the mill and grind for an additional 6 hours. After grinding, retrieve the powder in the same manner as outlined in section 2.1.1. It is not essential to frequently stir the ground, calcined powder as it should be homogenous and settling is not an issue. Once the powder has formed a thick paste, however, it should be stirred to complete the drying. After the powder is dry, it should be in large, solid chunks. These chunks should be broken up in an agate mortar and the powder should be ltered through a #50 sieve. It may be necessary to grind the powder several times in the mortar to allow it to pass

31 through the sieve. Using a recipe to make 50 grams of powder, at least 45 grams of reacted powder should be recovered after this step. After sieving, the ground powder should be stored in a clean 125 ml Nalgene bottle. The lid should be secured tightly. If the powder will not be used immediately or if the atmosphere is not environmentally controlled, the powder should be stored in a desiccator or under vacuum.

2.2

Preparing ceramic samples

The rst step in forming a ceramic from the calcined powder is to shape the

powder by pressing it into what is known as a green pellet. Here, green refers to any pressed powder pellet that has not been red in a furnace. To form a dense ceramic, it is often necessary to create a green pellet with a density of 55 to 60% of the single crystal density so that the powder is close enough to condense during ring. To aid in the formation of high density green pellets, organic binders are often added to the powders.

2.2.1

Binder The addition of organic binder to ceramic powders as an aid to forming green parts

is a common industrial practice for the manufacture of most ceramics. The binder helps lubricate both the powder and the die as the pellet is being shaped, minimizing stress gradients in the green pellets and allowing tighter packing. Binders typically improve cohesion of the unsintered pellets making them easier to handle. The most common binders are poly vinyl alcohol (PVA) and poly acrylate (PA). PVA is water soluble and often requires a dispersant to properly bond with ceramic

32 powder. Dispersants often contain elements such as sodium which can interfere with electrical properties. PA is acetone soluble and requires no dispersants to bond to PMNPT. As a result, PA was used as the binder for making PMN-PT ceramics. Because of the reactivity of barium, the process of adding binder was omitted for making BST ceramics. Binder typically constitutes as little as 1% of the total weight of pressed pellets to as much as 40% of the weight of pressed pellets for some special ceramic applications. For making PMN-PT, 4% weight of liquid binder is added to the powder, which becomes 1.5 to 1.7% of the total weight of the binder plus powder once the binder has dried. To add the binder, rst weigh 4% of the weight of the powder of binder and add it to a small, clean Pyrex dish. Mix in just enough acetone so that the binder completely dissolves. The more acetone that is added beyond this amount will increase the time it takes the binder to dry. Stir the powder into the dilute binder using a stainless steel spatula. Place the dish under an incandescent heat lamp and stir continuously until the mixture becomes too tough to stir. It is important to keep stirring because the binder can separate from the powder forming a skin on the mixture. If a skin forms, the binder may not properly attach to the PMN-PT powder, eventually resulting in poor sintered ceramics. If this has happened, the binder must be removed from the powder and the process needs to be restarted. To remove binder from powder, place the bindered powder in an open crucible. Place the crucible in the furnace and run the program found in table 2.9. The 3 hours at 325 C breaks down the compounds in the binder and the 10 hours at 500 C removes the carbon ash from the powder.

33 Instruction C01 T01 C02 T02 C03 T03 C04 T04 C05 T05 C06 T06 Setting 0 300 325 180 325 90 500 600 500 20 0 -121

Table 2.9. Furnace instructions for binder burnout

If the addition of binder was successful, the Pyrex dish should contain several large hard clumps of binder and powder. These clumps need to be broken up in an agate mortar and the bindered powder should be passed through a #50 sieve to lter out any large clumps of binder that may have formed. The bindered powder should pass readily through the sieve compared to the non-bindered powder.

2.2.2

Pressing ceramic pellets To form dense ceramics, the powder must rst be shaped as compactly as possible

into a pellet. For the property evaluations carried out in this thesis, the powder was pressed into 1/2 cylinders using a high strength steel die with high strength steel anvils on a uniaxial press. A schematic of the die is presented in gure 2.1. The anvil is placed inside the die. The powder is poured into the die and then the press forces the hammer down on the powder, compacting the powder between the hammer and the anvil.

34

111111 000000 111111 000000

Force gauge

Hammer

111 111 000 000 111 111 000 000 11111 00000 11 00 11111 00000 11 00 111 111 000 000 11111 00000 11 00 111 111 000 000 111111111111111 000000000000000 111 000 111 111 000 000 111 000 111111111111111 000000000000000 111 000 111 000 111111111111111 000000000000000 111 000 111 000
Die Anvil
Fig. 2.1. Die used to press ceramic pellets

35 To make BST ceramics, 1.5 grams of powder were pressed. The pressure was slowly increased to 200 MPa, which corresponded to a force of 5700 lbs on the press. The pressure was maintained for 30 seconds and then released. The compression cycle was then repeated two more times. To make PMN-PT ceramics, 0.7 grams of powder were pressed. The pressure was slowly increased until the press was just starting to measure a force on the die. Then, in one uid motion, the pressure was raised to 150 MPa, a force of 4500 lbs, and then immediately released. The compression was not repeated. Once compressed the pellets were extracted from the die. First, the die was inverted on the press and a stainless steel spacer was placed between the die and the press. The anvil was pushed three-quarters of the way out of the die so that it could be removed by hand. The inverted die was then placed back on the press with the spacer and the hammer was pushed through the die until the sample was clear of the die. Then a ne paint brush was used to push the green pellet onto a razor blade to be transported to the sintering vessel.

2.2.3

Sintering the pellets Sintering is the process of heating green pellets to just below the melting point

of the material so that the pressed powder condenses into a dense ceramic. All sintering was performed in the same furnace as the calcination. BST pellets were placed on a sheet of platinum foil in a yttria-stabilized zirconia calcination tray. The tray was then covered with another tray and placed in the furnace. Oxygen was fed into the furnace to prevent oxygen depletion in the ceramics at high

36 temperatures. To set the oxygen ow rate, a tube from a regulated oxygen cylinder was fed into a water bath. A needle valve on the regulator was adjusted until the oxygen owed out of the regulator at a rate sucient to produce one to three 3 mm bubbles per second in the water bath. The oxygen line was then connected to the oxygen inlet on the furnace. The furnace was programmed with the program found in table 2.10. The BST ceramics had to be cooled very slowly from high temperatures to avoid cracking and other structural damage.

Instruction C01 T01 C02 T02 C03 T03 C04 T04 C05 T05 C06 T06

Setting 0 80 400 60 400 367 1500 360 1500 750 0 -121

Table 2.10. Furnace instructions for sintering BST

PMN-PT ceramics were rst placed on platinum foil on a zirconia brick. The brick was placed in the furnace and the binder burnout program from table 2.9 was run. The pellets were then weighed to determine that they had lost approximately 1.5% of their weight and transferred to a piece of platinum foil on the lid of a small

37 alumina crucible that had been previously seasoned with lead oxide-based powder. The pellets were covered with another piece of platinum foil, the crucible was placed over the lid, covering the platiunum wrapped pellets. The crucible was placed in the furnace. Oxygen was fed into the furnace in the same manner as described above. The pellets were sintered according to the program in table 2.11. Lead oxide can evaporate out of PMN-PT solutions at temperatures above 1000 C, so the ceramics had to be cooled as quickly as possible to avoid changes in elemental composition. To combat this lead loss, industrial ceramics are often sintered while buried in some sort of lead donor powder. This was attempted with the PMN-PT samples, but this often lead to bizarre structural deformations of the ceramics.

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 128 1280 120 1280 20 0 -121

Table 2.11. Furnace instructions for sintering PMN-PT

High quality sintered ceramics should have a lustrous shine. BST should be a brown color and PMN-PT should be light tan to faint yellow color. Both BST and

38 PMN-PT should be translucent below a thickness of 1 mm. Samples meeting these visual properties are ready to be prepared for electrical property measurements.

2.3

Preparing samples for measurement

PMN-PT is a more stable ceramic than BST and is therefore more forgiving in

the preparation of thin slices. PMN-PT ceramics thicker than 1.0 mm can be cut on a wire saw. The ceramics should be mounted to an aluminum right angle jig with hot wax. A small piece of graphite should be placed just below the ceramic to help support the slices as they are cut and to keep the blade from falling into the aluminum jig. The ceramic should be sliced into 400 m or thicker slices and then each piece should be polished to thickness. The wire saw cuts very slowly compared to the wafering saw and the wire blade is more subject to travel. Sometimes the cut surface from a wire saw cut sample is wedge shaped or bowled, which requires careful polishing. Ceramics thinner than 1.0 mm should be hand polished down to a thickness of 250 m. The ceramics should be mounted to a at stainless steel polishing base by heating a small amount of wax on the base and pressing the sample rmly into the wax. Weight should be placed on the ceramic as it cools to ensure that the ceramic lies at against the steel base. After the wax has hardened, the sample can be polished using a South Bay polishing jig, starting with 120 grit emery paper, followed by 400 grit emery paper and nally with 9 m grit paper. In all cases, distilled water should be used to lubricate the polishing surface. Further polishing beyond 9 m grit paper is usually unnecessary because the friction between the polishing paper and the ceramic tends to pull grains out of the ceramic rather than break down the ceramic grain, itself.

39 After polishing, the samples need to be annealed to help repair any scratches, gouges, or microfractures that may have occurred during polishing. The samples should be placed on platinum foil on a zirconia brick. The brick is placed in the furnace and oxygen should be owing into the furnace at a rate of one to three 3 mm diameter bubbles of gas per second. The furnace program is shown in table 2.12. At a temperature of 900 C the material should not be in danger of decomposing. After the samples have cooled, they are ready for the application of electrodes.

Instruction C01 T01 C02 T02 C03 T03 C04 T04

Setting 0 180 900 600 900 180 0 -121

Table 2.12. Furnace instructions for annealing PMN-PT ceramics

2.3.1

Electrodes Electrodes turn out to have signicant inuence on the measurement of ferro-

electric properties. The dielectric constant and electrocaloric eect depend on a high mobility of surface charges both at ceramic grain surfaces and along ferroelectric domain boundaries. Industrially manufactured piezoelectric ceramics typically use a silver paint

40 electrode that is screen-printed, dried, then red onto the ceramic. The organic backing of the paint can leave behind a thin insulating lm, spoiling electrical property measurements. Because of the high reactivity of barium, it is best to minimize the contact of BST with any possible surface contaminant. The ideal electrode solution is to directly sputter metal lm electrodes directly onto each surface of the polished ceramic disk. The electrodes in the research were applied using a Perkin-Elmer model 4400 commercial sputter deposition system. Detailed operating instructions of the sputtering system are found in appendix B. To form the electrode, a layer of chrome was deposited for 10 minutes at a power of 500 W using an RF magnetron. Then, a layer of aluminum was deposited for 10 minutes at a power of 1000 W using a DC magnetron. The samples were then ipped over and a similar electrode was applied to the other side. The resulting electrodes had a thickness of one to two microns and a surface resistance of 1 to 3 . Because the sputtered metal can redeposit as it accumulates on the sample, a thin bridge of metal usually forms around the edge of the sample. After sputtering, this bridge of metal needs to be polished from the sample with some ne grit emery paper to isolate the two electrodes. With the application of the electrodes, the ceramic samples are ready for measurement of electrical properties.

