The GILDA projecthttp://www.esrf.eu/UsersAndScience/Experiments/CRG/BM08/

F. d'AcapitoCNR-IOM-OGG

dacapito@esrf.fr

LAYOUT

• Beamline Description• Facts and figures• Scientific Highlights• Perspectives

Description

4

Where ?

ESRFEuropean Synchrotron

Radiation Facility

ILLInstitut Laue-Langevin

Neutron Source

Grenoble (France)

The landscape

ILL

CEA

ESRF

LETIMINATEC

CNRS (LHCM)EMBL/PSB

ST-Microelectronics

2 Km

INPG

Surrounded by world-class institutes

General infos

Scientific goalStudy of the structure of materials

and its relation with their mocroscopic properties

Experimental techniques• X-ray absorption spectroscopy

• X-ray powder diffraction

FundingCNR + INFN

Operative since1994

General Features

Source: bending Magnet

• Energy range complementary to ELETTRA

• Energy range 4 – 85 keV• Resolution ∆E/E = 10-4-10-5

• Flux on the sample 109 – 1011 ph/s

• Spot size 1*1 > 0.1*0.1 mm2

3 Experimental cabins • XAS Hutch (Instrumentation for XAS experiments)

• Diffraction Hutch (Instrumentation for XRD experiments)• “Open Hutch” (Open to user’s experimental apparata)

Optic Hutch •beam sizing

•mono-chromatization• focalization

Control room• Remote

instrumentation control• Data analysis

Beamline layout

F. d’Acapito et al. ESRF Newsletter 30 (1998), 42

1st collimating mirror (Pd or Pt)Sagittally focusing monochromator2nd vertically focusing mirror (Pd or Pt)

X-ray optics

XAS

3 experimental chambers• Standard sample environment• User’s sample environment• ReflEXAFS

ReflEXAFS• Operative between 5.8 and 28

keV.• Record dilution: 5*1013 at/cm2 at

the In-K edge.• Program for data analysis (*)

The ReflEXAFS chamberF. d’Acapito et al. JSR (2003). 10, 260–264.

(*) F. Benzi et al. REV. OF SCI. INSTRUM. 79, 103902 (2008).

Contact mode AFM

Fluorescence detectors• 2* 13 elements HP-Ge• Resolution 200 eV @ 6.4 keV• Max CR 80kcps/element• Digital data collection

• Automatic refill

G. Ciatto et al. JSR 11 (2004), 278-283

2 104 2.2 104 2.4 104 2.6 104 2.8 104 3 104

Emissionfitgaussianbackground

X-r

ay E

mis

sion

Yie

ld fr

om sa

mpl

e (A

rb. U

nits

)Ex

cit.

ener

gy 2

8170

eV

Compton

ElasticIn-K

α

Energy (eV)

Time Resolved XRD- MAR 345 2D detector

- Si PIN photodiodoe for XAS collection

Sample conditioning:

• Heating Gun (RT-900 oC)

• Cryo-cooler (LN-RT),

• Reaction chamber

• Automatic gas distribution system

• Mass spectrometer

- sample holders: Capillaries, flat cell, translating slices

Experimental keypoints

Diluted samplesGrazing Incidence

-0.20

-0.15

-0.10

-0.05

0.00

0.05

0.10

3 4 5 6 7 8

XA

S si

gnal

χ(k

)

Photoelectron wavevector k (Å -1)

In

C-In

1013 In/cm2 in Si. In-K edge Reflexafs

F. d’Acapito et al. APL 88 (2006) 212102

In situ treatmentsTime resolution a few min.

Isothermal XRD spectra of hydratation of cementsM. Merlini et al. Pow. Diff. 22 (2007), 201.

Facts and figures

Legal stuff5 years contract with ESRFEvaluation just before the end of the contractContract constraints

Provide to ESRF 1/3 of the total beamtimeSupport users on the ESRF beamtimeMinimal staff 3 people 1 scientist 1 technician

CNR-INFN agreement 2/3 – 1/3 contribution

Maintenance IHRESRFCRG

Beamtime distribution ESRF beamtime: attributed by ESRF committees

CRG beamitimeAttributed by the italian committee

Impact of GILDA on the italian activities at ESRF

Total ESRF

GILDA

Number of experiments @ GILDA Beamtime for italian users

1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 20110

10

20

30

40

50

60

Esperimenti eseguiti

Italian Users ESRF Users

Anno

Espe

rim

enti

2006-I 2006-II 2007-i 2007-II 2008-I 2008-II 2009-I 2009-II 2010-I 2010-II 2011-I 2011-20

1

2

3

4

5

6

7

8

9

Ovl ESRF Ovl GILDA

Bea

mtim

e ov

erlo

ad

2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 20110

20406080

100120140160180

TotCRGESRF

Year

Num

ber o

f par

ticip

ants

Part

icip

ants

19

GILDA user community

INFNUniversities CNR

GILDA is a fundamental infrastructure for the italian scientific community

Investigation fields

Shift distribution per committee

CH

EC

HD

HE

HS

MA

MD

MI

MX

SC

SI

Chemistry

Hard Cond. Matter

Environm. & Cult. Herit.

Materials Engineer.

Life science

Surface Science

GILDA Publications

• About 510 publications on International journals in 17 years of activity

• Current performance: about 40 articles/year !

