Including Actinides

412 Pages·2015·60.26 MB·English

by  Jean-Claude Bünzli and Vitalij K. Pecharsky (Eds.)

HANDBOOK ON THE PHYSICS AND CHEMISTRY
OF RARE EARTHS
Advisory Editorial Board
GIN-YA ADACHI
Kobe, Japan
WILLIAM J. EVANS
Irvine, USA
YURI GRIN
Dresden, Germany
SUZAN M. KAUZLARICH
Davis, USA
MICHAEL F. REID
Canterbury, New Zealand
CHUNHUA YAN
Beijing, P.R. China
Editors Emeritus
KARL A. GSCHNEIDNER, JR
Ames, USA
LEROY EYRINGw
Tempe, USA
w
Deceased (2005)
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Contributors
NumbersinParenthesesindicatethepagesonwhichtheauthor’scontributionsbegin.
Christopher L. Cahill (163), Department of Chemistry, The George Washington
University, Washington, Districtof Columbia,USA
Marek Daszkiewicz (109), Institute of Low Temperature and Structure Research,
PolishAcademy ofSciences, Wrocław,Poland
Olivier Q. De Clercq (1), LumiLab, Department of Solid State Sciences, Ghent
University, Ghent, Belgium
Lubomir D. Gulay (109), Department of Ecology and Protection of Environment,
Eastern European NationalUniversity, Lutsk,Ukraine
Qiong Jia(287),College ofChemistry, JilinUniversity, Changchun, China
WupingLiao(287),StateKeyLaboratoryofRareEarthResourceUtilization,ERCfor
the Separation and Purification of REs and Thorium, Changchun Institute of
Applied Chemistry,Chinese Academyof Sciences, Changchun, China
Oleg V. Marchuk (109), Department of Inorganic and Physical Chemistry, Eastern
European NationalUniversity, Lutsk,Ukraine
Dirk Poelman (1), LumiLab, Department of Solid State Sciences, Ghent University,
Ghent, Belgium
PhilippeF.Smet(1),LumiLab,DepartmentofSolidStateSciences,GhentUniversity,
Ghent, Belgium
Robert G. Surbella III (163), Department of Chemistry, The George Washington
University, Washington, Districtof Columbia,USA
Koen Van den Eeckhout (1), LumiLab, Department of Solid State Sciences, Ghent
University, Ghent, Belgium
ZhifengZhang(287),StateKeyLaboratoryofRareEarthResourceUtilization,ERC
for the Separation and Purification of REs and Thorium, Changchun Institute of
Applied Chemistry,Chinese Academyof Sciences, Changchun, China
vii
Preface
These elements perplex us in our reaches [sic], baffle us in our speculations,
and haunt us in our very dreams. They stretch like an unknown sea before
us—mocking,mystifying,andmurmuringstrangerevelationsandpossibilities.
SirWilliamCrookes(February 16,1887)
Volume 48 of the Handbook on the Physics and Chemistry of Rare Earths
adds four chapters to the series, covering broadly different, but timely, sub-
jects ranging from luminescent materials to properties of chalcogenides, ura-
nyl hybrid materials, and separation processes. Featured themes include
persistent luminescence, a phenomenon used in emerging applications such
as signage and bioimaging, the phase diagrams, structure, and physical prop-
erties of quaternary rare earth/lead/group IV (Si, Ge, Sn)/sulfur or selenium
compounds, structural chemistry of crystalline uranyl-containing compounds
obtained via hydrothermal synthesis, as well as description of state-of-the-
artinseparationandpurificationprocessesofrareearthsalongwiththeprep-
aration of high-purity rare-earth and thorium metals.
The first chapter (Chapter 274) is devoted to persistent luminescence, a
phenomenon whereby a compound keeps emitting light for a long time after
excitation is switched off. Ancient civilizations knew about this curious
phenomenon, but the first account of it in the Western world dates back to
the seventeenth century when the Bologna stone, obtained by calcining barite,
wasdescribed.Theemissionoflightinsuchmaterialsdependsontrapsgener-
atedbytinyamountsofimpurities;hence,differentsyntheticconditionsleadto
widelydifferentemissioncolors.Studyingthisfascinatingphenomenonisdiffi-
cultsothatitremainedacuriosityuntilthetwentiethcenturywhenzincsulfide
dopedwithtransitionmetals(cobalt,copper)startedtoplayanimportantrolein
luminous paints. Contributions of lanthanides to the field started at the end of
the1960swhenstrontiumaluminatedopedwithdivalenteuropiumwasdiscov-
ered.Afurtheranddecisiveimpetusoccurredinthemid-1990sinitiatedbythe
finding that co-doping trivalent dysprosium in this material produced a much
brighterpersistentphosphor. Thechapterreviewsallaspectsoflanthanideper-
sistentluminescencealongwithacriticalevaluationofpotentialapplicationsin
marking, solar energy conversion, and biosciences.
Quaternary rare-earth chalcogenide systems R X dPbXdZX (X¼S,
2 3 2
Se; Z¼Si, Ge, Sn) are the subject of Chapter 275. These compounds are of
broad interest in both basic and applied sciences due to their intriguing
ix
x Preface
thermal, optical, electrical, and magnetic properties. The design of increas-
ingly complex chalcogenide compounds is indeed vital for modern materials
science, primarily in reference to the development of nonlinear optical
devices.Thesystemsbasedonlead,sulfur,andseleniumareofspecialimpor-
tance because substitution of lead with rare earths results in modified optical
and magnetic properties that can be modulated while preserving the parent
crystal structure. These new phases can also be obtained at the nanoscale,
whichconsiderablybroadenstheirpotentialapplications,forinstanceincatal-
ysis, biotechnology, or medicine. In this review, synthetic conditions are
detailed, followed by a systematic presentation of known phase diagrams,
structures, and magnetic properties.
Chapter276dealswithcrystallinehybridmaterialsofuranyl.Thesemateri-
alscombineasubstrate(organicorinorganic)withuranylionoritscomplexes
that are blended on the molecular scale. Generally speaking, hybrid materials
arefoundinnumeroussystemsandcanbebroadlydividedintosol–gel(glasses,
silica, organically modified xerogels), porous (metal-organic frameworks),
mesoporous(silicates,zeolites),polymeric,intercalation(layereddoublehydro-
xides), and nanocomposite (nanoparticles) materials. Uranyl hydrolysis and
complex aqueous speciation are the red thread of the review as they represent
drivers for structural diversity. The chapter explores covalent bonding with
O- and N-donor ligands before highlighting ways of programming targeted
coordinationgeometries,compositions,andconnectivitiesintothehybridmate-
rials. Purely supramolecular systems, assembled thanks to noncovalent bonds
from simple tectons under highconcentrations of anionssuchaschloride, bro-
mide,orisothiocyanate,arealsopresented.Finally,luminescencepropertiesare
described, particularly with respect to structure/property relationships.
The final chapter (Chapter 277) presents a historical insight as well as
recent progresses in separation processes of rare earths, with a special focus
on Chinese operations. Rare earth ores always contain a blend of several
elements, and if some applications rely on mixtures (e.g., the Mischmetal,
neodymium/praseodymium/dysprosium mixtures for magnets, or lanthanum/
cerium mixtures for nickel metal hydride batteries or catalysts), many
high-technology uses need high-purity individual elements. Separation and
purification operations are complex, time consuming, and have negative
environmental effects. This points to the importance of developing efficient
separation taking into account environmental issues, by making use of
“greener” reactants and/or by recycling the chemicals involved. Both funda-
mental and applied investigations have to be combined to reach this goal.
The chapter reviews the various extractants, methods, and equipment that
have been developed for achieving efficient methodologies, progresses being
sustainedbyadequatetheoreticalmodeling.Itendsbydescribingtechnologies
for the production of very high-purity rare-earth elements and thorium, a
by-product of rare-earth extraction.
