Nuclear energetics and nuclear chemistry - new trends 4 Topics: 1) Fast reactors as a modern axe of nuclear energetics by order from WU : 2) NMR applied to nuclear materials 3) Synchrotron radiation methods applied to analises of nuclear materials 4} Drawbacks of actinide theory

1. Recent advances in nuclear chemistry
III Schoolof Energetic and Nuclear Chemistry
Biological and Chemical Research Centre
University of Warsaw, Poland
Konstantin
German
Frumkin Institute of Physical Chemistry and Electrochemistry
of Russian Academy of Sciences (IPCE RAS), Moscow, Russia
Medical institute REAVIZ

2. First : THANKS to WARSAW UNIV. my lecture given herelast year leads with approx. 2000 readings = 3 times more popular than the best followers
Visit of Russian Academy delegation to PolskaAcademia Naukin 1957
Ac. TadeuszMarian Kotarbiński–President PAN
Ac. Viktor Spitsyn –Director IPC ( the left)

3. Scope
•
Nuclear prospects in Russia
•
NMR for radioactive materials analyses
•
Sync Radiation
•
Actinide hypothesis verification

4. Homo sapience sp. was the most efficient one in applying technologies to improving its life
Economist Kenneth Boulding(1956) : one who believes that exponential growth could be ethernalin the limited world is either mad or economist
Neand.sp. sp.
Cosmo sp.
Coal ‐
Steam
engin
Oil –
essengin
T E C H N O L O G Y

5. Petroleum energeticswiki :
•
Themodern historyof petroleum began in the 19thcentury with the refining ofparaffinfrom crude oil. The Scottish chemistJames Youngin 1847 noticed a naturalpetroleumseepage in theRiddingscolliery‐Derbyshire. He distilled a light thin oil suitable for use as lamp oil, at the same time obtaining a thicker oil suitable for lubricating machinery. •
In 1848, Young set up a small business refining the crude oil. The new oils were successful, but the supply of oil from the coal mine soon began to fail (eventually being exhausted in 1851).
•
Great sceptisismto petroliumburning was shown by D. Mendeleev… •
Once started it will once stop
WHAT After… ?

6. World state and preferences in energetic development
OilGas Coal Bio
NuclearHydro/ThermalWind/Sun

7. Discovery of radioactivity and estimation of its importance
Becquerel
•
In 1896 found out that Uranium ore is emitting some new kind of rays.
Curie and Sklodowska
•
FrenchphysicistPierreCurieandhisyoungPoleassistant(radio)chemistMariaSklodowskain1898foundoutthatnewRadiumsamplesaremorehotcomparedtotheenvironmentsformanymonths.Theyconcluded:radioactivityisnewandveryimportantsourceofenergyandproposeditsusageformedical, pharmaceutical,…,purposes.
•
Vernadsky in Russia in 1920 predicted that Ra and allied matter could be a very important key for new energetic in the World scale.

8. 2014 ‐60thanniversary of the First World NPP •
The first NPP was constructed in Obninsk, Russia , the first grid connection on June 26, 1954 providing the new city of Obninsk with electricity.
•
The power plant remained active until April 29, 2002 when it was finally shut down.
•
The single reactor unit at the plant,AM‐1had a total electrical capacity of 6MW and a net capacity of around 5 MWe. Thermal output was 30MW.
•
It was a prototype design using a graphite moderator and water coolant. This reactor was a forerunner of the RBMK reactors.

9. Potential of nuclear
•
To use the full potential of U (and Pu bred from it) requires fast‐neutron reactors
•
The stock of depleted UO2in the world when used in fast reactors will provide the energy equivalent to 4X1011t oil
http://www.world‐nuclear‐news.org

10. Fast neutron reactors•
Fast neutron reactors are a technological step beyond conventional power reactors.
•
They offer the prospect of vastly more efficient use of uranium resources and the ability to burn actinides which are otherwise the long‐lived component of high‐level nuclear wastes. •
Some 20 reactors were operated and 400 reactor‐years experience has been gained in operating them.
•
Generation IV reactor designs are largely FNRs, and international collaboration on FNR designs is proceeding with high priority.

11. Fast reactors with diff. coolants: LLMC (Na), HLMC (Pb, LBE = Pb‐Bi)
•
FN types:
•
BN‐60
•
Brest‐300
•
BN‐600
•
Shevchenko
•
Phoenix
•
Superphenix
•
BN‐800
•
BN‐1200 ‐project
•
FR = the key to really closed nuclear fuel cycle
LBE = Lead‐Bismuth eutectic

12. Fast reactors in Russia and ChinaBeloyarskNPP CEFR ‐China
•
The single reactor now in operation was a BN‐600 fast breeder reactor, generating 600 MWe. (1980 –2014)
•
Liquid Sodium is a coolant.
•
Fuel: 369 assemblies, each consisting of 127 fuel rods with an enrichment of 17–26% U‐235.
•
It was the largest Fast reactorin service in the world. Three turbines are connected to the reactor. Reactor core ‐1.03 m tall , Diameter = 2.05 m.
•
China's experimental fast neutron reactor CEFR has been connected to the electricity grid in 2011
•

13. FastBN‐800withmixedUO2‐PuO2fuelandsodium‐ sodiumcoolantstarted2014inRussia.
Fast BN‐1200 reactor with breeding ratio of 1.2 to 1.35 for (U,Pu)O2fuel and 1.45 for UN (nitride) fuel, Mean burn‐up 120 MWtXdXkg. BN‐1200 is due for construction by 2020 with Heavy Liquid Metallic Coolant (Pb‐Bi)
http://www.world‐nuclear‐news.org

14. Generation IVreactor design
•
The generation IVlead‐cooled fast reactorfeatures a fast neutron spectrum, molten Pbor Pb‐Bi eutectic coolant.
•
Options include a range of plant ratings, including a number of 50 to 150Mweunits featuring long‐life, pre‐ manufactured cores.
•
Modular arrangements rated at 300 to 400MWe, and a large monolithic plant rated at 1,200MWe. The fuel is metal ornitride‐based containing U andtransuranics.
•
A smaller capacity LFR such as SSTAR can be cooled by naturalconvection, larger proposals (ELSY) use forced circulation in normal power operation, but with natural circulation emergency cooling.
•
The reactor outlet coolant temperature is typically in the range of 500 to 600°C, possibly ranging over 800°C.

15. Some of
China’s NPP are based on Fast Reactors

16. •Develop and demonstrate fast reactor technology that can be commercially deployed
•Focus on sodium fast reactors because of technical maturity
•Improve economics by using innovative design features, simplified safety systems, and improved system reliability
•Advanced materials development
•Nuclear data measurements and uncertainty reduction analyses for key fast reactor materials
•Work at Los Alamos focuses on advanced materials development, nuclear data measurements, and safety analyses
Fast Reactors Program in USA
* ‐Gordon JarvinenVIII International Workshop ‐Fundamental Plutonium Properties . September 8‐12, 2008

17. Some of the concepts developed in the past or under development nowadays are the following:
•
—In the Russian Federation, the small 75–100 MW(e) LBE cooled power fast reactor SVBR˗75/100
•
—In Belgium, the 100 MW(th) multipurpose fast neutron spectrum MYRRHA facility, being designed to operate in both critical and subcritical mode
•
—In Japan, a small power reactor cooled by lead‐bismuth and fuelled with metallic and nitride fuel featuring extra long life time; a 150 MW(e) lead‐bismuth cooled fast reactor concept Pb‐Bi cooled direct boiling water fast reactor (PBWFR)) featuring direct contact steam generators (‘steam‐lift effect’ of lead‐bismuth coolants); and a medium sized lead‐ bismuth cooled fast reactor, lower breeding ratios in a Japanese scenario from 2030–2050 on
•
—In the USA, the modular lead‐bismuth cooled STAR‐LM concept featuring natural circulationand the lead or lead‐bismuth cooled Small, Sealed, Transportable, Autonomous Reactor(SSTAR) concept rated 10–100 MW(e)
•
—In Japan and the USA, the lead‐bismuth cooled encupsulatednuclear heat source (ENHS) concept, featuring natural circulation in both primary and intermediate circuits
•
—In China, a lead‐bismuth cooled and thorium fuelled fast reactor concept
•
—In the Republic of Korea, a lead cooled fast reactor dedicated to utilization and transmutation of long lived isotopes in the spent fuel

18. Small Modular Reactors (SMRs)
•
Small Modular Reactors (SMRs) are nuclear power plants that smaller in size (300 MWe or less) than current generation base load plants (1,000 MWe or higher).
•
These smaller, compact designs are factory‐ fabricated reactors that can be transported by truck or rail to where they are in need.

19. 367613365 Reactors for NPPs Under Construction ‐by region: Asia ‐Far EastAsia ‐Middle East and SouthEU 27Other EuropeAmerica
Sources: IAEA‐PRIS, MSC 2011

20. NMR ‐SR
technics

21. Nuclear Magnetic
Resonance
Spectroscopy
http://en.wikipedia.org/wiki/Nuclear_magnetic_resonance
Superconducting magnets 21.5 T
Earth’s magnetic field 5 x 10‐5T
NMR

23. Now we have both 600 and 300 MHzAvanceBruckerNMR spectrometersin disposition of my laboratory
Avance‐300 Bruker
Avance‐600 Bruker
D3‐12 NMR‐600MHz (12.3 AV600_CHEM)
OPERATED BY THE GROUP OF Prof. Valery P. TARASOV, Dr. G. KIRAKOSYAN AND V.A. IL’IN

24. Nuclei in operation
Nucleus
Spin
Natural Abundance
Relative Sensitivity
1H
1/2
99.985
100
2H
1
0.015
0.96
3He
1/2
.00013
44
13C
1/2
1.108
1.6
17O
3/2
0.037
2.9
19F
1/2
100
83.4
23Na
3/2
100
9.3
31P
1/2
100
6.6
39K
3/2
93.08
.05
99Tc
9/2
0 ( = 99.8 !)
high
36Cl
2
0 (30)
high
!

25. •
Number and type of NMR active atoms
•
Distances between nuclei
•
Angles between bonds
•
Motions in solution
•
Sternheimerconst
•
QQC
•
Etc…
Information obtained by NMR
•
Organic substances
•
Radioactive materials
•
Ga‐complexes
•
Etc…

26. 99gTc‐NMR (TcO4: O‐16, O‐17, O‐18)
99Tc NMR (67.55MHz) spectrum of 0.2 M NaTcO4solution in recycled water containing ∼72% H218O at 298K.
V. Tarasov, G.Kirakosyan, K.German, Phys.Chem.Russ, 2015.#1.2702802903003103203303400,400,410,420,430,44NH4Tc16O318O99Tc NMR H0=7.04TлТемпература, Т К Изотопный сдвиг ЯМР 99Тс, м.д.

27. O‐17 NMR
•
In water enriched in O‐17
280300320340130,4130,8131,2131,6132,0 КССВ 17O-99Tc КССВ 99Tc-17ONH4TcO4H0=7.04ТлТемпература, Т К КССВ, Гц

28. Tc‐NMR
ChemShifts in TcO4–“Puce hunting”
•
Solutions
•
Ionic pair formation
•
Receptor Complexes
Others
•
TcO4 –TcO6
•
Tc metal
•
TcO2

29. Changes in the 1H NMR spectrum of an equimolarmixture 1 + 2 in CD3OD after addition of one equiv. of HCl(26% aqueous solution).
The first spectrum represents the spectrum of dialdehyde1. Green signals belong to diamine2, violet signals belong to dialdehyde1 and red signals belong to complex L1∙2HCl.
MEANS for RECEPTOR SYNTHESIS CONTROL

30. Macrocyclicreceptor for pertechnetate and perrhenate anions by NMR and crystal structureG. Kolesnikov,K. German, G. Kirakosyan, I. Tananaev, Yu. Ustynyuk, V. Khrustalevand E. Katayev
DOI: 10.1039/c1ob05873h

31. 99Tc NMR titration of (Bu4N+)(TcO4‐) with L1 (a) and 1H NMR titration of L1 with (Bu4N+)(ReO4‐) (b) in CDCl3at 25 ◦C.
Macrocyclic receptor for pertechnetate and perrhenate anions by NMR and crystal structureG. Kolesnikov,K. German, G. Kirakosyan, I. Tananaev, Yu. Ustynyuk, V. Khrustalevand E. Katayev

32. 99TcЯМР, CDCl3
UV, dichloroethane
Imine-amide macrocycle
log(β11) = 3.2
log(β11) = 5.1
Cyclo[8]pyrrole·2(HCl)
log(β12) = 3.8
log(β12)= 6.0
99Tc-NMRtitration, Bu4N+ 99TcO4–in CDCl3
99Tc-NMR strengths
•
Clear signal
•
Good correlation withUV
KolesnikovG.V., German K.E, KirakosyanG., TananaevI.G., UstynyukYu.A., KhrustalevV.N., KatayevE.A. // Org.Biomol.Chem. ‐2011.

33. Back titration with 99TcNMR detection for the receptorL1 ( HYPER NMR2006. О –experiment, lines–calculated, black–Kb, blue –TBA99TcO4concentration, red–complexconcentration ).
L1
UV‐vis

34. Back titration with 99TcЯМРdetection for the receptorL2( HYPER NMR2006. О –experiment, lines–calculated, black–Kb, blue –TBA99TcO4concentration, red–complexconcentration ).
L2
UV‐vis

35. Chemical shift
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm

36. Intramolecularmode
•
The Berry pseudorotationis a classical mechanism for interchanging axial and equatorial ligands in molecules with trigonalbipyramidalgeometry
•
PF5
•
IF5
Intermolecular mode
•
Tarasovexchange in TcO4‐ TcO6 exchange spectra
Exchange spectra

37. Pseudorotationvia the Berry mechanism
•
Single‐crystal X‐ray studiesindicate that the PF5molecule has two disƟnct types of P−F bonds (axial and equatorial): the length of an axial P−F bond is 158.0 pm and the length of an equatorial P−F bond is 152.2 pm. Gas‐phaseelectron diffractionanalysis gives similar values: the axial P−F bonds are 158 pm long and the equatorial P−F bonds are 153 pm long.
•
Fluorine‐19 NMRspectroscopy, even at temperatures as low as −100 °C, fails to distinguish the axial from the equatorial fluorine environments.
•
The apparent equivalency arises from the low barrier for pseudorotationvia theBerry mechanism, by which the axial and equatorial fluorine atoms rapidly exchange positions.The apparent equivalency of the F centers in PF5was first noted by Gutowsky.[2]The explanation was first described byR. Stephen Berry.
•
Berry pseudorotationinfluences the19F NMR spectrum of PF5since NMR spectroscopy operates on amillisecondtimescale. Electron diffraction and X‐ray crystallography do not detect this effect as the solid state structures are, relative to a molecule in solution, static and can not undergo the necessary changes in atomic position.

38. Berry pseudorotation: NMR‐31P in PF5
Yellow atoms are axial
Blue atoms are axial
http://fluorine.ch.man.ac.uk/pics/berry.gif
http://pubs.acs.org/doi/pdf/10.1021/ed083p336.2
Mechanisms that interchange axial and equatorial atoms in fluxional processes:
Illustration of the Berry Pseudorotation, the Turnstile, and the Lever Mechanisms via
Animation of Transition State Normal VibrationalModes

39. TcO4 ‐‐‐TcO6 Intermolecular spectra

40. NMR‐99Tc in 3 –18 M H2SO4[Tc] = 0.001M

41. 99Tc‐NMR Tc(VII) in HClO4
разбавление водойC(HClO4)δ, ppm11,37124,0551188,810,666010,3336,2410,039,99,743,39,47-1,449,22-4,38,97-6,28,74-7,38,22-8,457,33-8,454,13-3,463,07-2,242,07-1,1300

42. 99Tc‐NMR Tc(VII) in HClO4разбавление водойC(HClO4)δ, ppm11,37124,0551188,810,666010,3336,2410,039,99,743,39,47-1,449,22-4,38,97-6,28,74-7,38,22-8,457,33-8,454,13-3,463,07-2,242,07-1,1300

43. Solid State NMR
Characterization of the Structure of solidPertechnicAcid HTcO4
Solid state 99Tc‐NMR of HTcO4(solid)
Provide some similarity to Re2O7*2H2O
Gives evidence for the absence of TcO4 !
Charge separated structure favorable

44. Solid‐State NMR Characterization of Electronic Structure in DitechnetiumHeptoxide
•
Herman Cho, W.A. de Jong, A.P. Sattelberger, F. Poineau, K. R. Czerwinski ‐J. AM. CHEM. SOC.
•NMR parameters were computed for the central molecule of a (Tc2O7)17 cluster using standard ZORA‐optimized all‐electron QZ4P basis sets for the central molecule and DZ basis sets for the surrounding atoms.
•The magnitudes of the predicted tensor principal values appear to be uniformly largerthan those observed experimentally, but the discrepancies were within the accuracy of the approximation methods used.
•The convergence of the calculated and measured NMR data suggests that the theoretical analysis has validity for the quantitative understanding of structural, magnetic, and chemical properties of Tc(VII) oxides in condensed phases.

45. EFG at anionic(Х) and cationic (М) positions in МХО4 crystals as a = f ( 1/V(cell) )

46. LINE SHAPE FOR 99Tc‐and 133Cs‐ NMR = f(T)inCsTcO4

47. Temperature dependencies of assimetryparameter QCC Tc- 99, tensor components EFG; qyy; qxxCsTcO4

48. Temperature dependencies of chemical shifts and QCC Cs-133 at the positions Cs(1) and Cs(2) inCsTcO4Scheme of the potential in Cs region at different temperature

49. •
NMR spectrum of Tc metal powder obtained by FT of free induction decay accumulated after excitation of the spin system was recorded and used as a reference for analyses of technetium states supported onto the surfaces and formed in Tc‐Ru alloys/intermetalics.
•
Knight shift of technetium metal is a linear function of temperature, K(ppm) = 7305 ‐1.52 x T. nQ(99Tc) = 230 kHz at 293 K, CQ(99Tc) = 5.52 MHz.
Typical NMR‐99Tc spectra of
a ‐metal powder ( Ф80‐150 μm)
b –nano‐dimensional Tc metal Ф = 50 nm

50. •
99Tc NMR study of bimetallic Ru‐Tc samples supported at different supports i.e.: g‐Al2O3 , SiO2, MgO, TiO2has shown that for all the supports (except for TiO2), there is an intense signal at –30 –40 ppm arising from the TcO2

51. Temperature dependence of Knight shift forbulk (b)and nano‐dimensial(a) metallic Tc
S Kn

52. Численная оценка сдвигов Найтадля качественной слоевой модели.
•
NTotal= NT(m) + NS(m+1)
NT(m)=10/3m3‐5m2+11/3 m‐1.
NS= 10m2+2
Kn‐K∞ = (K0 ‐K∞) exp ((‐n/m)
K∞ =7350 м.д. –предельный сдвиг технеция для объёмного образца.
K0 =7430 м.д. –сдвиг для технеция на поверхности частицы данного диаметра

53. Спектр ЯМР Тс‐99 катализатора 2%Тс/γ‐Al2O3
Результаты расчета для 5‐ти слоевой частицы составили при m=5
K1= 7417 м.д.
K2 = 7410 м.д.
K3 = 7397 м.д.
K4 = 7384м.д.
K5 = 7365 м.д.

54. СпектрЯМР Тс‐99 бинарного катализатора 1%Ru‐3%Tc/TiO2

55. 36Cl‐NMR study
36Cl‐NMR Parameters for Molten Salt Reprocessing Analyses: QuadrupoleMoment, Spin‐Lattice Relaxation and SternheimerAntishieldingFactor for Chloride and PerchlorateIons.
FROM: TarasovV., GuermanK., SimonoffG., KirakosyanG., SimonoffM. NRC5: 5‐th International Conference on Nuclear and Radiochemistry. Pontresina, Switzerland, September 3‐ 8, 2000. Extended Abstracts, Vol. 2, p. 641‐644.
36Cl is one of long‐lived b‐active isotopes with a half‐life of 3.105 years and rare nuclear structure –its odd‐odd nuclei contain 19 neutrons and 17 protons.
Being an artificial isotope, 36Cl is not today an environmental hazard because of its low abundance.
.
However, some of the scenarios for the development of atomic power, p.e. involving the use of molten chloride reactor systems for destruction of weapons plutonium and pyrochemicalreprocessing of spent nuclear fuel, may result in accumulation of 36Cl due to 35Cl(n,γ)36Cl reaction (s = 100 barn) in amounts that cannot be ignored as radioactive waste.

56. Nuclear characteristics of the isotope36Clwere reported: I = 2, μ= 1.31 μB, electric quadrupolemoment Q = ‐0.017 barn.
36Clmagnetic moment μ(36Cl) = 1.2838 nm was determined from the ratio of the resonance frequencies ν(36Cl)/ν(2H) = 0.74873 ±3. The magnetic moment was assigned the positive sign.
The Sternheimerantishieldingfactor (1 + γ∞) was known only for Cl‐ ions, but not for ClO4‐ions.
36Cl‐NMR study
NMR spectra (B = 4.6975 T) of an aqueous solution of KClO4+ KClat 300K: (a) 35Cl‐SI 8K, 0.24 Hz/pt, NS = 1070 (ClO4)and 2200 (Cl); (b) 36Cl—SI 32K, 0.03 Hz/pt, NS = 2800 (ClO4) and 2300 (Cl); (c) 37Cl‐‐SI 16K 0.06 Hz/pt, NS = 6400 (ClO4) and 15488 (Cl).
TarasovV., GuermanK., SimonoffG., KirakosyanG., SimonoffM. NRC5: 5‐th International Conference on Nuclear and Radiochemistry. Pontresina, Switzerland, September 3‐8, 2000. Extended Abstracts, Vol. 2, p. 641‐644.

57. 36Cl‐NMR study
TarasovV., GuermanK., SimonoffG., KirakosyanG., SimonoffM. NRC5: 5‐th International Conference on Nuclear and Radiochemistry. Pontresina, Switzerland, September 3‐8, 2000. Extended Abstracts, Vol. 2, p. 641‐644.
3.3 M Bu4NClO4in CH3CN of at 300 K:
(a)
35Cl—SI 4K, SW = 300 Hz, and NS = 8;
(b)37Cl‐‐SI 16K, SW = 300 Hz, and NS = 16;
(c)
36Cl—SI 16K, SW = 100 Hz, and NS = 8.
With the parameters determined in this study, the low level detectable for 36Cl is 0.5 ppm for
concentrated samples, 15 ppm in 0.1 M chloride solutions; LLD for 36Cl could be decreased by a factor of approx. 10 by addition of microamountsof paramagnetic ions (Cu2+, Ni2+).

58. 36Cl‐NMR study

59. 14N‐,77Se,187Re‐, NMR study applied to radioeco& biotechnology tests control
Nitrogen
N‐14
Selenium
Se‐77
Rhenium
Re‐187
… and also
U, Mn, Cs, etc…
etc…

60. Synchrotron Radiation as a Tool
ISTR 2011 Moscow
Electromagnetic radiation generated by ultrarelativisticelectrons/positrons traveling along circular orbits in light charged particles accelerators

61. Advantages compared to standard X‐ray sources
•
Intensity/Brightness higher by 6‐10 orders of magnitude
•
Continuum spectrum from IR to hard X‐rays
•
High natural collimation
•
Tunable polarization
•
Partial coherence

63. EUROPEAN SR

64. EUROPEAN SYNCHROTRONS incl. MOSCOW

65. European
synchrotron
Radiation
Facility,
Grenoble,
France
Production
of X-rays in synchrotron

67. European synchrotron
ESRF
Electron energy:
6 Gev

68. Bending magnets
Undulators

69. •
Siberian Center for Synchrotron Radiation(BINP, Novosibirsk) since 1970‐ies: Storage ringsVEPP‐3 (2 GeV, 120 mA), VEPP‐4(5 GeV, 40 mA) –both1stgeneration(ε~300 nm∙rad)11 beamlines.
•
Kurchatov Synchrotron Radiation Source(Moscow) in operatiionsince early 2000‐ies Siberia‐1 (booster, 450 MeV) –3 VUV beamlines, Siberia‐ 2 –dedicated2ndgeneration source(2.5 GeV, 300 mA, ε~75 nm∙rad), 16beamlines.
•
ZelenogradSynchrotron Rad. Facility (LukinIPP)–under construction•
DubnaElectron SynchrotronDELSI (JINR) –project development
•
International collaboration:
•
Russian‐German beamlineat BESSY II and Russian involvement in ESRF consortium,
•
Russian part in EuropeanXFEL project (X‐ray free‐electron lasers ‐M. Kovalchuk(NRC "Kurchatov Institute", Moscow), A. Svinarenko(OJSC RUSNANO,Moscow)(4thgenerationsource)
Synchrotron sources in Russia

70. •
Basics and typical applications of
‐EXAFS/XANES‐SAXS‐XRD
•
Combined application of X‐ray techniques to structural diagnostics of nano/materials
SR sources in Russia

71. SYNCHROTRON DIAGNOSTICS OF Radioactive and Functional Materialsin National Research Center “Kurchatov Institute” Department Head ‐Yan Zubavichus
10 years in user mode

72. ISTR 2011 Moscow
Kurchatov Synchrotron Source
Linac
Booster
Main storage
ring
Control room

73. 10.5010.7511.0011.2511.5011.7512.00Pt L3Re L2 Fluorescence Yield Photon Energy, keVRe L3
2. Diffraction
1. Spectroscopy
3. Imaging
Synchrotron techniques include
Especially protein
structure solutions
Unique :
Structures in solutions
and polymers

74. KSRC X-ray stations
1
ProteinCrystallography
2
PrecisionX-rayOptics
3
X-rayCrystallographyandPhysicalMaterialsScience
4
MedicalImaging
6
Energy-DispersiveEXAFS
7
StructuralMaterialsScience(SMS)
8
X-raySmallAngleDiffractionCinema(bioobjects)
9
RefractionOptics&X-rayFluorescenceAnalysis
10
X-rayTopography&Microtomography
VUV stations
11
X-rayPhotoelectronSpectroscopy
12
OpticalspectroscopyforCondensedMatter
13
Luminescence&OpticalInvestigations
Technological stations
14
X-rayStandingWavesforLangmuir-BlodgettFilms
15
MolecularBeamEpitaxy
16
LIGA

75. Characteristics of the beamline
TypeEnergy interval, keVΔE/E
Si(111)5‐1910‐4
Si(220)8‐3510‐4
Monochromator is driven by stepper motors(1‘‘ discrete steps)
•
Ionization chambers+ KEITHLEY 6487
•
Scintillation counter withNaI(Tl) crystals
•Linear gas‐filled detectorCOMBI‐1(“Burevestnik”, St. Petersburg)
•
2D‐detectorImagingPlate (FujiFilmBAS2025)
•
Semiconducting detector(pureGe)
Maximum3×3 мм2
Minimum10×10 μm2
Step of translations~4 μm
~ 0.5×108 photons/mm2with energy bandwidth Δλ/λ=10‐4
Monochromators:
Detectors:
Beam dimensions:
Photon flux:

76. In‐situcell for functional materials
3‐component gas mixtures
•
Inerts: He, N2, Ar
•
Oxidation and reduction:O2, H2
•
Catalytic substrate: CO, CH4, etc.
•
Vacuum 10 Pa
20‐550oC
Thermostabilization through the heating current & thermocouple feedback±1oC
4 ×350 W
Cooling down to ‐130oC with a flow of cold N2 gas

77. He closed‐cycle refrigerator (SHI, Japan)
Minimum temperature achieved10.0К + precise termostabilization up to room temperature

78. Combined use ofXAFS, XRD and SAXS•
XANES‐oxidation state of heavy atoms + coordination symmetry
•
EXAFS‐local neighborhoodof a given heavy atom•
XRD‐long‐range order, phase composition, size of crystallites
•
SAXS‐size and shape of nanoparticlesor pores in a range of 1‐100 nm

79. X‐ray absorption spectroscopy: basics
ISTR 2011 Moscow

80. Fermi
level
HOMO
LUMO
XANES: origin
Vacuumlevel
Core electronlevel
Valenceband
Forbidden gap
Conductionband
XANESprobestheenergydistributionofcertainsymmetry- allowedMOsorDOSfeaturesabovetheFermilevel
Fermi‘sgolden rule:
μ ~ |<f | V | i>|2, f,i–wave functions of the final and initial states,V –dipole moment operator

81. Photoionized atom
Neighbor atom
Photoelectron wave
Back-scattered photoelectronwave
Single scattering
Multiple scattering
EXAFS: origin
Local-structrureparametersofthecentralatom
canberetrievedfromEXAFS
Initial state: electron on the core level
Final state: outgoing photoelectron wave
Interference

82. )(/22222))(2sin(),( )( )(krkjjjjjjjjeekkrkfkrNkSkλσϕπχ−−+=Σ
χ-normalized background-subtracted EXAFS-signal
k–photoelectron vector modulus (≡2π/λ)
S –Extrinsic loss coefficient(0.7-1.0)
N–coordination number in thej-thcoordination sphere
r–interatomic distance
f–backscattering amplitude
ϕ–phase shift
σ
–Debye-Waller factors
λ
−photoelectron mean-free path

83. EXAFS/XANES: implementation at SMS
Detection modes:transmission(ion chambers)
fluorescence yield( NaI(Tl) scintillation counter, detection limit down to0.005 mass.%)
Data processing: IFEFFIT (Athena, Artemis, Hephaestus и др.) withab initiotheoretical phase and amplitude functions fromFEFF8, GNXAS
Ab initioXANES spectra simulation withFEFF8 , FDMNES, FitIt, etc.
Absorption edges measuredover 2004‐2014
К‐edges:
Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Br, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, In, Te
L3‐edges:
Ba, La, Ce, Nd, Pr, Sm, Eu, Gd, Hf, Ta, W, Re, Pt, Au, Hg, Pb, Bi, U, Pu

84. 1152511550115751160011625116500.00.51.01.52.0 Normalized Absorbtion, a.u. Photon Energy, eV Pt Pt2+ Pt3+ Pt4+ Pt L36.536.546.556.566.576.586.596.606.61 Mn2+ (MnCl2 6H2O) Mn3+ (Mn2O3) Mn4+ (MnO2) Mn7+ (KMnO4) Photon Energy, keVMn K1635016400164500.00.61.2 Normalized Absorption, a.u. Photon Energy, eV Bi0 Bi3+ (Bi2O3) Bi3+ (Bi(NO3)3.2H2O) Bi5+ (NaBiO3) Bi L1
XANES
Information retrieved fromXANES:
•
Effective oxidation state
•
Coordination polyhedron symmetry
Data analysis: “fingerpring” approach –comparison with reference spectra + theoretical simulations
1s→3d,4p
2p3/2→4d
2s→6p

85. Application to Tc
Tc K‐edge XANES

86. Application to Re
Re L3‐edge XANES

87. 01234561.4 Tc-C 1.76Å6.0 Tc-Tc 2.72Å TcCx |FT(k3χ(k))| R, ÅTc12 Tc-Tc 2.72Å
Tc METAL & Tc CARBIDE

88. 01234560.3 Re-C 2.14Å1.0 Re-C 2.46Å1.1 Re-Re 2.62Å 3.1 Re-Re 2.73Å ReCx |FT(k3χ(k))| R, ÅRe12 Re-Re 2.75Å
Re METAL & Re CARBIDE

89. PYROMETALLURGY
REPROCESSING OF SPENT FUEL

90. Structures of Tc halogenidesin solutions and melts1) fundamental studies of cluster Tc compounds2) Analyses of possible species in PRORYV technology (chloride melts)
Tc K‐край k3‐weight EXAFS spectra and its Fourier transform for Tc (+4, +2,5, +2) halogenides
(Cl, Br)

91. а
б
в
а-МоноядерныйбромидныйкомплексTcK-крайk3-взвешенныйEXAFSспектрипреобразованиеФурьеспектра(Me4N)2TcBr6:
Tc-Br:N=5,8(4),R=2,51(2)Å,σ2=0,004Å2,ΔE0=-16,9(5)eV,
б-Биядерныйкластер Tc K-край k3- взвешенный EXAFS и соответствующее преобразование Фурье спектра K3Tc2Cl8 EXAFS структурные параметры K3Tc2Cl8(лучшая из полученных предварительных аппроксимаций):
Tc-TcN=1,66(3), R=2.20(2) Åσ2=0,0069 Å2ΔE0= -1.1(9) eV
Tc-ClN=2,2(4), R=2,46(2) Åσ2=0,0107 Å2,
в-Спектр и Tc K-край k3-взвешенный EXAFS для полиядерногохлоридного кластера (Me4N)3[Tc6(μ-Cl)6Cl6]Cl2, для которого не удалось получить удовлетворительного преобразования Фурье в рамках FEFF-5 приближения
Spectra EXAFSof complex Tc halogenides

92. Proryv= Breakthrough http://www.atomvestnik.ru/content‐log/104‐redkomonopolnyj‐element.html
•
Since 2011, at SCC Rosatomimplements one of its most ambitious projects “PRORYV (Breakthrough)". Until 2020, it is planned to send 100 billion rubles. Its main goal ‐the development of fourth generation reactors, high power fast neutron, creating a closed nuclear fuel cycle technology, new types of nuclear fuel.
•
... Is the fuel carries the dream of mankind in a closed fuel cycle
•
The current generation of reactors 3 and 3+ does not work closed cycle, that is, the fuel is fulfilled, then it is stored. There is a partially closed loop when after unloading fuel processed, but not entirely ‐a significant portion enters the storage of radioactive waste. "Breakthrough" is to open the technology of the future ‐a vicious cycle: the production of fuel, energy recovery, recycling and re‐loading into the reactor.
•
Closed cycle, it is important to be near‐station, that is for fuel processing does not need to be transported. In general, the "Breakthrough" must solve several important problems for the nuclear industry.
•
According to the doctor of technical sciences, professor, chairman of the technical committee of the project "Breakthrough" EvgenyAdamov, “ is security, which does not lead to such accidents that require evacuation and resettlement of the population even more so, is to use the full potential of raw materials, not only uranium‐235 this final urgent solution to the problems of spent nuclear fuel.

93. UN fuelhttp://www.atomvestnik.ru/content‐log/104‐redkomonopolnyj‐element.html
•
The Siberian Chemical Combine is already running process chain to create the newest nitride fuel, the first assembly designed to be loaded into the reactor BN‐600 at Beloyarsknuclear power plant.
•
Scientists and Energy see how they manifest themselves in action, on this basis, it is decided whether to use nitride fuel in the reactors of the 4th generation.
•
DmitriyZozulya, project manager for the industrial production of dense fuel: "Two full assembly, filling nitride fuel: TVS‐4 prototype fuel assembly BN‐1200 and TVS‐5 ‐a prototype reactor" Brest ". This fuel carries the dream of mankind's closed fuel cycle with reprocessing of spent fuel, there is a need supplements only 238 uranium, plutonium in it remains almost the same with respect to the primary boot. "

94. XAFS analysis of electrode surface after corrosion
Æ
Determination of eventual Tc oxide: ‐In 1 M HCl(E= 800 mV)
‐In 1 M NaCl, pH= 2.5 (E= 700 mV)
XAFS measurement of: NH4TcO4, TcO2, Tc metal for comparison
Layer carefully removed
and analyzed by XAFS.
SEM x 50
Before
After
pH =2.5, 1 M NaCl, E = 700 mV during 1 hour
M. Ferrier, F. Poineau,G.W. ChinthakaSilva, E. Mausolfand K. Czerwinski “Electrochemical Behavior of Metallic Technetium in Aqueous Media” : ISTR-2008. Port Elizabeth, South Africa.

95. XANES
No pre‐edge : No TcO4‐sorbed on electrode.
No shift of edge for 1M HCl , shifted (~1 eV) at pH = 2.5
Æ
Product on electrode after corrosion : mainly Tc metal.
1 M NaCl, pH = 2.5
1M HCl
First deriv.

96. ÆEXAFS analysis also confirm presence of Tc metal on surface electrode after corrosion .
Æ
No oxide detected.
EXAFS after corrosion
XRD [5]
C.N
R (Å)
C.N
R( Å)
Tc0-Tc1
10
2.72
12
<2.71>
Tc0-Tc2
6
3.83
6
3.85
Tc0-Tc3
8
4.76
8
4.73
pH =2.5
EXAFS

97. NEXT : •
SAXS

98. X‐ray detector (0D,1D, 2D) I(s)
Scattering vector s = k1 ‐k0
s = 4πsin θ/ λ= 2π/ d
Sample in the transmission geometry
2θ
k0
k1
s
Point/Linear collimation
Monochro‐ matic X‐ray source
SAXS: Basics