2.4

Measurements on ceramic wafers

Both physical and electrical properties were measured to evaluate the ferroelectric

ceramics. Density and structure of the materials were probed rst to determine that the ceramics compared to those found in the literature. After the physical parameters were met, the dielectric constant and electrocaloric eect of the samples were measured.

41 Physical property measurement methods will be discussed in section 2.4.1. Electrical property measurement methods will be discussed in section 2.4.2. The results of these measurements will be presented and discussed in chapters 3 and 4.

2.4.1

Physical property measurement methods The rst test typically performed on the materials was x-ray diraction (XRD)

As this was rst performed just after calcination, this was discussed previously in section 2.1.2. Occasionally, XRD was used as a spot check on ceramic wafers to ensure that the phase and composition of the powder had not changed during processing. No signicant dierences were ever found between powder or ceramic XRD measurements. SEM microscopy was also used to characterize the structure of the grains within the ceramic. SEM micrographs along fractures of ceramic samples were made to determine the average grain size and porosity of the samples. After a reliable method for reproducing large grained, dense ceramics was established, most of the SEM microscopy was deemed unnecessary. The density of the ceramic samples is the fastest test outside of a visual inspection that can provide clues to the quality of the sample. Good ceramics for ferroelectric measurements should have a density 98 to 99 % of the single crystal density. The single crystal density of BST is 5700 kg/m3 and the single crystal density of PMN-PT is 8000 kg/m3 . Lower densities suggest that the ceramic has either large open pores between the ceramic grains or large empty regions inside the sample. Both high-porosity and voids in the sample increase the risk of dielectric breakdown and spoil the electrical properties.

42 2.4.2 Electrical property measurement methods Electrical properties were directly measured using the setup shown in gure 2.2. Copper leads were attached to the metal lms on the ceramic wafers using a conducting silver paint; one side was connected to ground and the other to a high voltage power supply. A thermocouple was attached to the grounded electrode. Figure 2.2 shows two PVDF sensors on the ground electrode of the sample. These were initially used to check the thermocouple data. As the sample was heated, the pyroelectric PVDF sensors produced a current corresponding to the heating rate. The heating rate from the thermocouple was always in excellent agreement with the PVDF sensors, so for simplicity, the PVDF sensors were deemed unnecessary for most ceramic samples. The thermocouple was connected in series with a second thermocouple which was attached to a large copper block with an alcohol thermometer attached to it. This block served as an isothermal reference and all temperature measurements were made relative to the isothermal block. Both dielectric and electrocaloric measurements were carried out under high vacuum to minimize the risk of arcing when large electric elds were applied to the sample and to maximize the thermal isolation between the sample and the environment, giving the longest possible time constant to observe thermal eects before the sample returned to thermal equilibrium. The dielectric constant was measured by connecting the sample in series with a 56.6 k resistor and applying a 100 mV AC electric eld at a frequency of 1 kHz. A schematic of the measurement is shown in gure 2.3. The voltage across the capacitor was measured using a computer controlled digital volt meter. Using Vo as the applied

43

Fig. 2.2. Setup to measure the electrocaloric properties of BST

44 voltage, VC as the voltage across the capacitor, R as the series resistance, and as the angular frequency of the applied AC eld, the capacitance of the sample is given as

C=

1 R

Vo 2 1. VC

(2.1)

Since the sample is a parallel-plate capacitor, the dielectric constant can be found from

Ct oA

(2.2)

where t is the thickness of the sample, A is the cross-sectional area of the sample and o is the permittivity of free space, 8.85 F/m.

Fig. 2.3. Schematic of dielectric constant measurement

45 The electrocaloric eect was measured by applying a large DC electric eld across the sample and recording the resulting temperature change observed on the thermocouple. The high resistivity of the ceramics mitigates any possible Joule heating. Also, Joule heating shows up like an exponential curve (as with an RC time constant) in the temperature data; there is an initial rapid change in temperature that gradually levels o as the system comes into thermal equilibrium. Under the conditions in this experiment, the time constant for this equilibrium was on the order of one minute. The observed electrocaloric temperature change established itself on the order of two seconds, the response time of the thermocouples. As the electric eld was kept on the sample, the temperature of the sample slowly returned to thermal equilibrium on a several minute thermal time constant scale. If the electric eld was removed after the system had returned to thermal equilibrium, the temperature of the sample would instantly drop below room temperature and recover to thermal equilibrium on a several minute time scale. The electrocaloric eect can also be measured as the heat required to restore a system to equilibrium in a calorimeter[26]. In the calorimeter, the sample and a reference material are mounted to heaters with a compensation system to ensure that they remain at the same temperature. To study phase transitions, the materials are heated at a slow consistent rate; if the sample has a change in heat capacity, the reference heater must change its output to match the eects in the sample. To measure the electrocaloric eect, the sample and the reference are heated at a slow, uniform rate. An electric eld is applied to the sample, inducing a temperature change in the sample. The reference heater must then do work to compensate for the change in the sample. The power of the heater can be recorded to nd the heat ow

46 in and out of the sample. It must be noted that this process is not inducing a phase transition and this is not latent heat. The proper term for measuring the electrocaloric eect through calorimetry is measuring the heat of polarization. Both direct temperature change data and calorimetry data can be compared by either converting the temperature change in an isolated environment to a heat of polarization or by converting the heat of polarization to a temperature change in an isolated environment. Assuming the temperature change occurs in isolation, the heat of polarization is given from hEC = cp TEC . (2.3)

Direct observation of the electrocaloric eect is not practical in thin lm systems. Polarization of thin lms can be mapped as a function of applied external electric eld and temperature. This surface can then be t numerically to calculate derivatives and these can be integrated to determine electrocaloric temperature change. Unfortunately, this calculation is only useful as an intellectual exercise and cannot be translated into real-world devices. Any exploitation of the electrocaloric eect needs to consider the thermodynamics of the entire system. If there is a 2 m thin lm on both sides of a 100 m thick rigid substrate there is only a 4% electrocalorically active region. Thermodynamically, there is 25 times more material that will be heated but not positively contribute to the electrocaloric eect. Any electrocaloric element based o a thin lm will have a useable temperature change of the theoretical thin lm eect divided by the ratio of electrocalorically inactive material to electrocalorically active material.

47

Chapter 3

Electrocaloric eect in barium strontium titanate

Recent trends have prompted global research for more environmentally friendly sources of energy and refrigeration. While ozone-depleting chlorouorocarbon refrigerants have been phased out, their replacements, hydrochlorouorocarbons tend to have global warming potentials 3000 times that of an equivalent amount of carbon dioxide[14]. Alternatives to vapor compression refrigeration suer from serious technical challenges. Thermoelectric technology provides an all-solid-state solution, but thermoelectric devices have typical eciencies around 7% of the Carnot limit. Although some recent advances[30] are pushing the technology to near 10% of the Carnot limit, typical household refrigerators operate with eciencies near 25% of the Carnot limit. As most electrical power in the United States is provided by carbon emitting sources, the reduced eciency contributes to the potential for global warming. Magnetocaloric materials are capable of very large temperature changes, greater than 17 K; however, they require magnets capable of generating large elds (1-5 T) which are not conducive to scalability[21]. The electrocaloric eect is a possible replacement for thermoelectrics in the development of all-solid-state heat pumps and refrigerators. Modern ceramic and single crystal material can withstand large electric elds, and high voltages can be generated from inexpensive sources. Most of the electrocaloric materials are perovskite ferroelectrics, and the general properties of these materials will be discussed next.

48

3.1

Ferroelectric-Paraelectric transition in BST

Ferroelectric materials exhibit large electrocaloric eects near the ferroelectric-to-

paraelectric phase transition. Barium strontium titanate, (BST), has a phase transition temperature which can be tuned from 233 o C, the transition temperature of SrTiO3 , to 118 C, the transition temperature of BaTiO3 . The chemical symbol is usually given as Bax Sr1x TiO3 , where x is the molar concentration of barium. The simple approximation of the transition temperature in C as a function of doping can be found with Tc = 371x 253.0[3] (3.1)

This assumes a linear shift in transition from pure SrTiO3 to pure BaTiO3 . Careful study of the transition temperature shows multiple regions of interest in the transition temperature[24, 58]. Below a Ba concentration of 20.0%, the Curie temperature increases as x1/2 with the temperature in C given by[58]

TC = 274(x 0.0002)1/2 273.15.

(3.2)

Above a concentration of 20.0% a better approximation of the Curie temperature in C is given by[24] Tc = 339x 221. (3.3)

Room temperature phase transitions occur with a doping of 0.65 < x < 0.70. A broad survey of transition temperatures found throughout the literature is presented in gure 3.1[2, 3, 4, 7, 6, 8, 16, 18, 19, 22, 23, 24, 25, 26, 28, 29, 33, 37, 41, 44, 45, 47, 52,

49

Fig. 3.1. A compilation of measured Curie temperatures in BST systems

50 53, 55, 56, 57, 58, 59, 63, 65, 66, 68]. The dashed line plots the linear shift in phase transition temperature that is predicted by equation 3.1. The solid curve plots the phase transition temperatures predicted by equations 3.2 and 3.3. It should be noted that both the theoretical curves usually tend to under-predict observed Curie temperatures. The Curie temperature can be very sensitive to both small variations from the assumed stoichiometric ratio of barium and strontium, and no paper surveyed made any eort to verify the exact composition of the sample studied. Small levels of impurity can have strong eects on the transition temperature and physical properties near the transition. Small levels of nickel and calcium can lead to strong changes in resistivity near the phase transition, creating a semiconductorlike material. At large electric elds, if the resistivity drops below 1012 m, Joule heating can begin to overwhelm the electrocaloric response. The electrocaloric materials, therefore, need to be good insulators. To achieve consistent, high-quality electrocaloricgrade BST ceramics, a precise preparation protocol is crucial. A considerable portion of the research of this thesis was directed toward developing such a protocol.

