Imaging in Cultural Heritage Research Neutrons and complementary - PowerPoint PPT Presentation

Imaging in Cultural Heritage Research Neutrons and complementary methods László ROSTA Wigner Research Centre for Physics Hungarian Academy of Sciences (Budapest Neutron Centre) Email: rosta.laszlo@wigner.mta.hu CRISPWIN 2014, Grenoble

Materials used by mankind – and neutrons

Materials used by mankind – and neutrons An early neutron study in 2002 at the Budapest Research Reactor

Iron helmet dated back to the 4. century B.C. The heavily rusted helmet was given to the Museum of Debrecen in 1920. It was investigated to help a modern restoration work. Different radiography methods and neutron diffraction were applied. This study revealed the decorations under the corrosion and the previous gluing by gypsum.

Radiography Inspection of an Archeological Object The structure of the helmet was studied by • Gamma radiography, • Thermal neutron radiography, • Epithermal neutron radiography, • X-ray radiography. The inner structure and the hidden decorations of the helmet are shown by the different radiations . Photo of the helmet Gamma radiography picture Epithermal neutron radiography picture X-ray radiography Thermal neutron radiography picture (button part) picture (button part) M. Balaskó, J. Dombóvári, K. Bíró

Neutron Diffraction Inspection of an Archeological Object The diffraction measurement has shown that the helmet material was iron, besides it only the corrosion products were found. 32000 Ca~0,4-4% Helmet Fe~50% Photo of the helmet O~35-40% 24000 C~8% M(111) H=? Neutron counts M(100) 16000 8000 Hematite ,  Fe 2 O 3  =0.144 nm 0 10 20 30 40 50 60 70 o ) 2  ( Fig.5. M. Balaskó, J. Dombóvári, K. Bíró

Budapest Research Reactor Hall

12 neutron beam instruments in the user program

Archaeometry applications at BNC 2004-2008 2009-2013 2000-2003 TOF-ND PGAA Highlight 2008 SANS RADIOGRAPHY

CHARISMA Rosta László (Wigner SZFI), Kasztovszky Zsolt (MTA EK) Szőkefalvi -Nagy Zoltán (Wigner RMI) Large European museums: Louvre, Brittish Museum, National Gallery, Prado, Rijksmuseum… Analytical Infrastructures: MOLLAB (IT, FR) and FIXLAB (FR, HU) 2009-2014

The Budapest Platform of the FIXLAB takes advantages of the large central facility of the Budapest Research Reactor. All the participating laboratories are members of the Budapest Neutron Centre (BNC), a consortium of research institutions of the Hungarian Academy of Sciences. The main attraction of the Budapest Platform for non- destructive study of art and archaeological objects is the ready availability of a variety of neutron-based experimental techniques (PGAA, TOF, SANS, etc.), further enhanced by the possibility to apply complementary non-neutron methods (external-beam PIXE, XRF, PIGE, etc.) on the same campus. TOF-ND SANS PIXE / pXRF PGAA NIPS/NORMA

PGAA / NIPS-NORMA station Prompt Gamma Activation Analysis Neutron Radiography Prompt Gamma Activation Imaging Neutron Tomography

Research Group Leader: D. Watkinson, Cardiff University Watkinson et al. Archaeometry 2013 photograph, X-ray radiograph, neutron radiograph, PGAI data

HIDDEN CONTENTS Terahertz X-ray tomography

HIDDEN CONTENTS Reveal of the organic content of a hermetically closed Egyptian Pottery

Results of the 2D and 3D Neutron Imaging Analyses Research Group Leader: E. Abraham, University of Bordeaux

NIPS – NORMA facility An application: NR & NT images of an Egyptian jar curved supermirror guides (2.5  ) imaging system (NR/NT) position-sensitive element analysis (PGAI) stopper various neutron and gamma collimation clay seal spatial resolution: 0.2-0.5 mm NT: Field of view: 48 mm × 48 mm string-like material PGAI: made of organic material e.g. a ball of linen Neutron beam internal content NR / NT NR: assumed to be organic nature PGAI: mainly composed of H, C, N, S and Cl elements, which supports the Sample assumption about its organic nature chamber Motorized composite 2D image of the sample whole jar from a set of tile stage images

Proof of meteoritic origin of mankind’s earliest iron artefacts, 3200 BC, by neutron and X-ray techniques Principal Proposer: Thilo Rehren – UCL London A predynastic cemetery was excavated near Gerzeh by G.A. Wainwright and J.P. Bushe-Fox in 1911

• 3 iron beads were investigated by non-destructive techniques ( NR, TOF-ND, PGAA, PIXE ) • The objective was to determine the nature of the iron from which these earliest iron beads are made - can we demonstrate that they are meteoritic in origin, as has been speculated based on their early date? • Meteoritic iron has several characteristics that distinguish it from smelted iron. Most prominent are the large crystal grain size, elevated bulk concentrations of Ni (1-10 wt%), Co (1000-10000 ppm) and Ge (200-400 ppm) Properties of The Petrie Museum of Egyptian Archaeology, London One of the beads had been analysed in the 1920s and found to contain about 7.5 wt% Ni

