The Analysis of Nuclear Materials and Their Environments

288 Pages·2017·2.04 MB·English

by  Claude André Degueldre

Claude André Degueldre
The Analysis
of Nuclear
Materials
and Their
Environments
The Analysis of Nuclear Materials
and Their Environments
é
Claude Andr Degueldre
The Analysis of Nuclear
Materials
and Their Environments
123
ClaudeAndréDegueldre
Engineering Department
Lancaster University
Lancaster
UK
and
Department ofAnalytical andMineral
Chemistry
University of Geneva
Geneva
Switzerland
and
Nuclear Energy Division
PaulScherrer Institute
Aargau
Switzerland
ISBN978-3-319-58004-3 ISBN978-3-319-58006-7 (eBook)
DOI 10.1007/978-3-319-58006-7
LibraryofCongressControlNumber:2017939092
©SpringerInternationalPublishingAG2017
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Foreword
I am very pleased to see this new book on The Analysis of Nuclear Materials and
Their Environments by Claude Degueldre. The challenge of analyzing nuclear
materials is that normal procedures are often difficult to use because of the
high-radiation field surrounding the material, say with spent nuclear fuel. At the
other end of the spectrum, the challenge is to analyze environmental materials in
which concentrations of radionuclide are extremely low. In both cases, it is
important to determine the solid-state chemistry of the nuclear material and the
speciation of the radionuclide in the environment. This is exactly the type of data
that are the foundation of safety analyses required by regulators for nuclear
facilities.
ProfessorDegueldrehaswrittenabookthatsystematicallypresentsandupdates
the full range of analytical techniques that can be applied to nuclear materials and
radionuclides in the environment. His treatment is comprehensive, dividing the
techniquesintotwobroadcategories—thosebywhichamaterialmaybeexamined
by passive techniques, such as particle scattering, and those that require an inter-
actionoftheenergyoftheprobewiththesample,suchasthosethatcauseelectron
excitations. For both cases, the explication of each technique emphasizes an
understanding of the interactions and detection methods for the probe energy and
solid/liquidinteractionsthatarethebasisforthedifferenttechniques.Bycombining
thediscussionofthetechniquesintoasinglevolume,thereadercanalsoappreciate
thedifferentlengthscalesatwhicheachprobesamplesthepropertiesofthenuclear
material. This allows scientists to match the proper technique to the scientific
questionthatisbeingasked.Iappreciatetheemphasisonthedetectionmethods,as
detection is often the major challenge of an analytical technique. As the author
emphasizes, the way forward with these challenging analytical problems is to
combine techniques, taking advantage of the range of particle/wave interactions
v
vi Foreword
with the samples. This book is a welcomed introduction to the panoply of
approaches that are available to the modern analyst faced with the challenge of
analyzing nuclear materials or radionuclides in the environment.
May 2017 Rodney C. Ewing
Frank Stanton Professor in Nuclear Security
Center for International Security and Cooperation
Stanford University
Preface
Nuclear materials and their environments require analyses before and during their
utilizationaswellasafterserviceduringdisposalnotonlyfromthecurrentnuclear
units but also from planned or foreseen nuclear installations or systems.
Prior analysis, sampling, and sample treatment must be carried out when the
analyticaltechniqueisnotappliedinsitu,inanon-invasiveway,orinanin-lineor
on-line mode.
Theanalysismaybecarriedoutinsitu,forexampleusingaremotesystem,orin
anundergroundlaboratoryinthephaseunderconsideration.Theanalysismayalso
be done ex situ with transfer of the sample and separation when needed. For all
analyses, sample volume, mass or amount, the flux of reagent, the size of the
analyzed part of the sample and the acquisition time or time of analysis are key
parameters that may affect the detection limit.
The information required—such as the chemical or radioisotope activity, the
mass orvolumeofthesampledandanalyzeditem, theconcentration asfraction or
molarityofdopantsorcontaminantsandthetypeorsizeofstructuresinthestudied
phases—hastobedeterminedinamulti-scaleapproachatthenuclearscale,atomic
or molecular scale, at the microscopic or macroscopic structural scale, at the bulk
scale, at the component or system scale, and/or at the environmental or geo-
graphical scale according to the requirements of the study. Identification concerns
theactinides,fissionproductsoractivatedproductsasisotopesorelements,butalso
their speciation that may not only be done at the molecular scale but also in a
broader sense such as at the environmental level. The time scale ranges from the
femtosecond, accessible during Free Electron Laser investigations to describe
ultra-fast phenomena, through the nanosecond to the mega-second, then to the
giga-second or penta-second the timescale of uranium-238 half-life or of the age
of the fossil natural geo-reactors. The explored energy range along the analytical
methods goes also from the nano-eV (Mössbauer or nuclear magnetic resonance
spectroscopy) to the giga-eV (muon-tomography), for example.
vii
viii Preface
Passive and active analytical methods have been revisited in this work, with
examples of their utilization in transmission, injection, diffusion or reflection
modes.Thesamplingarea,beamsizeandreagentquantitiesareeithermacroscopic,
microscopic or nanoscopic in size, while spatial-temporal conditions make exci-
tation incidence versus detection directions possible through solid angles, with
synchronous detection or with temporal delay.
Inthisworktheinvestigatedanalyticaltechniqueshavebeenclassifiedaccording