3.2

Sample preparation protocol

BST powder was prepared from carbonate precursors; the procedure is docu-

mented in Chapter 2 and a step by step summary is presented in Appendix A. Briey: powders were mixed for 4 hours in an acetone solution using a roller mill and dried. The dried powder was calcined at 1200 C for 6 hours. To verify the crystal phase of the BST powder, X-ray diraction (XRD) was performed on the calcined powder. The results of the XRD analysis are shown in gure 3.2. Table 3.1 lists the angular locations of the

51 expected XRD peaks for BST found in the PDF-4 in addition to the measured locations. The measured angles are all slightly below the expected angles for BST, however, it is likely that the sample in the reference database has a slightly dierent stoichiometric composition. The data from gure 3.2 are in good agreement with the expected XRD signature from the PDF-4. Also, there are no additional peaks beyond the six anticipated peaks. Large quantities of unreacted carbonate powder would show up as two additional peaks. As the calcination appeared to be complete the BST powder was ground to a suitable size for making ceramic pellets.

2theory [o ] 22.399 31.866 39.312 45.733 51.486 56.802

2observed [o ] 22.352 31.850 39.287 45.623 51.414 56.760

Table 3.1. Expected and observed XRD angular peaks in BST

The optimal procedure to grind the BST powder was found to be a 4 hour dry grinding using yttria-stabilized zirconia media, followed by a 6 hour grinding in an acetone slurry. A particle size analysis was performed using a laser diraction particle size analyzer. Figure 3.3 shows the distribution of grain sizes. The time listed is the total time for which the powder was ground. The 2 hour and 4 hour ground powder was only ground dry. The 6 hour, 8 hour and 10 hour all included both the 4 hour dry grinding

52

Fig. 3.2. XRD analysis of BST powder

53 in addition to acetone grinding to complete the balance of the time. As grinding time is increased, the mean particle size decreases and the distribution of particle sizes tends to increase. It is only at 10 hours of total grinding time that a signicant fraction of powder particles appear below 250 m. It is important to maintain a broad distribution of particle sizes to achieve optimal packing of powder when the powder is pressed into a pellet. Ceramic pellets were prepared by pressing 0.5 grams of BST powder in a 1/2 diameter die to a pressure of 200 MPa. As barium is highly reactive, even in solid solution, no binder was used to hold the pressed powder together. While binder is typically used in industrial ceramic manufacture, many binders are either water or solvent-based. Barium is highly reactive with water; even limited exposure to water vapor in a humidity controlled environment for more than three months can turn the surface of ceramic BST from brown to purple. In addition to the problems presented by water, the organic compounds that comprise the binder can inhibit the sintering of high-quality ceramics. The presence of carbon inhibits grain growth and leaves large deposits throughout the sample. Figure 3.4 shows the surface of a BST ceramic pellet made from powder that has been contaminated with an organic compound. The open porosity and small, poorly connected grains increase the occurence of dielectric breakdown. It is suggested that the pyroelectric coecient in BST increases as the ceramic grain size increases, with optimal values occurring between 10 and 20 m[23]. Figure 3.5 shows SEM micrographs of a cross-sectional fracture of BST ceramics. Table 3.2 shows the estimation of the average grain diameters of these ceramics. The sintering time

54

Fig. 3.3. Particle size analysis of BST powders

55

Fig. 3.4. SEM micrograph showing carbon contamination in BST ceramics

56 and temperature is sucient to reach the predicted sweet spot for optimal pyroelectric activity.

Sintering conditions 1460 C, 8 hours 1500 C, 9 hours

Average grain size ( m) 12.7 16.2

Table 3.2. Corresponding grain sizes of dierent sintering conditions

As grain size increases, the ceramics become increasingly brittle. Above a grain size of 15 m the ceramics could not be sliced thinner than 330 m. Polishing of the ceramics typically had a negative impact on the larger grained samples. As the grain size increased, the strength holding the grain together seemed to be stronger than the strength connecting the grains. This leads to grains pulling out of the ceramic causing a rough, cloud-like texture on the surface. The rough surface can create an uneven thickness, which leads to local spots of larger than average electric eld. These hotspots increase the likelihood of catastrophic dielectric breakdown. Once ceramic pellets exhibiting good physical properties were crafted repeatedly, the pellets were prepared for electrical properties measurements.

3.3

Electrical properties measurement

The sintered pellets were sliced to a thickness of 300-400 m and approximately

1-2 m thick chrome and aluminum electrodes were sputtered onto the wafers. Detailed

57

Fig. 3.5. SEM micrographs of fracture cross-sections of BST ceramics

58 instructions for operating the sputtering machine can be found in Appendix B. While it is more traditional in the ceramic industry to apply electrodes by ring a conductive silver paste onto the ceramic, the BST samples showed degraded properties after contact with the silvering compound. This degradation is most likely due to either the reactivity of barium, or a thin layer of the organic carrier of the paint remaining between the ceramic and the electrode. This paint layer could degrade charge mobility from the ceramic to the electrode, spoiling the measurement of dielectric and electrocaloric properties. Figure 3.6 shows a comparison of dielectric constants measured on samples prepared from the same powder: the top trace is for a ceramic with sputtered electrodes, the bottom trace is for a ceramic with silver paint electrodes. While the peak temperature is visible, the sharp peak is muted, and the maximum value of dielectric constant in the paint electrode samples are almost an order of magnitude smaller than the sputtered electrode samples. The electrocaloric eect was directly measured using the setup shown in gure 2.2. Copper leads were attached to the metal lms on the BST wafers using a conducting silver paint; one side was connected to ground and the other to a high voltage power supply. A thermocouple was attached to the grounded electrode. Figure 2.2 shows two PVDF sensors on the ground electrode of the sample. These were initially used to check the thermocouple data. As the sample was heated, the pyroelectric PVDF sensors produced a current corresponding to the heating rate. The heating rate from the thermocouple was always in excellent agreement with the PVDF sensors, so for simplicity, the PVDF sensors were deemed unnecessary for most ceramic samples. The dielectric constant of Ba0.67 Sr0.33 TiO3 is shown in gure 3.7. The lower curve was recorded as the sample was heated and the upper curve was recorded as

59

Fig. 3.6. Dielectric constant of BST ceramics with dierent electrodes

60 the sample cooled. Arrows have been imposed over the data to show the direction in which the data were recorded. The dierence in the two curves can be explained by the process of measuring the dielectric constant. The polarization does not truly spontaneously appear, especially because of the presence of the small AC electric eld present to measure the dielectric constant. Just as permanent ferromagnets can be degaussed with an oscillating magnetic eld, the dielectric measurement ghts the onset of the permanent polarization. Over time, small uctuations will begin ordering the electric dipole. As this remnant polarization sets in, the measured dielectric constant slowly decays to the lower curve. The sharp peak in the dielectric constant of just under 20000 occurs at a temperature of 25 C; this is the Curie temperature. Below 18 C and above 35 C the dielectric constant levels o. These upper and lower temperatures set the bounds for observing a large electrocaloric eect. Figure 3.8 shows the electrocaloric response of this sample under the application and removal of a 1 MV/m electric eld. The eect peaks at 24.5 C with an electrocaloric temperature change of 0.38 K. The electrocaloric response is larger than 0.25 K from 20 C to 33 C. Outside of this range, the eect drops quickly. The electrocaloric eect in the phase transition temperature region was mapped as a function of both temperature and applied eld and is presented in gure 3.9. As the eld is increased the maximum electrocaloric eect is observed at larger temperatures. This is due to the nature of the polarization in this region. Below the transition temperature, there is some net polarization, even at zero applied eld. There is a limit to the ability of the applied eld to polarize the material; at low elds, the eect is linear with applied

61 eld but the electrocaloric eect begins to saturate. Above the transition temperature, the BST has become a paraelectric and there is a growing contribution from the square of the electric eld, as mentioned in equation 1.12. At much higher temperatures, the electrocaloric response should scale exactly as the square of the applied electric eld. The largest absolute electrocaloric response observed in the BST sample was 0.45 K, which occurred at 24 C and an applied eld of 1.33 MV/m.

3.4

Comparison to other results

While this is not the rst experiment to measure the electrocaloric eect in

BST[26], the measurements are superior to those found in the literature. Lin measured a bulk BST ceramic using dierential scanning calorimetry. Lin reports his electrocaloric measurement as a latent heat; however, the terminology is not proper. The eect is more properly called a heat of polarization[10], which can be converted to an equivalent electrocaloric temperature change for easy comparison, as follows: assuming that the electrocaloric eect occurs in isolation, the electrocaloric heat of polarization is given as,

hEC =

cp

TEC .

(3.4)

The density of BST is 5700 kg/m3 and the specic heat is 2.7 MJ/m3 K[5], the observed heat of polarization is approximately 0.189 kJ/kg for a temperature change of 0.40 K. The only latent heat observations made on the electrocaloric phase transition in BST observe a heat of polarization of 0.12 kJ/kg at the transition temperature under

62

Fig. 3.7. The dielectric constant of Ba0.67 Sr0.33 TiO3

63

Fig. 3.8. Electrocaloric eect in BST at 1 MV/m

64

Fig. 3.9. Electrocaloric eect in BST as a function of temperature and applied eld

65 an applied eld of 1.0 MV/m[26]. Lins measurement corresponds to an electrocaloric temperature change of 0.25 K in an isolated sample. Extrapolating the peak electrocaloric eect to 2.5 MV/m, close to the limit of the onset of dielectric breakdown in bulk ceramics, we would anticipate to see an electrocaloric temperature change of 0.65 K and a heat of polarization of 0.3 kJ/kg.

66

Chapter 4

PMN-PT

During the last 10 years, one of the most interesting perovskite compounds to emerge is lead magnesium niobate-lead titanate, (PbMg1/3 Nb2/3 O3 ) (PbTiO3 )1x x (PMN-PT). Both ceramic and single crystal PMN-PT exhibit an interesting structure which have led to the observation of extremely large electrocaloric and piezoelectric properties. At lower PT concentrations, from x = 5 15%, PMN-PT has a nearroom-temperature pseudo-cubic to cubic phase transition, around which a very large electrocaloric eect occurs. At higher PT compositions, a morphotropic region exists between rhombohedral and cubic phases; in this region large piezoelectric eects are observed, making PMN-PT an ideal material for sensors and actuators. This uniquely structured material is at the forefront to revolutionize several technical elds[31].

4.1

Crystal structure
Though not obvious from its canonical chemical formula, PMN-PT has the same

perovskite unit cell structure as BST, ABO3 , shown in gure 1.3. To highlight this structure an alternate chemical formula, Pb(Mgx/3 Nb2x/3 Ti1x )O3 , could be used. The A sites in the unit cell are clearly occupied by Pb atoms. The oxygen atoms form octahedral cages about the B site atoms. The B sites are lled in proportion to the ratios set within the parentheses; for example, for (PbMg1/3 Nb2/3 O3 )0.9 (PbTiO3 )0.1 , or

67 (Pb(Mg0.3 Nb0.6 Ti0.1 )O3 ) in the alternate scheme, there would be 30% Mg atoms, 60% Nb atoms and 10% Ti atoms occupying the B site. Below the Curie temperature, it becomes energetically favorable for the B site atoms to settle either slightly above or below the centers of the oxygen octahedra, leading to a remnant polarization at low temperatures.

4.2

Relaxor transition in PMN-PT

Just as ferroelectrics exhibit large electrocaloric eects near the ferroelectric-to-

paraelectric phase transition, relaxors exhibit large electrocaloric eects in the region of the freezing temperature. As the ferroelectric-to-paraelectric phase transition is very sharp, the region of large electrocaloric eect in a ferroelectric such as BST is limited to a range of about 10 K. Because the relaxor transition is very broad, a large electrocaloric eect can be observed over a broader range, though the peak eect may be smaller because the changes in the polarization are smoother.

4.2.1

Transition temperature for PMN-PT As PMN is a relaxor and PT is a ferroelectric, the structural transition becomes

rather complicated. Room temperature phase transitions occur for two dierent concentrations of PT. At PT concentrations of 27-33%, PMN-PT exhibits a morphotropic transition from the low-temperature rhombohedral phase to a low temperature tetragonal phase. This transition allows very large piezoelectric coupling coecients[15, 62, 64]. Figure 4.1 is based on the phase diagram presented by Zekria, et. al. At a composition of 6-12% PT there is a transition from the rhombohedral phase to the high-temperature

68

Fig. 4.1. Phase diagram for PMN-PT mixtures[62]

69 cubic phase. It should be noted that diuse neutron scattering experiments fail to show the distinct change in the physical structure along this transition[61] that is seen in XRD measurements[62, 64]. Gehring has speculated that this transition is really a skin eect, the part sensitive to XRD, and that the bulk of the material, the part sensitive to neutron scattering, does not experience any change[13]. This could explain some observations of larger electrocaloric eects in thinner samples[31, 40].

4.3

Single crystal PMN-PT

Recent data suggests a strong dependence of crystal orientation on the observation

of large electrocaloric eects[39]. Table 4.1 shows the electrocaloric eect observed by Sebald, et al., in three orientations of single crystal 0.75PMN-0.25PT as well as ceramic PMN-PT. The orientations investigated were [111], [110], and[100]. While Sebald fails to draw the connection between crystal orientation and electric eld, the result is straight forward. The energy in and electric dipole in an electric eld is E = P Eq , where P is the dipole moment vector and Eq is the applied electric eld vector. For a single crystal, the dipole moment vector is the direction of net polarization, which seems to occur in the [111] orientation. The column in table 4.1 labeled cos [111] is the cosine of the angle between the listed crystal orientation and the [111] orientation. Sebalds data show good agreement with the simple estimate of maximum polarization occurring along the [111] orientation. Note that for the ceramic sample mentioned in table 4.1 the fraction of the polarization which remains when the bias eld is removed is presented in lieu of the cosine

70 Orientation [111] [110] [100] Ceramic cos [111] 1.000 0.817 0.578 0.866 TEC,[111] cos [111] 0.40 0.33 0.23 0.35 Observed TEC (J/g)[39] 0.40 0.32 0.18 0.36

Table 4.1. Eect of crystal orientation on the electrocaloric eect in PMN-PT

of the rotation angle. Because the largest electrocaloric response seems to occur in [111] oriented, single crystal PMN-PT was initially investigated. Single crystal PMN-PT plates were provided by Omega Piezo Technologies, Inc. of State College, PA. The plates measured 18 mm by 22 mm by 0.2 mm thick. The plates were very fragile and the edges could not be safely polished if metal from the electrode redeposited around the side of the sample. A special deposition mask was prepared for use in the sputtering system and is shown in gure 4.2. The edges of the mask overlap the sample edges by 0.5 mm to maintain a large gap to prevent arcing through air between the electrodes when large elds were applied to the plates. The mask had holes over one corner of the plate to ease connection to the electrical leads in the proposed solid-state heat pump. When the rst sample was mounted in the electrocaloric apparatus, no peak in either dielectric constant or electrocaloric eect was observed below 80 C. A special high temperature setup was constructed in an oven and is shown in gure 4.3. The sample is still suspended by the electrical connections with a thermocouple attached to the grounded electrode; however, the sample was not measured under high vacuum.

71

Fig. 4.2. Mask for electroding rectangular plates

72 The presence of air increased both the uncertainty of the absolute temperature and diminished the size of the measured electrocaloric eect. These considerations are reected by the large error bars in gure 4.4. The lower set of data, presented as boxes, show the electrocaloric eect measured at 1 MV/m. The upper set of data, presented as Xs, show the electrocaloric eect measured at 1.5 MV/m. The peak eect observed was 0.56 K at 1 MV/m and 0.74 K at 1.5 MV/m, both occurring at 141 C. A transition temperature of 141 C would suggest that the composition of the material is (PbMg1/3 Nb2/3 O3 )0.73 (PbTiO3 )0.27 . The manufacturer of the sample quoted the sample as having between 12 and 15% PT. An electron backscatter measurement was made on the ceramic, and an analysis of the electron absorption measured the relative concentration of constituent ions. The results are presented in table 4.2. The magnesium, niobium and titanium ratios suggest that the composition is closest to (PbMg1/3 Nb2/3 O3 )0.8 (PbTiO3 )0.2 though this material would be signicantly magnesium decient. This deciency could explain why the Curie temperature was observed to occur at 141 C when it should occur at 88 C in (PbMg1/3 Nb2/3 O3 )0.8 (PbTiO3 )0.2 . To help control compositional variance and produce PMN-PT with a Curie temperature near room temperature, a protocol to produce ceramic PMN-PT samples was developed.

4.4

Ceramic PMN-PT
PMN-PT powder was prepared in a two reaction process[48, 49]; the procedure

is documented in Chapter 2 and a step-by-step summary is presented in Appendix A. Briey: magnesium niobate was prepared rst by mixing magnesium oxide and niobium

73

Fig. 4.3. High temperature electrocaloric measurement setup

74

Fig. 4.4. Electrocaloric eect in single crystal (PbMg1/3 Nb2/3 O3 )0.8 (PbTiO3 )0.2

Ion Pb Mg Nb Ti O

Number per unit cell 0.98 0.21 0.57 0.20 3

Expected 1.00 0.27 0.55 0.18 3

Percent dierence 2.1 21.8 3.6 8.3 0

Table 4.2. Compositional analysis of PMN-PT crystal

75 (V) oxide for 12 hours in an ethanol solution using a roller mill and drying the powder. The dried powder was calcined at 1200 C for 6 hours and ground for a total of 10 hours in a vibratory mill. The magnesium niobate was then mixed with lead oxide and titanium dioxide for 12 hours in an ethanol solution in a roller mill and dried. This powder was then calcined at 800 C for 10 hours and ground for a total of 10 hours in a vibratory mill. The ground powder was run through a #50 mesh sieve and binder was added to the powder to aid the pressing of ceramic pellets. For the ceramics measured in this research, a PT concentration of x = 0.15 was chosen. PMN-PT powders with concentrations of x = 0.10 were also prepared; however, they were found to contain extremely high levels of lead, and the ceramic samples were not studied in detail. Properly reacted PMN-PT powder should have a uniform faint yellow color. Excess amounts of lead typically show up as a reddish color throughout the powder. To ensure there is minimal excess lead and that the PMN-PT powder has the proper crystalline structure, XRD must rst be performed on any calcined powder.

4.4.1

XRD of PMN-PT powder To verify the crystal phase of the PMN-PT powder, XRD was performed on the

calcined powder. The results of the XRD analysis are shown in gure 4.5. The vertical lines superimposed over the intensity data are the expected locations and relative intensities for the XRD peak in perovskite PMN-PT found in the PDF-4. Perovskite PMN-PT has one very strong peak at an angle of 2 equal to 32.3o and two small peaks at 2 equal to 22.1o and 38.8o . The small peaks at 29.2o and 33.9o are evidence of a small amount of non-ferroelectric pyrochlore material in the powder, most likely Pb6 MgNb6 O23 . The

76 small peak at 30.5o could be unreacted lead oxide powder. Figure 4.6 shows XRD data from a sintered ceramic. The parasitic peaks have mostly disappeared, except for tiny peak around 30.2o . The reaction to form PMN-PT does not always complete during calcination but often will complete during the sintering process. With the proper chemistry and structure ensured, the PMN-PT cermaics can be prepared for electrical property measurements.

4.4.2

Electrical property measurements on ceramic PMN-PT To form thin samples for measurement, sintered ceramics thicker than 1.0 mm can

be cut on a wire saw using the procedure from section 2.3. Sometimes the cut surface from a wire saw cut sample is wedge shaped or bowled, which requires careful polishing by hand. Sintered ceramics thinner than 1.0 mm should be hand polished down to a thickness of 250 m using the procedure documented in section 2.3.. Initially, electrodes were applied by silk screening a conducting silver paste onto each face of the ceramic. These electrodes were then dried and red onto the ceramic. This process is standard in the piezoelectrics industry and avoided when working with BST only because of bariums known high reactivity. Later, electrodes were applied to the PMN-PT ceramics using the same sputter deposition process that was developed for BST. Figure 4.7 shows dielectric constant measurements in a PMN-PT sample with red silver electrodes and sputtered chrome/aluminum electrodes. The arrows represent the direction in which the data were taken. Both curves show the heating and cooling asymmetry typical of relaxors and both have the freezing and Curie temperatures occurring at roughly the same temperature. However, the dielectric constant is three times larger

77

Fig. 4.5. XRD of calcined 0.90PMN-0.10PT powder

78

Fig. 4.6. XRD of a sintered 0.90PMN-0.10PT ceramic

79 when sputtered electrodes were used compared to red silver electrodes. The eects were not limited to the dielectric constant. Figure 4.8 shows the electrocaloric eect measured in two identical samples, one with sputtered electrodes, (the data are presented as the Xs), the other with red electrodes, (the data are presented as the crosses). With the exception of one data point taken at high temperatures, the sputtered electrode sample consistently showed a 20% larger electrocaloric eect. These electrical and thermodynamic eects arise from the mobility of electric dipoles in the ceramics. In addition to dipole boundaries, there are also grain boundaries within the ceramic. It is possible that large surface charges could move over these grain boundaries to attempt to cancel changes in polarization. If a very thin layer of non-ferroelectric insulating material, such as remnants of the organic carrier of the silver paint, is left behind between the electrode and the ferroelectric material, it is conceivable that surface charges in this insulating layer could screen the macroscopic elds applied to the sample, mitigating the dielectric and electrocaloric measurements.

4.4.3

Results for (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15 Both the dielectric constant and electrocaloric eect were measured in a 0.85PMN-

0.15PT ceramic. The dielectric constant data are shown in gure 4.9. The lower curve was taken heating the sample and the upper curve was taken cooling the sample. Arrows have been imposed over the data to show the direction the data were taken. All measurements were made at a frequency of 1 kHz; at lower frequencies larger dielectric constant values would be expected below the Curie temperature. The curves begin to diverge at a temperature of 90 C. The expected Curie temperature for 0.85PMN-0.15PT

80

Fig. 4.7. Eect of dierent electrodes on dielectric constant in ceramic 0.85PMN-0.15PT

81

Fig. 4.8. Eect of dierent electrodes on electric eect in ceramic 0.85PMN-0.15PT

82 is 70 C. The peak of just under 25000 occurs at a temperature of 72 C, the freezing temperature for this sample. As this is where polarization changes most rapidly, this is the temperature around which the largest electrocaloric eect is expected. The electrocaloric data are shown in gure 4.10. The eect peaks at 60 C with a temperature change of 0.375 K. The electrocaloric eect is larger than 0.35 K from 55 C to 81 C, and is larger than 0.30 K from 50 C to above 95 C. While the absolute maximum electrocaloric eect is about the same in PMN-PT as it is in BST, large electrocaloric eects occur in a 45 degree temperature span rather than a 10 degree temperature span. At lower PT concentrations, similar dielectric and electrocaloric eects would be expected to occur at lower temperatures.

4.5

Comparison to other measurements

The largest reported electrocaloric is eect in bulk 0.85PMN-0.15PT is 1.8 K

under an applied electric eld of 1.6 MV/m at 18 C[40]. This peak temperature contradicts most reports of peak properties in 0.85PMN-0.15PT, which should occur above 63 C[15][62][64]. In Shaobos description of the electrocaloric eect, the large temperature gradient establishes itself over a period of many seconds to several minutes [40]. However, the electrocaloric eect should be an almost instantaneous change in the temperature of the sample. Figure 4.11 shows a typcial electrocaloric measurement taken on a PMN-PT ceramic. The horizontal axis shows the time and the vertical axis shows the temperature reading of the thermocouple. A DC electric eld of 1 MV/m is applied for 25 seconds and removed. A DC electric eld of -1 MV/m is then applied for 25 seconds and removed. The circuit supplying the electrical eld has a time constant of 20 ms to

83

Fig. 4.9. Dielectric constant of ceramic (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15

84

Fig. 4.10. Electrocaloric eect in ceramic (PbMg1/3 Nb2/3 O3 )0.85 (PbTiO3 )0.15

85 prevent damage to the sample. The temperature response of the thermocouple occurs with a time constant of less than a second. The temperature change provided by Shaobo could, however, be described if the sample was joule heating because of the application of the electrical eld. Ferroelectrics and relaxors are supposed to have very high resistance, though contaminents can change the structure of the material. Contaminated BST powder created semiconductor-like ceramics, as was mentioned in section 3.1. While the low voltage resistance measurement of a typical multimeter measured high resistance, a measurement of the resistance of the contaminated sample under a large electric eld showed resistances less than 10 M. When attempting to measure the electrocaloric eect in this sample by applying a 200 V electric eld, the result was a 5 mW of joule heating. Figure 4.12 shows the thermocouple response due to joule heating of a ceramic sample. The temperature rises quickly, but with a time constant on the order of several seconds. Even though this particular sample was dissipating only 5 mW of power, this would have led to a steady-state temperature gradient of 10 K if the electric eld would have been left on for several minutes. Other groups using measurement techniques similar to both Shaobo and the techniques described in this research report electrocaloric temperature changes ranging from 0.4 to 1.2 K under an applied electric eld of 1.5 MV/m[67]; however, these data show very erratic behavior, large amounts of scatter and peak eects outside the expected temperature range for the stated concentration. One group has measured the electrocaloric eect in both single crystal and ceramic 0.75PMN-0.25PT using a calorimetry technique[38, 39], which measures the heat generated by the electrocaloric eect. In calorimetry-based electrocaloric measurements,

86

Fig. 4.11. Strip chart recording of the electrocaloric eect in PMN-PT

87

Fig. 4.12. Strip chart recording of joule heating in a ceramic sample

88 samples are slowly heated in a temperature regulated environment. A temperatureregulated heater is connected directly to the sample. If the temperature of the sample starts to drop, the power to the heater is increased; if the temperature of the sample starts to rise, the power is decreased. The power input to the heater is recorded. When an electrocaloric measurement is made, the power of the heater is measured and then integrated to nd the total heat released by the sample when the eld is applied and the total heat absorbed by the sample when the electric eld is removed. In ceramic PMN-PT a peak electrocaloric eect of 0.13 J/g was measured under an applied eld of 1.0 MV/m at a temperature of 130 C[38]. This corresponds to an electrocaloric temperature change of 0.35 K, slightly below the average peak electrocaloric eect of 0.38 K reported in this dissertation. In [111] oriented single crystal 0.75PMN-0.25PT the largest reported electrocaloric eect is 0.23 J/g under an applied eld of 1.0 MV/m at a temperature of 110 C[39]. This corresponds to an electrocaloric temperature change of 0.61 K, compared to the peak electrocaloric eect of 0.56 K reported in this dissertation. While none of the samples in this research have the same compostition as Sebalds samples, the directly observed electrocaloric temperature is consistent with calorimetry measurements in similar materials. Other groups have estimated the electrocaloric eect of PMN-PT in thin-lm samples[31]. While the thin-lms are too small to directly probe, they are grown on a substrate with an electrode and the polarization is mapped as a function of temperature and applied electric eld. The presented data is the electric eld integral of the temperature derivative of the polarization. While the astounding result of a 12 K electrocaloric

89 eect is presented, this must be taken with a mine of salt. This estimation of the temperature change in the thin lm neglects the substrate, which account for nearly all of the thermodynamics. The proper way to treat the thin lm is as a latent heat source; however, the heat capacity of the substrate plus the thin lm must be considered to derive the useful contribution. For a 1 m thin lm on a 100 m substrate, there would be a two order of magnitude reduction in the useful electrocaloric contribution. Polarization measurements in PMN-PT suggest that it should be capable of producing an electrocaloric eect greater than 1 K over a temperature span of 30 to 50 K. While 1 K has yet to be reliably observed, single crystal PMN-PT is capable of producing electrocaloric eects greater than 0.5 K over a 30 K temperature span. Better ceramic processing techniques may allow ceramics to withstand electric elds greater than 2.0 MV/m, increasing the electrocaloric eect. Dependence of the electrocaloric eect on concentration of PT should also be studied. Even though the maximum electrocaloric eect in a PMN-PT plate may be limited to 0.5 to 0.75 K, this may be more than enough to serve as the working medium for a refrigerator capable of cooling an object by 30 K.

90

Chapter 5

An electrocaloric solid state heat pump

While vapor compression refrigeration has tended towards safer, more environmentally friendly working uids, better environmental benets would come from the development of high-eciency all-solid-state refrigerators. Currently thermoelectric heat pumps are used as chip coolers for computer processors, and they have been adapted as plug-in refrigerated chests. A key drawback to more widespread use of thermoelectric technology are low eciencies, typically 7 to 11% of the Carnot limit. Thermoelectric research has focused on designing better materials with larger temperature changes to raise eciencies. While there is no theoretical upper limit to the performance of thermoelectrics, few breakthroughs have occurred since the discovery of semi-conductor thermoelectrics. The slow pace of discovery for thermoelectrics has helped spur research into other solid-state cooling technologies. The focus in cooler design has been to develop new materials capable of producing the largest possible temperature changes. Larger temperature changes allow simpler designs. If a working material can produce a 30 K temperature change, it can cool an object almost 30 K through direct contact and relatively slow cycles. Figure 5.1 shows a schematic of a typical solid state cooler. A heat switch connects a caloric element to the object to be cooled as the element is engaged. As the two objects come into thermal equilibrium, the switch connects the caloric element to the hot heat exchanger

91

Fig. 5.1. A heat switching heat pump

92 to recharge the caloric element. The process is then repeated. If the caloric elements can produce temperature changes smaller than the desired temperature span, the caloric elements could be run in series to create a step-up cooling system[36]. This simplicity has focussed development towards a search for caloric elements with larger and larger temperature changes. Recent research into magnetocaloric and electrocaloric materials[21, 34, 35, 42, 43, 31, 39] has led to the discovery of many new compounds capable of generating large temperature changes. Gadolinium-based materials exhibit a magnetocaloric temperature change of 11 to 17 K under the application of 5 T magnetic elds[34]. Demonstration coolers based o these materials can produce cooling spans of 30 to 50 K[21]. The limit to magnetic refrigeration, however, is the ability to scale devices. Large magnetic elds are not easy to create. Most 5 T magnets require superconducting wires with a separate cryogenic cooling system, making it dicult to build a small, portable system. It is also dicult to raise and lower a magnetic eld quickly. Electrocaloric materials avoid most of the problems with magnetocalorics; large electric elds are relatively cheap and easy to produce and electrical power supplies are highly scalable. The drawback to the electrocaloric eect has been the lack of discovery of materials capable of producing large temperature changes. In this research, the largest measured electrocaloric eects were 0.75 K at electric elds of 1.5 MV/m in single crystal PMN-PT. The largest reports in the literature of a directly measured electrocaloric eect is 1.8 K at 2.0 MV/m in lead scandium tantalate at temperatures around 300 K[42]. The limitation may not be in the thermal properties of the materials, but in the design of devices to exploit the cooling power of these materials.

93 If the thermoacoustic eect discussed in section 1.2 could be generalized to describe a device using a generic thermally-active element in a process analogous to the Stirling cycle, such a device could achieve greater cooling power and larger temperature spans than current solid-state cooler designs. In this chapter, an all-solid-state heat pump analogous to the thermoacoustic eect in uids will be described. Though the design may be adapted to exploit one of many thermal eects, this heat pump is designed to use electrocaloric elements as a working medium.

5.1

A theoretical model
So long as some physical symmetry is broken[60], a small, cyclical temperature

change can be used to establish temperature gradients much larger than the local temperature change. Thermoacoustics provides a model for a novel thermodynamic cycle to more eectively use solid-state thermodynamic eects.

5.1.1

A quick review of thermoacoustics

Fig. 5.2. The thermoacoustic cycle

94 Literally, thermoacoustics is the interaction of heat and sound. Specically, thermoacousticians design closed-cycle heat engines using the inertia, compliance, and dissipation of acoustic media to replace the mechanical pistons and linkages of conventional heat engines and refrigerators. While normal sound is adiabatic, standing waves along a solid interface can interact with the interface to pump heat. Figure 5.2 shows a diagram of the thermoacoustic cycle. In the rst panel, the gas moves to the right and is compressed. In the next panel, the compressed gas transfers a small amount of heat to the solid, compressing further. In the third panel, the gas moves to the left and expands. In the nal panel, the gas absorbs a small amount of heat from the solid and expands. A small amount of heat has been moved from left to right, and the cycle repeats. Just before and just after this parcel of gas is another small parcel of gas, which allows a bucket-brigade-like eect to occur, building a large temperature gradient from a small local temperature oscillation in the gas. Schematically, it is easy to envision a generic temperature oscillation interacting across an interface. In the next section I will generalize the heat transport equations in thermoacoustics to present a theory for a general cycle analogous to the thermoacoustic cycle.