Preface xi
CHAPTER 274: PERSISTENT PHOSPHORS
Philippe F. Smet, Koen Van den Eeckout, Olivier Q. De Clercq, and
Dirk Poelman
LumiLab, Department of Solid State Sciences, Ghent University, Ghent,
Belgium. E-mail: [email protected]
Synthesis
Outlook Characterization
release
capture
In vivo
absorption emission traps Visibility
imaging
Mechano- Materials
luminescence overview
Thermoluminescence
Persistent luminescence is the phenomenon whereby a material keeps
emittinglightforsecondstohoursaftertheexcitationhasstopped.Thischap-
ter describes the history of this class of materials and how the discovery of a
new family of very efficient persistent phosphors has given a boost to the
development of both new materials and applications. Synthesis conditions
and analytical techniques specific to persistent luminescent compounds are
described, together with ways to evaluate their performance in terms of
human eye perception. A state of the art is presented about the materials—
hostsanddopants—currentlyinvestigatedforpersistentluminescence,consis-
tently referring to the original literature. Finally, in vivo medical imaging is
shown to be a promising but challenging application of long-wavelength per-
sistent luminescence and the relation between persistent luminescence and
mechanoluminescence are described.
xii Preface
CHAPTER 275: QUATERNARY R X dPbXdZX
2 3 2
(X5S, Se; Z5Si, Ge, Sn) CHALCOGENIDES
Lubomir D. Gulay*, Marek Daszkiewicz†, and Oleg V. Marchuk**
*DepartmentofEcologyandProtectionofEnvironment,EasternEuropean
University, Lutsk, Ukraine
†InstituteofLow-TemperatureandStructureResearch,PolishAcademyof
Sciences, Wroclaw, Poland. E-mail: [email protected]
**Department of Inorganic and Physical Chemistry, Eastern European
National University, Lutsk, Ukraine
Complex ternary, quaternary, and multicomponent chalcogenides contain-
ingrareearthsareinterestingbecauseofpotentialapplicationsinthefieldsof
ionic conductivity and nonlinear optics. The current knowledge about experi-
mental investigations of phase diagrams, crystallographic relationships, and
magneticpropertiesofquaternaryrare-earthchalcogenidesR X dPbXdZX
2 3 2
(X¼S, Se; Z¼Si, Ge, Sn) is the focus of the chapter. The initial section
describes typical preparation of these novel materials in small quantities for
studiesoftheirbasicphysicalpropertiesandservesasaguideforthoseinter-
estedinpreparinglargerquantitiesinordertoexploretheirpotentialforprac-
tical applications. Then the structure types of ternary PbdZdX (X¼S, Se;
Z¼Si, Ge, Sn) systems are presented, before the review concentrates on the
rare-earth-containing quaternary chalcogenides that are discussed according
to their structure type. Description of superstructures and known magnetic
properties concludes the chapter.
Preface xiii
CHAPTER 276: HYBRID MATERIALS OF THE f-ELEMENTS
PART II: THE URANYL CATION
Robert G. Surbella III and Christopher L. Cahill
The George Washington University, Washington, DC, USA. E-mail:
[email protected]
Thecatalogofuranyl-bearinghybridmaterialshasexpandedconsiderably
over the past 10–15 years. Researchers have drawn inspiration from the rich
portfolio of structural topologies found in naturally occurring uranyl mineral
phases where uranyl oligomerization stemming from hydrolysis is the norm.
With these phenomena as guiding principles, our group in particular has pur-
sued a program of exploring the relationship between synthetic reaction con-
ditions, including ligand geometries and functionalities, with solid-state
structure. As the synthetic efforts have flourished, a wide variety of structure
types have emerged, yet the ability to fully correlate reaction conditions with
resulting topologies remains elusive. As such, this chapter provides an over-
view of (whenever possible) synthetic “causes and effects” in the hydrother-
mal synthesis of uranyl hybrid materials. It then progresses to more recent
developments wherein milder, high anion conditions are utilized to develop
themes of assembly via noncovalent interactions between a more restricted
suite of uranyl species.
xiv Preface
CHAPTER 277: PROGRESS IN THE SEPARATION PROCESSES
FOR RARE EARTH RESOURCES
Zhifeng Zhang1, Qiong Jia2, Wuping Liao1,*
1State Key Laboratory of Rare Earth Resource Utilization, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun.
E-mail: [email protected]
2College of Chemistry, Jilin University, Changchun, China
RE mines
Novel extractants
Ion exchange
Solvent Separation
Extraction equipment
extraction processes
Double salt precipitation
Theoretical modeling
RE oxides High-purity REs
Rare earth elements have widespread applications in materials critical for
many high-technology applications, including catalysts, permanent magnets,
phosphors, lasers, and rechargeable batteries. Individual rare-earth elements
are oftenneeded sothat separation and purification ofrare-earth concentrates
are crucial. Importantly, these operations are suffering from environmental
problems and viable utilization of the resources. The chapter gives an over-
view of the evolution in fundamental research and industrial separation pro-
cesses for rare earths. First, the progresses in extractants, novel equipment,
alternative technologies, and theoretical modeling are summarized. Industrial
hydrometallurgy processesare discussedand evaluatedwith respecttodiffer-
ent ores of various origins. The preparation of highly pure rare earths and
associated elements such as thorium is then presented. Easily accessible
resources and environmentally friendly processes are essential issues to deal
with in order to ensure sustainable developments in rare earth metallurgy.
Jean-Claude G. Bu¨nzli
Vitalij K. Pecharsky
Contents of Volumes 1–47
VOLUME1:Metals
1978,1strepr.1982,2ndrepr.1991;ISBN0-444-85020-1
1. Z.B.Goldschmidt,Atomicproperties(freeatom) 1
2. B.J.BeaudryandK.A.GschneidnerJr,Preparationandbasicpropertiesoftherare
earthmetals 173
3. S.H.Liu,Electronicstructureofrareearthmetals 233
4. D.C.KoskenmakiandK.A.GschneidnerJr,Cerium 337
5. L.J.Sundstr€om,Lowtemperatureheatcapacityoftherareearthmetals 379
6. K.A.McEwen,Magneticandtransportpropertiesoftherareearths 411
7. S.K.Sinha,Magneticstructuresandinelasticneutronscattering:metals,alloysand
compounds 489
8. T.E.Scott,Elasticandmechanicalproperties 591
9. A.Jayaraman,Highpressurestudies:metals,alloysandcompounds 707
10. C.ProbstandJ.Wittig,Superconductivity:metals,alloysandcompounds 749
11. M.B.Maple,L.E.DeLongandB.C.Sales,Kondoeffect:alloysandcompounds 797
12. M.P.Dariel,Diffusioninrareearthmetals 847
Subjectindex 877
VOLUME2:Alloysandintermetallics
1979,1strepr.1982,2ndrepr.1991;ISBN0-444-85021-X
13. A.landelliandA.Palenzona,Crystalchemistryofintermetalliccompounds 1
14. H.R.KirchmayrandC.A.Poldy,Magneticpropertiesofintermetalliccompoundsof
rareearthmetals 55
15. A.E.Clark,MagnetostrictiveRFe intermetalliccompounds 231
2
16. J.J.Rhyne,Amorphousmagneticrareearthalloys 259
17. P.Fulde,Crystalfields 295
18. R.G.Barnes,NMR,EPRandM€ossbauereffect:metals,alloysandcompounds 387
19. P.Wachter,Europiumchalcogenides:EuO,EuS,EuSeandEuTe 507
20. A.Jayaraman,Valencechangesincompounds 575
Subjectindex 613
VOLUME3:Non-metalliccompounds–I
1979,1strepr.1984;ISBN0-444-85215-8
21. L.A.HaskinandT.P.Paster,Geochemistryandmineralogyoftherareearths 1
22. J.E.Powell,Separationchemistry 81
23. C.K.Jørgensen,Theoreticalchemistryofrareearths 111
24. W.T.Carnall,Theabsorptionandfluorescencespectraofrareearthionsin
solution 171
25. L.C.Thompson,Complexes 209
26. G.G.LibowitzandA.J.Maeland,Hydrides 299
27. L.Eyring,Thebinaryrareearthoxides 337
28. D.J.M.BevanandE.Summerville,Mixedrareearthoxides 401
xv