99. ISTR 2011 Moscow
Indirect FT
I(s) –experimentalscattering
curve
P(r) –volumedistributionof hard spheres

100. ISTR 2011 Moscow
SAXS: implementation at SMS
Sample-to-detectordistance,mm
2θmin-2θmax,°
qmin-qmax,nm-1
E=25keV
qmin-qmax,nm-1
E=6keV
120
0.95-45.00
4.2–179
1–43
500
0.23-13.50
1–59
0.24–14.2
1000
0.11-6.84
0.5–30
0.12–7,1
2390
0.05-2.87
0.2–12.7
0.05-3
Only transmission geometry (no GISAXS for the moment)
Scattering vectoris oriented vertically;
sample‐to‐detector distance up to 2.5 m;
Photon energy5‐30 keV(the possibility to employ anomalous scattering)
Treatment of experimental data: GNOM, MIXTURE, DAMMIN, SAXSFIT, IsGISAXS, Fit2D (for preliminary data processing of 2D images)
Simulation:
Single size distribution of spherical particlesR=20±4 Å
IsGISAXS
GNOM

101. 1 . Small‐angle diffraction on mesostructured materials
2 . SAXS application: aqueous colloids
p.e. ‐of Tc sulfide nanoparticles
3 . Quantitative interpretation of the SAXS curve for not‐interacting particles and aggregates (DAMMIN)

102. V.F. Peretrukhin, G.T. Seaborg, N..N. Krot
LNL, Berkley, 1998

103. Periodic Table and heptavalent state of elements
‰
Period is variable :2, 8, 8, 18, 18, 32…?
‰
Zones of implacability exist
‰
For huge part ‐It works ! ! !
VII

104. •
Interatomic distances in metals/simple matter A.Wells “Struct.Inorg.Chem.”
•
Lost :P,S, Br, I, Po, At, Fr, Ra, Ac, Np, Pu, Am, Cm, Bk, Cf
TRU
5
Detailed fig
In: Jarvinen et all
Plutonium

105. Synthesis and the types of An(VII)
•
CrystallinecompoundsofAn(VII)canbepreparedbydeepoxidationofactinidesinstronglyalkalineconditions.
•
Bothinteractionofsolidcomponentsandalsoconductingtheoxidationinalkalinesolutions.
•
CompoundsofAn(VII)arestableonlyinstrongalkali,andrapidlydecomposeinneutraloracidicconditions.
•
An(VII)arequitevariableincomposition:formallytheycouldbeconsideredtocontainanionsAnO65-,AnO53-,[AnO4(OH)2]3- ,[An2O8(OH)2]4-andAnO4-butthelatterisnotsupportedbyX-rayanalyses.
•
AshortnumberofthesolidcompoundscontainingAnO65-, andAnO53-anionswereisostructuraltocorrespondingortho- andmeso-rhenatesReO65-,ReO53-(butnoanalogyinsolutions).
6

106. MAnO4(·nH2O) (M–alkali metal)
•
It was estimated by N.N. Krot and the followers that the transuranium(VII) compounds like MAnO4(·nH2O) (M–alkali metal) have the structures similar to uranates(VI) of alkali earth metals.
•
They contain shortened linear groupsAnO23+and O– bridges collecting all into anionic layers.
Structural type of BaUO4.
(Reis A.H. et al. JINC, 1976).
7

107. BaUO4structural type compounds
•
Lattice parameters for different U(VI), Np(VI) (lit. data) and Np(VII) compounds (IPCE data)
•
1 –U compounds
•
2 –Np compounds
•
Chemical properties of Np(VI) and Np(VII) compounds are different
•
LiReO4*1.5H2O contra LiTcO4*3H2O
8

108. IR spectral data indicates Np‐O and Np=O difference
Evident splitting at the CsNpO4spectrum indicates/supports the presence of two types of Np‐O bonds:
•
O=Np=O
•
Np‐O‐Np
In Li5NpO6all the Np‐O bonds are of the same nature
9

109. Mossbauer spectra of Np(VII) compounds
•
1 –CsNpO4
•
2 –Na3NpO4(OH)2*nH2O
•
3 –Li5 NpO6
•
4 –frozen solution of Np(VII) in 10M NaOH
•
Dots ‐experiment, curve – squared plotting

110. Inthisway:
Transuranic(VII) MAnO4(·nH2O) compounds are completely different :
from
MXO4xnH2O(X–elementsofthe7thGroupfromPeriodicTable,Mn,Tc,Re,n=0,1,1.5,3)
fromTc(VII)acid
German,Peretrukhin2003
Poineau,German2010
fromRe(VII)acid
BeyerH.etall.
Angew.Chem.,1968
fromI(VII)acid
fromCl(VII)acid
Структурный тип BaUO4.
(Reis A.H. et al. JINC, 1976).
(Maruk A.Ya. et al. Russ. Coord. Chem.2011)
and from TcO3+
Pertechnetyl Fluorosulfate, [TcO3][SO3F] –ZAAC, 2007
J.Supeł, U. Abram et all.
Berlin, Freie Universität.
11

111. 111
Isostructural:
LiBrO4∙3H2O
LiClO4∙ 3H2O
LiMnO4∙ 3H2O
LiTcO4∙6/2H2O6/2=3
LiReO4∙1.5H2O
LiReO4∙ H2O
‐
Analogous are absent
More diffused 4d electrons in Re compared to 3d electrons in Tc

112. 112
Isostructural pertechnetate salts withcation : anion = 1:1
Cation
Anion
ClO4-
MnO4-
ReO4-
[Li · 6/2Н2O]+
+
+
*
Na+
–
*
+
K+
–
–
+
Rb+
–
–
+
Cs+
–
–
+
NH4+
–
–
+
Ag+
–
–
+
[(CH3)4N]+
+
–
+
[(C3H7)4N]+
–
*
+
[(C4H9)4N]+
*
*
*
[(C6H5)3PNH2]+
*
*
+
[C7H14N3]+
*
*
+
[C7H10N3(C3H5)4]+
*
*
+
[C7H10N3(C6H5)4]+
*
*
*
[C6H8N]+
–
*
+
[C4H10NO]+
–
*
+
[CN3H6]+
+
*
+
*Notdetermined.doesn’texists
–NosimilaritytoTc
+Isostructural

113. Anionic chain [(Np2O8)(OH)2]n4n‐in the structure
of Li[Co(NH3)6][(Np2O8)(OH)2]∙2H2O
(Burns J., Baldwin W., Stokely J. Inorg. Chem., 1973).
12
Np(VII) & I(VII)
•
Two types of Np in Np(VII) compound while only one Iin I(VII)
•
One bridging O in Np(VII) while two bridging O in I(VII)
•
Np(VII) is stable in alkali while I(VII) –in acids
Neutral chains in HIO4.
( Smith, T. et all. Inorg.Chem., 1968)

114. The first Pu(VII) single crystal
13

115. 14

116. Na4[AnO4(OH)2](OH)∙2H2O
Np1‐O1 1.891(2)Pu1‐O1 1.8824(15)
Np1‐O2 1.888(2) Pu1‐O2 1.8805(18)
Np1‐O3 1.917(2) Pu1‐O3 1.9109(15)
Np1‐O4 1.880(2)Pu1‐O4 1.8811(19)
Np1‐O5 2.315(2) Pu1‐O5 2.2952(19)
Np1‐O6 2.362(2)Pu1‐O6 2.339(2)
An‐OH distances are more sensible to actinide contraction than An=O distances
15

117. Several mixed cation compounds of Np(VII) and Pu(VII)
NaRb2[NpO4(OH)2]∙4H2O(I):a=8.2323(2),b=13.4846(3),c=9.9539(2)Å,β=102.6161(12)°, sp.gr.P21/n,Z=4,R1[I>2σ(I)]=0.0179.
NaRb2[NpO4(OH)2]∙4H2O(II):a=5.4558(2),b=12.4478(3),c=7.9251(2)Å,β=103.6310(13)°, sp.gr.P21/n,Z=2,R1[I>2σ(I)]=0.0218.
NaCs2[NpO4(OH)2]∙4H2O(III):a=15.0048(4),b=9.1361(2),c=10.6747(3)Å,β=129.7361(9)°, sp.gr.C2/c,Z=4,R1[I>2σ(I)]=0.0148.
NaRb5[PuO4(OH)2]2∙6H2O(IV):a=6.4571(1),b=8.2960(1),c=10.8404(2)Å,α=105.528(1),β=97.852(1),γ=110.949(1)°,sp.gr.P‐1,Z=2,R1[I>2σ(I)]=0.0189.
NaRb2[PuO4(OH)2]∙4H2O(V):a=8.2168(2),b=13.4645(3),c=9.9238(2)Ǻ,β=102.6626(12)°, sp.gr.P21/n,Z=4,R1[I>2σ(I)]=0.0142.
NaCs2[PuO4(OH)2]∙4H2O (VI):a= 11.1137(2), b=9.9004(2), c = 10.5390(2) Ǻ, β = 101.0946(11)°, sp. gr. C2/c, Z= 4, R1 [I > 2σ(I)] = 0.0138.
Anion of [PuO4(OH)2]3‐
in the structure of IV
16

118. Selected interatomic distances and torsion angles
in the structures I –VI :
IIIIIIIVVVI
Bond(Å)
An=O 1.8790(12)2×1.8690(9) 2×1.8884(9)1.8695(15)1.8685(12)2×1.8868(15)
1.8855(13) 2×1.9138(9)2×1.8944(9)1.8724(15)1.8761(12)2×1.8876(14)
1.8955(13)1.8919(15) 1.8897(12) 1.9223(13)1.8985(16)1.9144(12)
An‐O(OH)2.3259(13)2×2.3750(9)2×2.3643(9)2.3197(16)2.3083(13)2×2.3236(15)
2.3382(13)2.3556(15)2.3229(13)
Angle(º)IIIIIIIVVVI
H‐O…O‐H145(4)180133(4)39(4)140(3)48(5)
17

119. RecentlyanewwayforNp(VII)compoundpreparationwasproposedbyFedosseevandco-workers[(2008)]: electrochemicaloxidationinacetatesolutions.
Thenewcompoundsof
МNpO4·nH2Otype,whereМ–unichargedcationofalkalimetal,ammonium,silver,guanidiniumortetraalkylammonium
and
Np(VII)withbichargedcationsofalkalineearthmetals,andalsoCu,CdandZn.
Allthesecompoundshavebeenthoroughlycharacterizedbymeansofchemicalanalyses,IRandUV-visspectroscopy.Thestudyconfirmed,that…
18

120. Pu(VII) compounds
are close structural and chemical analogues
of Np(VII) ones
19

121. Tc(VII) & Pu(VII), Np(VII)
Pu(VII) and Tc(VII) are very different in (cryst, electr)‐structure,
ligand arrangement, stability and chemical properties !
1000 ppm
Poineau, German, Czerwinski

122. Periodic Table and heptavalent state of elements
‰
Period is variable :2, 8, 8, 18, 18, 32…?
‰
Zones of implacability exist
‰
For huge part ‐It works ! ! !
VII
4

123. An(VII) ‐Tc&Re(VII)
•
Structural and chemical data obtained in recent years by X‐ray‐s‐ c, IR and EXAFS investigations of the new compounds of
•
heptavalent neptunium and plutonium,
•
heptavalent technetium and rhenium
•
confirmtheearlierprevailingopinionabouttheabsenceofadeepsimilarityinphysico‐chemicalpropertiesbetweentheheptavalenttransuranicelementsandtheelementsofGroupVIIoftheshortformofthePeriodictableandtheformalnatureofsomeofthestructuralsimilaritiesamongtheconsideredheptavalentcompounds.
•
PrincipallyonecanattendtheformationofPu(VIII)butitisnottheaqueousmediathatcouldstanditsoxidizingpower.
20

124. 8th International Symposium on Technetium and Rhenium: Science and Utilization. September 29th to October 3rd 2014. Proceedings and selected lectures. La Baule‐Pornichet, France. Eds. K.German, F.Poineau, M. Fattahi., Ya. Obruchnikova, A. Safonov. Nantes – Moscow –Las Vegas : GranicaPublishing Group, 2014. 561 p.
WHAT SHOULD WE KNOW ABOUT TECHNETIUM AND RHENIUM :

125. BessonovPerminovKrot, GrigorievPeretrukhinGermanCzerwinskiPoineau
Thank you for your Attention!

126. PAN ‐RAN
•
Россия‐Русская академия наук (РАН)12.07.2002 р.‐ Русская академия сельскохозяйственных наук (RANR)12.07.2002 р.‐Русская академия медицинских наук (Ранма)12.07.2002 р.‐Русская академия наук (соглашение награды)16.10.2001.‐ Русская академия наук (соглашение о научном сотрудничестве в области фундаментальных исследований космоса)14.03.2005 р.
ТадеушКотарбинский,

127. Thank you for your attention !