5.1.2

Generalizing the thermoacoustic cycle While gure 5.2 shows a schematic of the actual thermoacoustic eect, gure 5.3

shows an abstraction of the eect. The uid half of the interface has been replaced by a solid capable of producing a temperature oscillation. Every other solid plate is free to move parallel to the interface. Provided that the move plate travels farther

95

Fig. 5.3. A generalized Stirling-like heat pump cycle

96 laterally than the heat generated by the temperature oscillation, the resulting eect should be completely analogous to the thermoacoustic eect. Two length scales would need to be observed for this analogy to hold. First, the plates would have to be within one thermal penetration depth of each other. This would allow heat to be transferred between the plates within the time span of the oscillation. Second, as previously stated, the relative displacement of the two plates would have to be much greater than the thermal penetration depth, breaking a physical symmetry that would cancel out any net heat transport. For BST and PMN-PT, the thermal pentration depth for a 30 Hz oscillation is about 100 m. A 200 m thick plate would be nearly totally thermally active. 2 cm square, single crystal PMN-PT plates 200 m thick have already been produced. Ceramic PMN-PT and BST samples have been polished thinner than 250 m, though the largest areas made have been 1 cm cylinders. To break the heating symmetry, the plates would need to be displaced a distance greater than 1 mm relative to each other. This could easily be accomplished using a loudspeaker cone as an actuator. Thermoacoustics also provides a framework to estimate the maximum possible cooling power of an analogous relative motion device. The cooling power for a uid-based thermoacoustic cycle is found by the relation[50]:

1 Q = Tm p pa ua (1 RT ) 2

(5.1)

where is the perimeter, =

2/2f is the thermal penetration depth, Tm is

the average temperature, p is the thermal expansion coecient of the uid, pa is the

97 amplitude of the pressure oscillation, ua is the amplitude of the velocity oscillation and RT is the ratio of established temperature gradient to a critical temperature gradient given by RT = m cp ua T 2Tm p pa f l (5.2)

where m is the mean density of the uid, cp is the specic heat at constant pressure, T is the temperature span, f is the frequency of the oscillation and l is the length of the interface. The critical temperature gradient

Tcrit =

2f Tm p pa m cp ua

(5.3)

is the point in thermoacoustics where temperature changes due to pressure oscillations exactly cancel the temperature changes due to displacement oscillations[50]. The expressions for Q and RT can be elucidated with a few substitutions. First, the pressure amplitude pa can be converted to a temperature oscialltion Ta with the relation Ta = Tm p p m cp a (5.4)

The velocity amplitude ua can be expressed in terms of the displacement amplitude a = ua /(2f ). Finally, the thermal working volume of the device is V = l . This simplies the temperature gradient ratio to

RT =

(T /l) (Ta /a )

(5.5)

98 The numerator in the temperature gradient ratio is the mean temperature gradient established across the device while the denominator is an eective temperature gradient given by the temperature oscillation amplitude Ta and the displacement amplitude a . The cooling power density Q/V can now be written as

Q 1 2 = f m cp Ta R (1 RT ) V T T

(5.6)

This density has a maximum value when the ratio RT = 1/2. The maximum cooling density can then be dened as

Q T = m cp Ta f a V 4 T

(5.7)

The factor m cp Ta is the amount of heat per unit volume generated in one cycle of the device. The frequency converts the heat per cycle to the heat per second. Ta /T is the fraction of the total temperature lift T provided by the temperature oscillation Ta . Table 5.1 shows the theoretical maximum cooling power density for a heat pump described by equation 5.7. The maximum cooling power density and total span achieved by the device are inherently trade-os; the larger a temperature span sustained, the less cooling power available for the device. As this is a rst principles theory, loss eects have been neglected. As a result, cooling power density is not reported when it drops below 1.0 W/cm3 K. Since the cooling power increases as the square of the

99

Lift (K) 0.5 1.0 1.5 2.0 2.5 3.0 4.0 5.0 7.5 10.0 12.5 15.0 20.0 25.0 30.0 40.0 50.0

(Q/V )M ax (W/cm3 ) 0.50 0.66 1.00 1.50 2.00 35.3 61.6 141 318 565 23.5 30.8 94.3 212 377 11.8 20.5 47.1 106 189 8.8 15.4 35.3 79.5 141 7.1 12.3 28.3 63.6 113 5.9 10.3 23.6 53.0 94.3 4.4 7.7 17.7 39.8 70.7 3.5 6.2 14.1 31.8 56.6 2.4 4.1 9.4 21.2 37.7 1.8 3.1 7.1 15.9 28.3 1.4 2.5 5.7 12.7 22.6 1.2 2.1 4.7 10.6 18.9 1.5 3.5 8.0 14.1 1.2 2.8 6.4 11.3 1.0 2.4 5.3 9.4 1.8 4.0 7.1 1.4 3.2 5.7

Ta

Table 5.1. Cooling power at a given temperature span (lift) of a thermoacoustic-like device operating at 30 Hz

100 driving temperature oscillation Ta , even small improvements in the caloric elements could signicantly reduce the size of a potential device. It is important to note that the theoretical performance summarized in table 5.1 is for any physical mechanism capable of producing temperature oscillation Ta at a frequency of 30 Hz. While in the traditional thermoacoustic picture only the uid is capable of generating a temperature oscillation, one could double the eective temperature oscillation using two thermally active solids properly phased with each other. Hence, a temperature oscillation of 0.5 K in one element translates to a working temperature oscillation of 1.0 K.

5.2

Description of device
Figure 5.4 shows a plan for a demonstration solid-state heat pump. At the heart

of the heat pump is a stack of rectangular caloric plates. Every other plate is rotated 90o so that the ends of the plates stick out slightly from each side. Beryllium copper exures are attached to the protruding ends of the rotated plates. A conductive paint is used to electrically connect an electrode on the plate stack to the copper exure. Four electrical connections are needed to apply opposite electric elds on every other plate but have no potential dierence in the small gap between electrodes. Copper blocks are attached to the stationary plates for structural support and also serve as heat exchangers. The moving plates can be driven by a piezoelectric actuator, a loudspeaker with a linkage, or some other type of piston. The caloric elements could be either BST or PMN-PT; estimations of the performance of each of these materials in this proposed device are presented in the next section.

101

Fig. 5.4. Proposed design of all solid state heat pump

102

5.3

Predicted performance using ferroelectric ceramic elements

Max Ta = 1.0W/cm3 Span at Q/V Q/V at 30 K Span

2.0 K 150 K 9.4 W/cm3

Table 5.2. SSHP performance using 1.0 K caloric elements

Table 5.2 shows the performance characteristics of a hypothetical relative motion heat pump using caloric elements capable of producing a temperature oscillation of 1.0 K. If each layer could generate this temperature change and the device could be properly phased, the total net temperature oscillation would be 2.0 K. Given this temperature oscillation, equation 5.7 predicts that the device could produce a temperature span greater than 200 K at almost no cooling load. To sustain a cooling over a 30 K temperature span, the device could theoretically achieve a cooling density of 9.4 W/cm3 . Cooling the volume the size of a human body would require about 150 W of cooling power. If the caloric elements could achieve the 1.0 K oscillation, the proposed device would require 16 cm3 of active material to achieve this cooling over the 30 K span; this would require a device with a length of 2.5 cm on each side. While measurements made on BST and PMN-PT ceramics only observed maximum electrocaloric eects between 0.4 and 0.5 K, these ceramics may still be useful

103 BST 0.45 K 10 K 5K 15 K 1.8 W/cm3 PMN-PT 0.38 K 50 K 35 K 30 K 3.1 W/cm3 1.0 W/cm3

Max T T > 0.25K T > 0.33K Span at Q/V = 1.0W/cm3 Q/V at 10 K Span Q/V at 30 K Span

Table 5.3. SSHP performance using BST and PMN-PT ceramic elements

in designing and building small-scale coolers. Table 5.3 shows performance characteristics of a relative motion solid-state heat pump using both BST and PMN-PT elements. While the maximum electrocaloric eect observed in BST is slightly larger than that measured in PMN-PT, the electrocaloric eect in BST drops o rapidly as the temperature diers from the peak eect temperature. PMN-PT has an electrocaloric eect larger than 0.25 K over a 50 K temperature span compared to a 10 K temperature span in BST. PMN-PT has an electrocaloric eect greater than 0.33 K over a 35 K temperature span compared to only a 5 K temperature span in BST. This limits a BST-based heat pump to a maximum operating span of 15 K whereas PMN-PT could operate over a 30 K span. Q/V > 1.0W/cm3 was chosen as the threshold of operation because the theory of operation currently does not account for losses, such as thermal conduction, which must be overcome in a practical device. Over a 10 K operating span, a PMN-PT solid-state heat pump should be able to achieve a cooling density of 3.1 W/cm3 . If the device was constructed from 10 layers with dimensions of 22 mm by 18 mm by 0.2 mm,

104 a demonstration cooler should be able to produce 12 W of cooling power about the same power as other thermoacoustic demonstration coolers[50].