Distribution of the IF

0

5

10

15

20

25

30

35

40

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

IF Value

Num

ber

of P

aper

s

1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 201005

101520253035404550

pubblicazioni su riviste internazionali

Anno

Pubb

licaz

ioni

Personnel & BudgetStaff

1 responsible II lev Permanent1 scientist III lev Permanent

1 technician VI lev Fixed Term

Capital 3 M€Budget 120 K€/y

Decommissioning 0.3 M€

Evaluation

ESRF Beamline Review Panel 2009

ESRF Beamline Review Panel 2004

Timely evaluation (5y) via international Review Panels

A fast lane to international science

S. PascarelliPermanent position ESRF

G. VeronesiPost DocESRF

P. L. SolariPermanent position Soleil

G. CiattoPermanent position Soleil

L. GiachiniPost Doc.Australian Synch.

M. RovezziPost Doc ESRF

H. G. PaisPermanent position Soleil

Sonia PINPost DocSLS

Scientific Highlights

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Fields of activitySemiconductors

SuperconductorsEnvironmental

Science

Earth Science

BiologyFood Science

Cultural Heritage

EnergyCatalysis

Nanotechnology

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Environmental science

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Environ. Sci. Technol., 2011, 45 (24), pp 10492–10500DOI: 10.1021/es201002g

Hexavalent chromium (Cr(VI)) in soils is a major contaminant. It is generally quantified using an extraction step to transfer it to the liquid phase.

The performance of the most common extraction procedure (EPA Method 3060A) is evaluated using X-ray absorption near edge structure spectroscopy (XANES) on 3 soil samples.

The EPA Method 3060A procedure underestimated the Cr(VI) content in all studied samples

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Definition of a calibration curve for the quantification of CrVI in soil samples

30

Breathable SiO2 particles

31

Fe on surface analysis

X-cut

Z-cut

Y-cut

Shannon 69 Tetra (Å) Octa (Å)

Fe2+ 2.03 2.17

Fe3+ 1.89 2.05

Model surfaces X, Y, Z cutReflexafs

Work in progress

Fe in breathable SiO2 powders from work site

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Materials science

f

Double perovskites Sr2FexMoyO6

Study on the nature of Fe/Mo disorderComparison XAS/Diffraction

High cation order (XAS) even in disordered samples (XRD)

Clustering of the antiphase domains

Explanation of the magnetic properties

Hi dielectric constant materials needed for device scale reductionZrO2 in tetragonal (unstable) form has κ=47T-ZrO2 is stabilized by adding Ge. Why ?

Look at the environment of GeCompare XAS data with structural modelization with DFT and MD

Ge-doped zirconia

Ge in t-ZrO2 substitutes for Zr

Ge creates 4 short Ge-O bonds

XAS data in agreement with theoretical predictions for Ge in t-ZrO2

XAS analysis

Chemistry

Production of supramolecular materials

Process in the solid state, no solvent involved

Alternance of crystalline and amorphous (polymers) regions

Time resolved XRDAbout 2'/ pattern

A) Close packed TPP (monoclinic, black)B) porous TPP (hexagonal, green)

Inclusion of the block copolymer in the hexagonal holes (red)

Time resolved diffraction patterns

Origin of the H conductionCombined XAS, XRD, IR study

Ga-K edge XAS shows the rigidity of the GaO4 units

- Proposed structure for the GaO4 chains- NO corner sharing tetrhedra- O1-H●●●O4 bonds- Stiffness of GaO4: no intraTetrahedral H diffusion

Cultural Heritage

GILDA in the international landscape

GILDA represents a considerable instrument for the italian Cultural Heritage community

L. Bertrand & al.

Thanks to Marine Cotte

F. Rosi et al. J. Raman Spectrosc. 42 (2011) 407.C. Miliani et al. Acc. Chem.Res. 43 (2010) 728

SbO6 Symm. StretchingOrange

Yellow

Example on Putto con trofei by Mastro Giorgio Andreoli (VAM, London), portable RAMAN spectrometer (MOLAB project, http://www.eu-artech.org/)

Example in ceramics

Zn was found in Naples Yellow ceramics of Umbrian production (Muser Civici di Pesaro)

XAS + ab initio structural modeling permitted to demonstrate that Zn occupies a Sb site

Perspectives

Short term

- Renewal of some hardware- Improve high throughput capability- Automation / remotization- Increase time-resolved capability

Long term

MonoToroidal mirror

Reflecto-meter

Conventional EXAFS bench

Filters

23m28m30m37m50m

Cil.mirror

25m

OHEH1EH 2&3

0

1

2

3

4

5

6

7

0 1 104 2 104 3 104 4 104 5 104F

lux

(10^

10 p

h/s)

Energy (eV)

Spot size

Flux

Refurbished Beamline layout

Project

Project discussed with ESRF and the Italian User community

Well received

Funding needed

Conclusion GILDA is a major infrastructure for the italian scientific community Inserted in a unique scientific environment Privileged place for student formation and insertion in international resarch

Highly appreciated by the Review Committees High impact in the overall italian activity at ESRF Performs experiments in a wide range of scientific fields High production and reliability

Thanks to…

F. d’Anca, F. Bardelli, C. Battocchio, F. Benzi, S. Cammelli, G. Ciatto, T. Costanzo, N. Daldosso, M.C. Dalconi, J. Frascaroli, P. Ghigna, F. la Manna, C. Maurizio, H. Pais, S.

Pin, A. Rizzo, M. Rovezzi, P.L. Solari, S. Thorpe, A. Trapananti.

Technicians, students and scientists, who have contributed to the success of GILDA: