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Nuclear Analysis and Radiography Department (NARD), Centre for Energy Research, Hungarian Academy of Sciences (MTA EK),

1525 Budapest, PO Box 49, Hungary

The Role of Nuclear Methods in Energy ResearchThe Role of Nuclear Methods in Energy Research

Tamás Belgyatamas.belgya@energia.mta.hu

3rd European Energy Conference27-30 October 2013

Hotel Flamenco, Budapest

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Content

Introduction Research facilities of the Budapest Neutron

Centre (BNC) Applications of the R&D facilities of MTA EK The Prompt Gamma Activation Analysis Some of our recent results Summary Partners

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Introduction, challenges Climatic change: EU 320% 20 % CO2 emission reduction, 20% renewable

energy, 20% energy saving by 2020 EU recommendation (COM(2010) 639):

Smart grid Research of new energy storage technologies Research of 2nd generation bio fuels Partnership of smart cities (energy usage, transport, information

technology) National energy strategy 2030 „5 goals” (Co2 , renewable

14,65%, savings 10% by 2020) Energy saving (about 17%, Varró László, Energy Outlook 2012

presentation 2013.02.22) Increase of renewable energy Use of safe nuclear energy Foundation of two-pole agriculture (energy prod. – food) Join to the European energy infrastructure

To achieve these goals R&D is needed The goal of my presentation: to give a taste of the results of

our neutron based research in the field of energy research

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The research infrastructure of BNCBudapest Neutron Centre (1993)

NAANAA

Nuclear analytical and imaging tools of MTA EK Prompt-gamma Activation Analysis (PGAA) (mm) PGAI-NORMA elemental and structural imaging ( 2 mm, 200 m) Neutron-, gamma- and X-ray radiography (RAD) ( 100 m) Neutron Activation Analysis (NAA) Mössbauer spectroscopy (chemical environment)

Material microstructure tools of Wigner FK (not all listed) Neutron powder diffractometer (PSD) ( 0.1 nm) Small angle scattering (SANS) (10-250 nm ) Reflectometer (REF and GINA) ( nm surface structure) TOF diffractometer (TOF) (nm lattice distance)

Macroscopicstructure,

composition

Microscopicstructure

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R&D areas of facilities operated by MTA EK

BNC is open for users and runs peer review of applications (EU FP7 NMI3-2, CHARISMA, ERINDA support)It is open for national users as well, who can apply for support to MTA EK

R&D areas (PGAA-NIPS, RAD, NAA): Energy research: high tech turbine blades and fuel cell radiography

behavior of supercritical water, quality of primary cooling water, boron in silicon wafers, impurities of reactor graphite

Material sci.: Hydrogen storage, hydrogen in fuel cladding, boron distribution in turbine blade material, elemental composition of samples

In-situ catalyst: selective hydrogenation, Deacon reaction Nuclear data: neutron cross sections, prompt fission gamma and neutron

yields Nuclear waste: gamma-spectroscopy of actinides Safeguards: uranium detection, active interrogation of shielded U sample Geology : Study of geology samples from nuclear waste repository,

composition of volcanic samples Archaeometry: provenance and source identification, 3D elemental analysis

and tomography

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The Prompt Gamma Activation Analysis Idea of (PGAA)

(a nuclear analytical method)

NAANAANAANAA

• The gamma-ray spectrum emitted by the sample is measured • The gamma energy is characteristic for the element or isotope• The intensity of gamma-rays are characteristic for the amount of

elements or isotopes in the sample

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The features of PGAA

• Non-destructive nuclear analytical method• Multi-elemental and multi-isotope • Independent from the chemical state of the sample• Bulk method (provides an average composition)• Exact for homogeneous samples• Good for main components and sensitive for some trace

elements (B, Cd, Sm, Nd, Gd)• Unique for the analysis of H and B• The sensitivity is changing widely for neighboring

elements• Good for solid, liquid and gas samples

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Analysis steps of PGAA

Endröd i zöldpala PGAA spektruma

0.000 01

0.00 01

0.0 01

0. 01

0 .1

1

10

1 00

10 00

0 100 0 200 0 300 0 400 0 500 0 600 0

Energ ia ( keV)

beüté

sszám

(cps)

0.0 0000 01

0 .0000 01

0.000 01

0.00 01

0.0 01

0. 01

0 .1

1

10

60 00 700 0 8000 900 0 10000 1100 0

Spectrum :C:\HYPC\SPECT RA\ARCHEO\ZOLDPALA\FV41I03C.MCA Live Time :3290.48

Z El M m un c% m(bkg) un c% m(n et) n(ox) m(ox) un c%

c%atom

c%el/el

c%el /ox

c%ox/ox un c%

1 H 1.00794 0.0729 1.2 0.00018 3.0 0.07272 0.5 0.6499 1.2 0.027 0.904 0.484 4.328 1.25 B 10.811 6.7E-05 1.1 1E-08 0.0 6.7E-05 1.5 0.00022 1.2 3E-04 8E-04 4E-04 0.001 1.2

11 Na 22.9898 0.39095 2.5 0 0.0 0.39095 0.5 0.52699 2.5 3.36 4.859 2.604 3.51 2.512 Mg 24.305 0.93332 3.6 0 0.0 0.93332 1 1.5477 3.6 8.48 11.6 6.216 10.31 3.613 Al 26.9815 1.21162 1.6 0.00273 5.0 1.20889 1.5 2.28416 1.6 12.19 15.03 8.051 15.21 1.614 Si 28.0855 3.09038 1.5 0 0.0 3.09038 2 6.61136 1.5 32.45 38.41 20.58 44.03 1.516 S 32.066 0.03361 5.8 0 0.0 0.03361 3 0.08391 5.8 0.403 0.418 0.224 0.559 5.817 Cl 35.4527 0.0015 7.0 1.8E-05 20.0 0.00149 0 0.00149 7.1 0.02 0.018 0.01 0.01 7.119 K 39.0983 0.04832 12.4 0 0.0 0.04832 0.5 0.05821 12.4 0.706 0.601 0.322 0.388 12.420 Ca 40.078 0.75737 2.0 0 0.0 0.75737 1 1.05972 2.0 11.35 9.414 5.044 7.058 2.021 Sc 44.9559 0.00063 14.5 0 0.0 0.00063 1.5 0.00097 14.5 0.011 0.008 0.004 0.006 14.522 T i 47.867 0.1515 1.0 0 0.0 0.1515 2 0.25277 1.0 2.711 1.883 1.009 1.683 1.023 V 50.9415 0.00471 6.8 0 0.0 0.00471 2.5 0.00841 6.8 0.09 0.059 0.031 0.056 6.824 Cr 51.9961 0.00984 7.9 0 0.0 0.00984 1.5 0.01438 7.9 0.191 0.122 0.066 0.096 7.925 Mn 54.938 0.01509 2.4 0 0.0 0.01509 1 0.01948 2.4 0.31 0.188 0.101 0.13 2.426 Fe 55.845 1.3222 1.2 0.00144 5.0 1.32076 1.5 1.88835 1.2 27.57 16.42 8.796 12.58 1.227 Co 58.9332 0.00531 4.0 0 0.0 0.00531 1 0.00676 4.0 0.117 0.066 0.035 0.045 4.062 Sm 150.36 5.4E-05 2.1 0 0.0 5.4E-05 1.5 6.3E-05 2.1 0.003 7E-04 4E-04 4E-04 2.164 Gd 157.25 7.6E-05 2.0 0 0.0 7.6E-05 1.5 8.7E-05 2.0 0.004 9E-04 5E-04 6E-04 2.066 Dy 162.5 0.00014 18.3 0 0.0 0.00014 1.5 0.00017 18.3 0.009 0.002 1E-03 0.001 18.3

8.04523 15.0151 0.806 100 100 53.58 100- O calculated 6.96985 46.42 %

mass w/o O 8.04523Factor 1

Facto

r 2

ZP23

ZP30

ZP32

FCS2

E39

KK

BL

-0.15

-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.978 0.982 0.986 0.990 0.994 0.998 1.002

BVII

FCS1BI

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The determination of composition

m : Mass of element or isotope

in the sample

S : sensitivity

Ag : peak area

NA : Avogadro number

M : molecular weight

: isotope composition

0 : Radiative neutron capture

cross section

P : gamma decay probability

: neutron flux

(E) : Detektorhatásfokf(E) : gamma absorption

)()(; 0

EfEPM

NStSmA A

From fitting of spectra From our PGAA library

Zs. Révay, Determining Elemental Composition Using Prompt-gamma Activation Analysis. Analytical Chemistry 81 (2009) 6851-6859;

Belgya, T.: Prompt Gamma Activation Analysis at the Budapest Research Reactor, Physics Procedia, 31 (2012) 99-109

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In-situ catalysis, PGAA steup (2009-2012) DEACON reaction

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The reactions studied by PGAAIn-situ PGAA (EU FP6 és FP7 NMI3, Fritz-Haber Intézet)

• Selective hydrogenation of acetylene (H-C≡C-H)• Selective hydrogenation ethylene (H2-C=C-H2), and suppression

of production of ethane (H3C─CH3)!

• Goal was to replace Pd-black with cheaper catalyst

• Replacement is Al13Fe4 intermetallic compound

• Deacon-reaction (2 HCl + 1/2 O2 → Cl2 + H2O)

• To get back Cl2 from hydrochloric acid (HCl)

• This is an energy saving solution compared to electrolysis of NaCl

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In-situ PGAA, new catalystsAl13Fe4, Pd3Ga7, PdGa

M. Armbruster, K. Kovnir, M. Friedrich, D. Teschner, G. Wowsnick, M. Hahne, P. Gille, L. Szentmiklósi, M. Feuerbacher, M. Heggen, F. Girgsdies, D. Rosenthal, R. Schlogl, and Y. Grin: Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation, Nature Materials, 11(8) 690-693 (2012)

M. Armbrüster, … Zs. Révay,… L. Szentmiklósi, D. Teschner, et al., How to control the selectivity of palladium-based catalysts in hydrogenation reactions: The role of sub-surface chemistry, ChemCatChem (2012) 4 1048 – 1063