to their interactions, if any, between incident waves, particles or injected reagents
and the analyzed sample, and, for their detected or recorded signals. For passive
techniques, excitations are absent and phonons, photons, leptons, neutrons or ions
are detected or quantified for their energy, flux, activity, quantity or mass. For
interactive techniques, irradiations or reagent additions are made with phonons,
photons,leptons,neutronsorionswithaknownenergy,flux,activityormass.The
irradiation or injection is done locally while the reception may be carried out in a
given space at a given angle from the stimuli direction or the incident beam,
instantaneously or after a certain delay after irradiation.
Thedetectiontoolsarespectroscopy,microscopy,radiography,andtomography.
The reaction takes place within or without a specific field such as electrical,
magnetic,flowormechanicalacceleration.Thedetectedsignalmaybethesamein
natureastheincidentone,withthesameenergy,elasticinteraction,orasignalwith
lowerenergyandinelasticinteraction,withparticlesbeingagainphonons,photons,
leptons,neutronsorions.Inadditiontotheseanalyticaltoolsortechniques,neutral
species such as atoms or molecules may also be used to interrogate the material.
Theyaretreated asions fromamassandchargepointofview.Thetechniquesare
classifiedaccordingtoincreasingenergyofreagentsorincidentparticlesorwaves.
Thecombinationofallexcitationorreagentadditionandproductdetectionsmakes
theanalyticpotentialveryrichtoperformtheidentificationofmolecules,elements
or isotopes, their quantitative determination, and their spatial speciation.
There has been an optimization of techniques and the discovery of new ana-
lytical tools over the last century. Some of the techniques are found today to be
obsolete, others re-emerge due to new interests; some may be completed by
combiningthepotentialofonetechniquewithanother.Inaddition,therehasbeena
constant challenge in pushing the use of the analytical techniques toward lower
detectionlimits,betterlateralanddepthresolutions,moreextremeapplicationsand
more flexible uses.
Asfarasthenuclearmaterialsareconcerned,studiesmustreflectthedemanding
conditions of temperature, pressure and irradiation under which they are used.
These materials act as barriers and their properties are investigated with emphasis
on mechanical performances, durability, plasticity and stability when damaged or
loadedbydopantsorcontaminants.Thesematerialsrangefromfuelsforthermalor
fastreactors,tostructuralmaterials.Fuelsareanalyzedpriortoandafterirradiation,
after their reprocessing for recycling and later as waste forms. Macro-properties
such as thermodynamic, thermophysical and mechanical as wellas microstructural
analysis of these materials have to be analyzed, for example comparing again
properties prior to and after irradiation.
Preface ix
As far as the environments of nuclear materials are concerned, one has to think
about the way the analyst and the environmental scientist would collaborate
together to produce data that can be used by modelers or by authorities. The
challenge is to understand the behavior of actinide elements, fission products and
other contaminants in the environment. Biogeochemical pathways have to be
described, quantified and understood. Transport of actinides, fission products and
other contaminants in fluids such as air or water include particulate or colloidal
phases. These analyses must be integrated in the analytical strategy as specific
species for modeling their biogeochemical behavior.
Data are provided by the analysts for the scientists and the modelers. The
problem is to understand the behavior of radionuclides in the systems or the
material properties with regard to its integrity. In the environment, contaminant
pathways have to be described. The contaminated systems interact with the local
environment that may modify radionuclide speciation by physical-chemical pro-
cesses. The analytical results must be integrated in the study for modeling their
chemical and physical properties.
Achallengeforfutureinvestigationswillbetofindanddevelopdirectanalytical
probes for full nuclear material characterization at very low defect, dopant or
contaminantconcentrationstobettercharacterizethedamages,speciesorstructures
and to predict their behavior in homogeneous, heterogeneous or complex nuclear
materials and in their environments.
Aargau, Switzerland Claude André Degueldre
Acknowledgements
The author would like to acknowledge several scientists who participated in dis-
cussions, providing material or notes. Specifically thanks are due to
– F. Aiouache, Lancaster University, UK
– R. Bellin, CEA Cadarache, France
– S. Caruso, Nagra, Switzerland
– M. Döbeli, ETHZ, Switzerland
– J. Griffin, Chemistry Department, Lancaster, UK
– M. Hertrich, Nagra, Switzerland
– M. Joyce, Lancaster University, UK
– A. Kerridge, Lancaster University, UK
– K. Patel, University of Cambridge, UK
– D. Shuh, BNL, USA
– S. Stefanovsky, All Bochvar Institut, Moscow, Russia.
– N. Toulhoat, CNRS/IN2P3, IPNL, France
– M. Tylka, ANL, USA
– E. Vance, ANSTO, Australia
– M. Veleva, PSI, Switzerland
The work has been the fruit of analytical practice over the last 45 years, mainly in
Algeria, Belgium, France, Germany, Japan, Switzerland, the UK and USA. The
work was however self-financed and its elaboration required intensive personal
work.Thedatareportedinthistextbookarenotspecificallythedataoftheauthorof
this work. They are taken from the open literature, and their use requires citation.
The author of this work is consequently not responsible for their quality. His
liability is restricted to the novel form of presentation of the analyses of nuclear
materials and their environment.
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