Spencer, Joel Quintus (1996) the Development of Luminescence Methods to Measure Thermal Exposure in Lithic and Ceramic Materials
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Spencer, Joel Quintus (1996) The development of luminescence methods to measure thermal exposure in lithic and ceramic materials. PhD thesis http://theses.gla.ac.uk/3557/ Copyright and moral rights for this thesis are retained by the author A copy can be downloaded for personal non-commercial research or study, without prior permission or charge This thesis cannot be reproduced or quoted extensively from without first obtaining permission in writing from the Author The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the Author When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given. Glasgow Theses Service http://theses.gla.ac.uk/ [email protected] The Development of Luminescence Methods to Measure Thermal Exposure in Lithic and Ceramic Materials by Joel Quintus Spencer Submitted to University of Glasgow (Faculty of Science) for the degreeof Doctor of Philosophy September,1996 This researchwas conductedat the Scottish Universities Researchand Reactor Centre, East Kilbride ®J. Q. Spencer,1996 Abstract Thermometric analyses provide extremely useful information about heated archaeological materials and fire-damaged modem structures. A number of non-luminescence thermometry methods have been developed for analysing pottery firing temperatures. However, many of these methods are limited in analysis range and accuracy, or are time consuming, expensive and complex. In addition to these techniques there are a number of thermoluminescence (TL) thermometry methods but they are also limited in analysis range and the majority have been developed for specific thermometry problems. The aim of this study was to investigate the use of thermoluminescence (TL) and photostimulated luminescence (PSL) methods to develop rapid, precise, inexpensive thermometry techniques that were applicable to a wide range of thermal events and materials from archaeological and modem contexts. A basic theoretical treatment of luminescencekinetics in silicate systemswas undertakento develop an understanding of TL glow curve alterations arising from thermal exposure. Kinetic studies showed that a combination of temperature and duration parameters is expectedfor single trap systems.Kinetic theory was developedto produce a new first order multi-trap system which provides a theoretical means of separatingtemperature and time components, which may be applicable to synthetic phosphors. Additionally heat transfer solutions were investigatedto examinethe temperaturedistribution in heatedsolids and TL instrumentation. Isothermal annealingexperiments on IAEA F-1 potassium feldspar showed a highly precise progressive thermal exposuremonitor, whereby the position of the first rise of an annealed TL glow curve is characterisedby a linear increase in temperature and a logarithmic increasein time. First order kinetic simulations and initial rise measurementsdemonstrated a continuous linear distribution of traps in IAEA F-1 feldspar. Using a high temperature TL system (maximum temperature 700°C) the progressive thermometry method was successfully applied to separated feldspar minerals and polymineral samples from archaeological (ceramics, burnt stones and hearthstones) and modem (fire damaged concrete) materials. PSL excitation spectroscopy showed potential thermometric behaviour but for some samplesthe sensitivity of the systemwas too low. Pulsed infra-red PSL showed there may be a limited trap distribution over which a small range of thermal exposureswill operate. Combined TL/PSL measurementsshowed it may be possible to deconvolute temperature and time parameters. Acknowledgements I would like to thank my supervisor Dr. David Sanderson for his continuing help and guidancethroughout this project. This thesishas also benefited from stimulating discussions and commentsfrom Prof. Roger Scott. A big thank you must also go to membersof the luminescenceand aerial survey group at SURRC (past and present) for their continuing help and good humour, and providing a stimulating working atmosphere: Peter, Lorna, Christine, Robert, Drew, Simon, Andy, Dave, Keith and Jacqui I would also like to thank many other members of staff at SURRC for their help and friendship during my researchin East Kilbride. And now on to the people who kept me sane(just) by topping me up with regular pints of beer: East Kilbride and Glasgow Kt, Juan, Sarah, Brucey-babes,Ian, Gawen, Jackie, Ellieeeee, Susan, Tony, Jane, Jamie, Dave P., Pauline, Marie... Aberdeen Hughsey, Cric & Andy M., Archie, Andy C., Johnny, Stevie, Nick, Helen, Chris, Gill, Cath, Sarah,Stefano, Polly & Neddy, Kathryn & Keith, Lucky Lips, Mengfang... A special thank you to Shark for all the virtual times... Finally a big thank you to my ever expandingfamily for all their love and support: Eric & Norma Matthew, Gaye & Louis Damian & Sarah Ben Onion Edney &Vanessa This research was made possible by receipt of a studentship from the' Science Based Archaeology Committee of the Science and Engineering Research Council, and additional support from my parents. Contents Chapter 1 Introduction 1 ........................................................................................................... 1.1 Importance history 1 of thermal ................................................................................. 1.2 Introduction luminescence 2 to ................................................................................... 1.2.1 Thermoluminescence(TL) Photostimulated luminescence(PSL) 2 and ........ 1.2.2 Historical 2 perspectives................................................................................ 1.3 Thermoluminescencethermometry 3 .......................................................................... 1.4 Non-luminescence 6 archaeothermometry.................................................................. 1.5 Thesis 8 aims and content ........................................................................................... Chapter 2 Theory 9 .................................................................................................................... 2.1 Introduction 9 ............................................................................................................. 2.2 Analytical the TL 9 modelsof process....................................................................... 2.2.1 Energyband 10 model................................................................................... 2.2.2 Assumptions first kinetics 14 of order ............................................................ 2.2.3 Solutionfor TL 14 peakshape: ...................................................................... 2.2.4 Isothermaldecay: Phosphorescence 16 .......................................................... 2.2.5 Relative for threetrap 17 retention a system.................................................. 2.2.6 Trap filling 19 ................................................................................................. 2.2.7 Continuousdistributions 21 of traps.............................................................. 2.2.8 Second kinetics 21 and generalorder ............................................................. 2.2.9 Summary 22 ................................................................................................... 2.3 Photostimulatedluminescence (PSL) 24 .................................................................... 2.4 Heat transfer thermal 26 and gradients....................................................................... 2.4.1 Generalheat transfer 26 equations................................................................. 2.4.2 Onedimensional steady state solution for a solid boundedby two 27 parallelplanes ............................................................................................ dimensional 28 2.4.3 One transientsolution for a semi-infiniteslab ........................ 2.4.4 Thermalproperties 29 ....................................................................................30 2.4.5 Thermalgradients in archaeologicalstructures and artefacts.................... 2.5 Heat in TL 31 transfer experiments............................................................................ 2.5.1 Static distribution in heater 31 temperature the strip ...................................... Heat between interfaces 34 2.5.2 transfer strip-sample and sample-gas .................. 2.5.3 Summary discussion 41 and ........................................................................... 3 Instrumentation 42 Chapter and measurementmethods .................................................... 3.1 TL 42 measurement.................................................................................................... 3.1.1 TL oven heating and system..................................................................... 42 3.1.2 Detectionand TL recordingof ..................................................................46 3.1.3 Specifications andperformance ................................................................. 49 3.2 Measurementof TL signals 500°C 49 above .............................................................. 3.2.1 Discussion of possible methods for > 500°C TL 50 ....................................... 3.2.1.1 Restricting PMT detection to ultraviolet wavelengths..................................................................... 50 3.2.1.2 Maskingand the light 51 restricting path.............................