• Controlled placement of transition metal in crystalline lattice by quantum chemical design

• To block of formation of metal hydride

• Comparable selectivity to Pb-black, but lower cost

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Deacon catalysts• Sumitomo, Bayer: RuO2/SnO2

• Studied cheaper alternatives: CeO2, CeO2 (Hf)

The absorbed Cl on the RuO2 surface poisons the catalyst

The Cl2 introduced to the input decreases the reaction rate, but application of O2 regenerates the catalyst

Teschner, D., G. Novell-Leruth, R. Farra, A. Knop-Gericke, R. Schlogl, L. Szentmiklósi, et al.: In situ surface coverage analysis of RuO2-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis Nature Chemistry, 4(9) 739-745 (2012)

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Co-17Re-23Cr ötvözetekEU FP7 NMI3 (D. Mukherji, TU Braunschweig)

• Replacement of Ni based alloy Replacement of Ni based alloy at high temperature applications at high temperature applications (T>1600 (T>1600 ººC)C)

• Jet turbines with higher Jet turbines with higher efficiencyefficiency

• In In 20 20 yearsyears +200 +200 ººCC!!• Development of Co-Re-Cr(-Ta) Development of Co-Re-Cr(-Ta)

alloys in TU Braunschweig from alloys in TU Braunschweig from 19971997

• Cr decreases the oxidationCr decreases the oxidation• B increases the hardnessB increases the hardness, , if it is if it is

on domain boundarieson domain boundaries• The goal is to check this!The goal is to check this!

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Check the nominal, bulk boron content - PGAA

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B imaging with solid state track detection

Neutron beam

20×20 mm

Sample 10×10×3 mm

Solid state track detector(, 7Li sensitive)

D. Mukherji, J. Rösler, M. Krüger, M. Heilmaier, M-C. Bölitz, R. Völkl, U. Glatzel, L. Szentmiklósi: Scripta Materialia 66 (2012) 60D. Mukherji, J. Rösler, J. Wehrs, P. Strunz, P. Beran, R. Gilles, M. Hofmann, M. Hölzel, H. Eckerlebe, L. Szentmiklósi, Zs. Mácsik: Metallurgical and Materials Transactions A, doi: 10.1007/s11661-012-1363-6

10B(n, )7Li

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NORMA10 – Neutron radiographand tomograph

(NAP VENEUS08 and Baross Gábor support)

Since December 2011

workplace

PGAA NIPS (NORMA)

PGAI(maging)/NT

0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

0.0030

0.0035

0.0040

0.0045

0.0050

03

69

1215

1821

2427

3033

36d

ista

nc

e fro

m to

p (m

m)

ma

ss_ra

tio C

l / Fe

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Cadmium sulfate solution helped to reveal the low cross section ceramic residue

Hightech Turbine blades(Alcoa collaboration)

Radiographic pictures at RAD and NORMA

Goal to find Zr ceramic pig residue by neutron radiography at the RAD and NORMA10 facilities

Belgya, T., Z. Kasztovszky, Z. Kis, and L. Szentmiklósi, Hidegneutronok alkalmazása elemanalitikai és magfizikai kutatásokban, Nukleon, V. évf. Art. num. 121 1-6 (2012)

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Oberstedt, S., T. Belgya, R. Billnert, R. Borcea, D. Cano-Ott, A. Göök, F.J. Hambsch, J. Karlsson, Z. Kis, T. Martnez, A. Oberstedt, L. Szentmiklósi, and K. Takács, Correlation measurements of fission-fragment properties in: EPJ Web of Conferences 8, Paris, France (2010) 03005

Measurement with VERDI (IRMM) at the PGAA-NIPS facility

The v, E distribution of fission products and the correlation of prompt fission -ray were measured

n-beam

LaCl3:Ce és LaBr3

Fission spectroscopy(EU FP6 EFNUDAT

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Summary and future plans

We are capable to perform a large variety experiments related to the field of energy research

Our current tools provides macroscopic information in the material research, which yielded a number of nice results

In the future we want to combine these results with microscopic information that is necessary to answer a broader range of scientific questions in the field of energy storage and conversion

To achieve this we will collaborate with the Wigner FK and other stake holders

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Our collaborators Fritz-Haber Institute, Berlin, Germany Director General JRC Institute for Rreference Materials and

Measurements, Geel, Belgium Institute of Energy and Climate Research - Nuclear Waste Management

and Reactor Safety, Forschungszentrum Jülich GmbH, Germany Technical University Braunschweig, Germany Novotny Tamás, Perezné Feró Erzsébet, MTA EK Fuel and Reactor

Materials Department Balaskó Márton, Sziklainé László Ibolya, Lázár Károly, MTA EK NARD Bagi János, Hlavathy Zoltán, MTA EK Nuclear Security Department

A. Simonits, Zs. Kasztovszky, Z. Kis, J. Weil, Zs. Révay

V. Szilágyi, Z. Tóth, T. Belgya, K. Gméling

MTA EK NARDPGAA-NIPSgroup

Thanks for your attention!

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Thanks for your attention!