105

Chapter 6

Conclusion

Many challenges in the realm of physics, materials science and engineering exist before a practical electrocaloric refrigerator is ready for the market. First and foremost, we need to construct a working prototype to verify AC-to-DC temperature conversion. With a working prototype, research in better electrocaloric materials will need to be conducted to further understand ferroelectric properties. To bridge the electrocaloric measurements in bulk materials and estimated electrocaloric eect in thin lms, a detailed study of polarization in bulk materials should be conducted to conrm the integral relation. The mapping would need to include measurements of the dielectric constant, (Eq , T ), as a function of temperature and external electric eld. In addition, the pyroelectric eect will need to be measured with no external electric eld to determine any temperature eects of the constant of integration. The electrocaloric temperature change, TE (Eq , T ), could then be mapped as a function of
q

temperature and external electric eld to conrm the relation. Thin lms should also be tested to try to directly observe any electrocaloric eect. Thin lms can reportedly withstand electric elds in excess of 20 MV/m[31, 32]. The mechanism which supports larger elds should be investigated further, beacuse if thinner single crystal or ceramic plates could be made which could safely accept electric elds larger than 2 MV/m, larger electrocaloric eects may be measured in bulk BST or PMN-PT. While it is dubious to

106 calculate electrocaloric temperature changes from thin-lm polarization measurements, it may be possible to observe some temperature change. If a thin lm 2 m thick can truly create a 12 K electrocaloric temperature change[31], some direct temperature change should be observable on a 150 m thick substrate. Provided that the specic heats of both the thin lm and the substrate are comparable, a 12 K temperature change in an isolated lm would translate to a 0.16 K temperature change in a thin lm-substrate system. The direct electrocaloric temperature measurement setup has a resolution capable of seeing temperature changes as small as 0.4 K, so direct observations of the eect from a thin lm are possible. While thin lms may lead to larger temperature changes in BST or PMN-PT, there are other reported ferroelectrics capable of producing 1 K electrocaloric eects. If reports of electrocaloric eects larger than 1 K in perovskite ferroelectrics such as lead scandium titanate are true[42], these materials could open the door for better exploitation of thermoacoustic-based solid state heat pumps. In addition to a better understanding of the materials themselves, processing techniques need to be developed to produce thinner samples with larger areas. Previous research[23], conrmed by data in chapter 3, shows that better electrocaloric eects are achieved by larger grained ceramics. However, larger grained ceramics tend to be more brittle. A detailed study of mechanical properties such as Youngs modulus must be performed to better understand the limits to aspect ratio of caloric plates for building larger devices. Achieving a sustained temperature gradient through a moving temperature oscillation is still just a rst step. Even with advances in elements themselves, an eective

107 heat exchanger would need to be designed to convert the temperature gradient into useful cooling power in a practical device. Each element added in the process of converting work into cooling power introduces new loss mechanisms and engineering challenges. While a caloric element capable of 30 K temperature changes remains the holy grail of solid-state cooling, making better use of easier to control caloric eects can open up a new eld of development for all-solid-state devices capable of producing a greater cooling density compared to current technology.

108

Appendix A

Protocol for preparing ceramics

A.1

BST Protocol, July 2007

Preliminary steps, as necessary: a) Burn out oven, crucibles, and mixing/grinding media. b) Use high purity metal oxide and carbonate powders, 99.99% or better. c) Use only reagent grade acetone (99.5% purity or better) to mix the powder or to clean any vessel contacting the BST. 1. Weigh powder. For 50 g Ba0.67 Sr0.33 TiO2 : 25.346 g BaCO3 ; 9.339 g SrCO3 ; 15.313 g TiO2 . 2. Form a slurry with 50 g powder and 150 ml acetone in a 1 l Nalgene bottle. 3. Add 500 ml Zr media; media should be just below level of slurry. 4. Mix on roller mill at 22 rpm for 4 hours. 5. Pour through SS strainer (to separate media) into a 1 l Pyrex bowl; rinse media in strainer with acetone once into bowl. Wash media, discarding acetone, for future use. 6. Dry slurry at 80 C; stirring occasionally to promote drying. Place under vacuum after initial drying. 7. Grind to ne powder in agate mortar and pestle. 8. Sieve through 250 m mesh into Zr trays. 9. Calcine in oven. Ramp up at 5 C/min to 1200 C for 6 hours; ramp down at 5 C/min. 10. Put dry calcined powder in 1 l Nalgene bottle with 150 ml Zr media. Dry-grind in balanced vibratory mill for 4 hours. 11. Perform x-ray diraction (XRD) analysis on sample of dry-ground powder. Determine if calcining eliminated non-BST materials. 12. Add 150 ml acetone to the grinding bottle, then add more Zr media to reach just below slurry level. 13. Wet-grind in balanced vibratory mill for 6 hours.

109 14. Dry slurry as in step 6. 15. Grind to ne powder in mortar and pestle. 16. Clean die with lint-free tissue. 17. Weigh 0.5 g powder on small square of waxed massing paper and sieve through #50 mesh screen into 1/2 inch die. 18. Uniaxially press to 5700 lbs (29,000 psi = 200 MPa for 1/2 inch die) and hold for 30 seconds. 19. Cold isostatic press (CIP) to 200 MPa (if available). 20. Place green pellets on Zr tray and cover with second tray; place in oven. 21. With O2 diverted to water in beaker, adjust needle valve for ow rate of 1 bubble/s; reconnect O2 to oven. 22. Heat oven at 5 C/min to 400 C and hold for 1 hour; heat at 3 C/min to 1500 C and hold for 6 hours; cool at 2 C/min. 23. Cut 250 m thick wafers of sintered pellets using commercial ceramic wafering saw. 24. Sputter Cr/Al electrodes on each wafer face using Perkin-Elmer 4400 sputtering machine.

A.2

PMN-PT Protocol, July 2008

Preliminary steps, as necessary: a) Burn out oven, crucibles, and mixing/grinding media. b) Use high purity components, 99.9% or better. To avoid the pyrochlore phase, the powder is made in two stages. A.2.1 Stage I: MgNb2 O6 preparation

1. Weigh powder. For 50 g MgNb2 O6 : 6.697 g MgO; 43.302 g Nb2 O5 . (2% mol MgO is added to inhibit the pyrochlore phase.) 2. Form a slurry with 50 g powder and 150 ml ethanol in a 1000 ml Nalgene bottle. 3. Add 500 ml Zr media; media should be just below level of slurry. 4. Mix on roller mill at 22 rpm for 12 hours. 5. Pour through SS strainer (to separate media) into 1000 ml Pyrex bowl; rinse media in strainer with ethanol once into bowl. Wash media, discarding ethanol, for future use. 6. Dry slurry at 80 C. Stir occasionally to promote drying. 7. Grind to ne powder in agate mortar and pestle.

110 8. Sieve through a #50 mesh into a zirconia crucible. 9. Calcine in oven. Ramp up at 5 C/min to 1000 C for 6 hours; ramp down at 5 C/min. 10. Put dry calcined powder in 1000 ml Nalgene bottle with 150 ml Zr media. Drygrind in balanced vibratory mill for 4 hours. 11. Perform x-ray diraction (XRD) analysis on sample of dry-ground powder. Determine if powder has the proper columbite phase and is free of unreacted powder. 12. Add 150 ml ethanol to grinding bottle, then add more Zr media to reach just below slurry level. 13. Wet grind for 6 hours in a balanced vibratory mill. 14. Recover the powder following steps 5 through 8. 15. Dry the powder in the oven at 200 C for 12 hours. 16. Transfer dry powder to a 250 ml Nalgene bottle. 17. Store powder under vacuum to prevent absorption of moisture. A.2.2 Stage II: 0.92PMN- 0.08PT preparation

1. Weigh powder. For 50 g PMN-PT: 34.501 g PbO; 14.549 g MgNb2 O6 ; 0.988 g TiO2 . (5% mol of PbO is added to compensate for loss during ceramic processing.) 2. Form a slurry with 75 g powder and 150 ml ethanol in a 1000 ml Nalgene bottle. 3. Add 450 ml Zr media; media should be just below level of slurry. 4. Mix on roller mill at 22 rpm for 12 hours. 5. Pour through SS strainer (to separate media) into 1000 ml Pyrex bowl; rinse media in strainer with ethanol once into bowl. Wash media, discarding ethanol, for future use. 6. Dry slurry at 80 C. Stir occasionally to promote drying. 7. Grind to ne powder in agate mortar and pestle. 8. Sieve through a #50 mesh into Al2 O3 crucible and cover. 9. Calcine in oven. Ramp up at 5 C/min to 800 C for 4 hours; ramp down at 5 C/min. 10. Put dry calcined powder in 1000 ml Nalgene bottle with 100 ml Zr media. Drygrind in balanced vibratory mill for 4 hours. 11. Perform x-ray diraction (XRD) analysis on sample of dry-ground powder. Determine if powder has pyrochlore phase.

111 12. Add 150 ml ethanol to grinding bottle, then add more Zr media to reach just below slurry level. 13. Wet grind in balanced vibratory mill for 6 hours. 14. Recover the powder following steps 5-7. 15. Sieve all the powder through a #50 mesh screen and store in a 250 ml Nalgene bottle. 16. Add 35 g of PMN-PT powder into a 200 ml Pyrex dish. 17. Measure out 4% of powder weight of binder resin into another 200 ml Pyrex dish. For 35 g of powder, this corresponds to 1.4 g of binder resin. 18. Dilute binder resin with acetone until the resin completely dissolves into a clear liquid. 19. Pour the diluted binder resin into the dish containing the powder and stir the liquid into the powder using a stainless steel spatula. 20. Continue stirring until the acetone has completely evaporated. Transfer the powder to a mortar. 21. Grind the powder with a mortar and pestle, sieve through a #50 mesh screen and store powder until it is ready to be pressed. A.2.3 Stage III: Pressing 1/2 ceramic disks

1. Measure 0.7 g of binderized powder. 2. Wipe o die with lint-free tissue. 3. Increase the pressure in the press until the force gauge is just beginning to get a reading. 4. In one motion, press to a force of 4500 lbs and hold for 10 seconds. 5. Remove the pellets from the die and measure their mass. 6. Place the pressed pellets on Pt foil on a Zr plate. Place the plate in the oven. 7. Burn out the binder by heating the oven at 1 C/min to 325 C and hold for 3 hrs. Heat oven at 2 C/min to 500 C and hold for 10 hrs to remove the ash. Turn o the heating elements and let the oven cool. 8. Measure the mass of the pellets just after coming out of the furnace. The pellets should have lost about 1.5 to 1.7% of the initial mass. Measure the thickness of the pellets to compute the green density. The green density should be between 4.4 g/cc and 4.8 g/cc.

112 9. Place the pellets on Pt foil in the lid of an Al2 O3 crucible. Cover with a second sheet of Pt foil. Cover with the crucible and place in the oven. 10. Sinter the pellets heating the oven at 10 C/min to 1280 C. Hold the oven at 1280 C for 2 hours. Turn o the heating elements and let the oven cool. 11. Polish the sample on one face to create a at, smooth surface. 12. Polish the samples other face until the sample has a total thickness of 300 m or less. 13. Measure the mass of the pellets just after coming out of the oven. Measure the thickness and diameter to compute the density. The ceramics should have a density within 2% of 8.0 g/cc. 14. Anneal the polished samples to remove any excess lead that may have built up in the ceramic. 15. Sputter Cr/Al electrodes on each wafer face using Perkin-Elmer 4400 sputtering machine.