PGAA Zsolt Kasztovszky, Boglárka Maróti & Tamás Belgya Spectr. Nr. 578 579 586 580 589 588 Sample code UC10738 UC10739 UC10740 CdC3C 28848/12 28848/1 Conc. / Conc. / Conc. / Conc. / Conc. / Conc. / Abs. Unc. Abs. Unc. Abs. Unc. Abs. Unc. Abs. Unc. Abs. Unc. Element wt% wt% wt% wt% wt% wt% +/- +/- +/- +/- +/- +/- H 1.65 1.58 2.03 0.114 1.16 1.36 0.03 0.03 0.03 0.003 0.03 0.03 B 0.0473 0.0575 0.0810 0.00172 0.00465 0.0009 0.0010 0.0012 <D.L. 0.00004 0.00010 Na 0.13 0.23 0.20 0.059 0.090 0.01 0.02 0.01 <D.L. 0.004 0.012 Mg 0.66 0.46 0.37 0.47 0.09 <D.L. 0.04 <D.L. 0.06 0.06 Al 0.18 0.31 0.10 0.12 0.06 0.07 0.02 0.03 <D.L. 0.02 0.02 Si 1.5 3.0 1.3 0.6 0.2 0.1 0.1 0.05 <D.L. 0.04 0.06 P 0.8 0.6 1.0 0.24 0.2 0.1 0.1 0.05 <D.L. <D.L. S 0.2 0.2 0.2 0.11 0.063 0.02 0.01 0.01 0.01 0.007 <D.L. Cl 0.709 0.625 0.806 0.0050 0.118 0.167 0.017 0.011 0.015 0.0001 0.003 0.004 K 0.028 0.077 0.080 0.023 0.021 0.002 0.003 0.005 <D.L. 0.003 0.004 Ca 0.48 0.55 0.67 0.80 0.28 0.03 0.02 0.03 <D.L. 0.03 0.02 Ti 0.016 0.047 0.009 0.002 0.002 0.001 <D.L. <D.L. <D.L. Mn 0.023 0.0160 0.050 0.008 0.027 0.003 0.0004 0.001 <D.L. 0.0005 0.0007 Fe 50.2 48.7 48.5 64.1 60.2 60.0 0.4 0.4 0.3 0.2 0.2 0.2 Co 0.203 0.237 0.170 0.284 0.006 0.008 0.006 0.010 <D.L. <D.L. Ni 3.55 4.10 2.75 4.88 0.10 0.10 0.06 0.15 <D.L. <D.L. Nd 0.002 <D.L. <D.L. 0.0005 <D.L. <D.L. <D.L. Sm 0.00002 0.00002 0.000002 0.000001 <D.L. <D.L. <D.L. <D.L. Gd 0.000023 <D.L. 0.000003 <D.L. <D.L. <D.L. <D.L. O (calculated) 39.6 0.1 39.7 0.1 41.6 0.1 30.3 0.1 36.5 0.1 37.3 0.1 PGAA showed that the beads consist predominantly of Fe and O in broadly similar amounts, which is consistent with their corroded state. Of more interest, the beads contain 2.8-4.1 wt% Ni , 0.6-1.0 wt% P , and 1700-2400 ppm Co . Ge was below the D.L.

Exernal milli-beam PIXE station Practicle Induced X-ray Emission

PIXE - Imre Kovács & Zoltán Szőkefalvi -Nagy • PIXE analysis of the beads’ surfaces confirmed the presence of Fe as the main element, followed by Ni at an estimated 5 wt%, and the light elements from the soil. Individual spots have different concentrations of Cu, Pb, As, Zn and Mn . Two of the beads showed spots with Ge , estimated to be at 30 ppm, and reaching up to 100 ppm.

TOF - Time of Flight Neutron Diffraction Metallurgy Archaeometry High-entropy alloys Carbon steel blades AlNiFeCrMn 1.0 sc Fe 0.8 3 176° x10 0.6 0.4 CuNiFeCrMn Fe 0.2 Cu 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 8 AlNiFeCrMn 6 sc 3 Fe x10 4 60° 2 0 High-Entropy Alloys "pure" cementite 0.5 1.0 1.5 2.0 2.5 1000 200 Fe3C 006 211 High carbon content blade 220 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 8 d-spacing [Å] Medium carbon content 6 d-spacing [Å] Pure Iron 4 neutron/sec/Å/10g ferrit 2 • Phase analysis 100 8 6 Fe-Cr system 4 • Structure determination 2 10 8 (Al) 6 • Texture and stress anlysis 4 2 Fe - Cr Fe 3 C structure factor 5 10 Fe 8 5 6 4 1.1 1.2 1.3 1.4 4 rácstávolság [Å] 3 2 Lapis lazuli 2 4 10 1000 Bronze artefacts 8 e e 6 625 Egyptisch Blau 625 Egyptisch Blau 6 4 5 d d 4 2 3 619 AFG 103 619 AFG 103 c c 2 621 FEYZ1AK 621 FEYZ1AK 100 b b 6 622 AFG LL100 622 AFG LL100 0.8 0.9 1.0 1.1 1.2 a a d-spacing [Å] 623 KB3 623 KB3 0.6 0.6 0.8 0.8 1.0 1.0 1.2 1.2 1.4 1.4 1.6 1.6 1.8 1.8 d-spacing [Å] d-spacing [Å]

TOF-ND György Káli & László Rosta • By ToF-ND testing for grain size and crystal lattice structure of any metallic phases present in the beads, no metallic form of iron was found. No definite Bragg peaks were observed, consequently they should consist of a larger number of low symmetry crystalline phases (probably with non-uniform chemical compositions, as oxides), imperfectly crystallized or amorphous compounds • This is considered typical for the corrosion products of iron