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Appendix B

Perkin Elmer 4400 Operators Reference

B.1
B.1.1

Start up procedure:
Start up from shutdown:

1. Open the N2 purge gas regulator. 2. Turn on the cryopump water using the middle valve located on the wall between the two windows about 10 ft high. 3. Turn on the compressed air line, located behind the sputtering unit about 12 feet high. 4. Make sure that all keys are set to Manual and the all switches are set to o or closed. 5. Turn on the main breaker on the back of the sputtering unit under the load lock. 6. Locate the Ultek Auto Pumpdown Control (APC). 7. Turn on the mechanical pump. 8. Turn on the Hi-Vac pump. 9. Open the throttle valve. 10. Open the Plexiglas door on the lower right side of the unit. Locate the cryo-pump regeneration control. 11. Turn the cycle time minutes control knob to the right, slightly o the 0 mark and push the red start button. At the end of the cycle, all adsorbed gases in the cryo-pump should be vented and the temperature should reach 10 K. B.1.2 Start up from overnight:

1. Turn on the network water by opening the valve below the cryopump water valve. Check the ow meters on the cryopump panel below the Ultek Lock Control (ULC) to make sure that water is owing. 2. Make sure that the vent fan is on and the purge gas cylinders are open. 3. Check the key on the APC. If the key is set to Manual or Manual (interlock), set the key to Auto. Pump down the chamber by holding the Start button on the APC and pressing the Pump button. When the trip light comes on the hi-vac valve should open. 4. When the convectron gauge reads 0-1 mTorr, turn on the ion gauge. If the chamber is kept under vacuum the ion gauge should read below 5.0 107 Torr after 2-3 hours. If the unit has not been used in a while, the ion gauge may take a while to reach this value. 5. Vent the load lock. When the ATM light turns on, close the vent line and set the ULC key to Auto. 6. Open the gas regulators on the Ar and N2 cylinders.

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7. Turn on the target water using the valve located below the cryopump water valve. 8. Turn on the RF generator and the DC power supply located to the right of the sputtering unit. If the DC sputtering controller is beeping, press the blinking red light to silence the alarm. The light will continue to ash until the gas solenoid valve is opened.

B.2

Automatically controlled operating procedures:

1. With the ATM light on, depress both Up switches on the load lock lid. As the lid opens, the elevator will automatically raise the pallet for loading substrates. 2. Load substrates on the pallet. If working with a non-standard substrate, the total height must be kept below 3/4 or the pallet will not clear the gate valve. 3. Depress both Down switches on the load lock lid. Wait for the elevator to fully lower and seat before completely closing the lid. When the lid closes, the automatic loading sequence should begin. 4. To interrupt the pumpdown and loading sequence hold down Start and press Standby on the ULC. To resume loading hold Start and press Load. 5. Monitor the progress of the pallet as it loads into the sputtering chamber. Look through the viewport to make sure that the pallet is evenly balanced on the table and that nothing will catch on the chamber shutter as the table rotates. 6. If you need to use the DC sputtering target, wait for the chamber pressure to drop below 7.0 107 T orr as read by the ion gauge. 7. To add gas to the sputtering chamber, hold down Start on the APC, press Gas and then quickly press Pump. Pressure can build up behind the gas solenoid valve causing the chamber pressure to rise too quickly when the valve is opened. If the chamber pressure rises to much and the hi-vac valve closes, pump the system down by holding Start and pressing Pump on the APC. Wait for the trip light to illuminate and the hi-vac valve to reopen. 8. Repeat Gas, Pump, Gas bursts until the convectron holds at 0 mTorr with the gas light indicated. Open the ow controller cuto valve of the desired sputtering gas, located on the right side of the sputtering unit. Make sure the ow controller of the desired gas is turned on and set to ow. Run the gas pressure up to the desired level for sputtering. The convectron should read 8-10 mTorr. For Ar, the ow controller should be set point should be 3.7. 9. With the gas running, make sure the motor speed control is set at the yellow mark. Look in the viewport and conrm that the table is rotating. The pallet is now ready for sputtering. Detailed instructions can be found in the Sputter Procedures section of this guide. 10. When you have nished sputtering, turn the ow controller set point back to 0.0. When the convectron reads 0 mTorr close the ow controller cuto valve. Shut the gas solenoid by holding Start and pressing Pump on the APC panel. Check the chamber viewport to make sure that the pallet table has stopped rotating. If the table is still rotating 5 seconds after turning o the gas, tap on the front of the APC to free the relay. If you cannot free the relay, turn the rotation control all the way counterclockwise to stop the motor. Never attempt to load or unload the pallet if the table is rotating as this can damage the system. Contact the sputtering unit supervisor immediately.

115
11. With the pallet table stationary, unload the pallet by holding Start and pressing Unload on the ULC panel. The pallet will automatically unload and the load lock will vent to atmospheric pressure. 12. The purge gas line will run until the load lock is opened. To conserve N2 , open the load lock as soon as the ATM light is illuminated.

B.3
B.3.1

Sputtering Procedures:
DC Sputter Deposition:

1. Set the selector switches on the RF control panel to Sputter Deposit and Target 1. 2. The DC power supply is controlled by an interface panel in the bottom right corner of the sputtering unit. After Target 1 has been selected an alarm on this panel should sound. Press the ashing red button to silence the alarm. If the button is still ashing, check that gas is owing and that water is owing through the switches in the lower left panel. 3. Make sure that all of the yellow Remote lights are out and that the regulation mode is set to Power (left green regulation button lit). 4. Set the cathode power by holding down the Level button and turning the knob. For coarse adjustments, the Vernier button should not be lit. For ner adjustments, press the Vernier button. 5. Set the power ramp up time by holding the Ramp button and turning the knob. The system can easily handle a ramp of several kV per minute. 6. Set the sputtering time by holding the Ramp button, pressing the Set Pt button, and 1 turning the knob. Note: All time settings are displayed in 100 s of a minute. 7. If the target has not recently been used, clean the target as follows: 8. set the shutter position switch to Close and wait for the light above the shutter position switch to go out. The open section of the shutter should be closest to the sputtering chamber viewport. 9. Begin sputtering by pressing the green On button on the DC control panel. You can monitor power, voltage, and current on the top monitor of the panel and power, voltage, current, energy (kW-hrs), and time elapsed on the bottom monitor. 10. When the process stops, press the blinking red O button to silence the alarm. 11. To sputter onto a substrate, set the shutter position switch to Open. Wait until the light above the switch goes out. The open section of the shutter should be toward the left side of the chamber. The target is now ready for sputtering. If needed, adjust the deposition power and time by following the above procedure. B.3.2 RF Sputter Deposition:

1. Set the selector switches to Sputter Deposit and either Target 2 or Target 3 2. Make sure the RF power knob is turned all the way down and the Auto toggle switch on the digital clock timer panel is down (o). 3. If the selected target has not been recently used, clean the target as follows: 4. Set the shutter switch to Close and wait for the light above the shutter switch to go out. The open section of the shutter should be by the viewport of the sputtering chamber.

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5. Tune the system by turning on the RF power on/o button and slowly turning up the RF power adjust knob to the desired forward power. Carefully monitor the RF reected power meter and adjust the Load and Tune switches to minimize reected power, adjusting the RF power adjust as needed to maintain forward power. Keep the reected power below 10 Watts. 6. When the system is tuned, press the RF power on/o button to turn o the power. Flip the Auto toggle switch on. Set the sputtering time on the timer by holding down the blue button and punching in the desired time in tenths of seconds. Start sputtering by pressing the RF power button. The plasma impedance will vary slowly over time; monitor the reected and forward power and adjust tuning settings as necessary. The system will automatically turn o when the timer has nished counting down. After the power has been shut o, press the RF power button once to cycle the button. 7. Set the shutter switch to Open and wait for the shutter indicator light to go out. The target is now ready for RF sputtering. If necessary, forward power and deposition time can be changed using the above procedures. B.3.3 RF Sputter etching:

(Note: As the auto tune system is currently oine, Etch mode is not recommended at this time) 1. Set the selector switches to Sputter Etch and Etch 2. Make sure the RF power knob is turned all the way down and the Auto toggle switch on the digital clock timer panel is down (o). 3. During sputter etching mode, there is no way to prevent plasma from contacting the substrate. Keep in mind that the plasma starts bombarding the substrate as soon as it is lit. It is best to use the auto tune system if there is concern of thermally damaging the substrate due to prolonged exposure to hot gas ions. To manually tune the system, see the procedure for RF sputtering. 4. When the system is tuned, turn o the RF power. Flip the Auto toggle switch on. Set the etching time on the timer in tenths of seconds. Start etching by pressing the RF power button. The system will automatically turn o when the timer nishes counting down. When the etch has nished, press the RF power button once to cycle the button.

117

B.4
B.4.1

Shutdown procedures:
Overnight:

1. Turn o the RF generator and DC power supply. 2. Close all sputtering gas feed and make sure that the purge gas cylinder remains open. 3. Check that the pallet is unloaded. 4. Set the ULC key to Manual. 5. Pump down the load lock until the pressure falls below the trip point. 6. Turn o the ion gauge. 7. Check that the hi-vac and mechanical pumps switches are on and that only the throttle valve is switched open. 8. Close only the target water line. Water must remain owing through the cryo-pump compressor whenever the compressor is on to prevent damage. 9. If the cryo-pump temperature is above 50 K, the cryo-pump needs to be regenerated. Set the APC key to Manual and follow the procedure outlined in the start up from shutdown section to regenerate the cryo-pump. B.4.2 Longterm shutdown:

1. Check that the RF generator and DC power supply are turned o. 2. Check that the pallet is unloaded. 3. Pump down the load lock until the pressure falls below the trip point. 4. Check that the ion gauge is turned o. 5. Set all keys to Manual. 6. Close all valves. 7. Turn o the hi-vac pump. 8. Turn o the mechanical pump. 9. Close all gas cylinders and shut o the regulators. 10. Turn o the vent fan and compressed air line. 11. Make sure that the target water line is closed. 12. When the cryo-pump compressor has cooled (after about 30 minutes) close the cryo-pump water line. 13. Turn o the main breaker on the power distribution box located in the back of the sputtering system under the load lock.

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Vita

Matthew G. Hilt EDUCATION: May 2009 Ph. D. Physics The Pennsylvania State University May 2002 B. S. Physics Worcester Polytechnic Institute PRESENTATIONS: Matthew G. Hilt, K. A. Pestka II, Jin H. So, and J.D. Maynard (2007, March). Elastics constants and sound velocities in single crystal transition metal scandates. Paper presented at the annual meeting of the American Physics Society, Denver, CO. Matthew G. Hilt, K. A. Pestka II, G. D. Mahan, J. D. Maynard, D. Pickrell, B. Na, and J. Tamburini (2006, May). Unconventional thermoacoustic heat engines (A). Journal of the Acoustical Society of America, 119, 5, p. 3414. J. D. Maynard, Matthew G. Hilt, and Logan Marcus (2005, September). Thermophysical properties, as functions of pressure and temperature, for over 300 uids, in vapor or liquid phase (A). Journal of the Acoustical Society of America, 118, 3, p. 1927. TEACHING EXPERIENCE: 2008 Instructor, Fluids and Thermal Physics (PHYS 213), The Pennsylvania State University 2008 Instructor, Wave Motion and Quantum Physics (PHYS 214), The Pennsylvania State University 2005 Teaching Assistant, Mechanics (PHYS 211), The Pennsylvania State University 2004 Lab Instructor, Senior Labs (PHYS 458/402), The Pennsylvania State University