Brief Tutorial On X Ray Powder Diffraction Data Analysis

Brief tutorial on X raypowder diffractiondata analysis Essential bibliography X-ray powder diffraction (XRPD): briefsummary Qualitative Analysis: evaluate your patternand look for possible phase(s) Quantitative Analysis: Rietveld refinementDr Carlo MeneghiniDip. Di Scienze, Università di Roma Tremeneghini@fis.uniroma3.it

WarningThese notes represent an introduction to x-ray powderdiffraction analysis, far from exhaustive but intended todrive the Reader, who has collected its first XRD data,through the different steps that will bring him to:i. inspect the diffractograms in order to check the data quality andobtain preliminary rough information about sample nature,crystallinity, etc.;ii. compare the experimental diffractograms with those of modelsand reference compounds, in order to make preliminary hypothesisabout sample structure and composition;iii. perform the full pattern structural refinement (Rietveld method)in order to achieve a first quantitative understanding of thecrystallographic structure of the samples.However the Reader must keep in mind that XRPD data analysis is farfrom automatic, instead it is a complex procedure requiringcompetence and experience, and often tumbles across a slow learningprocess via trial and error process.

RepositoryGrado 2013 XRD tutorial.pdfhttps://db.tt/7UXhsrWRXRPD tutorial Grado2013.ziphttps://db.tt/wopyl8TS

Essential bibliography XRPD B.E. Warren, X-Ray Diffraction (Addison-Wesley, 1990). H.P. Klug and L.E. Alexander, X-Ray Diffraction Procedures (Wiley Interscience, 1974). B.D. Cullity, Elements of X-Ray Diffraction (Wiley, 1978). Modern Powder Diffraction Reviews in Mineralogy, Vol. 20 Mineralogical Society of America, (1989). Fundamentals of Crystallography IUCr Texts on Crystallography -2 C. Giacovazzo, (Oxford Science Publication,1992. The Rietveld Method IUCr Monographs on Crystallography - 5 R.A. Young, Editor Oxford Science Publication,1993. X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials H.P Klug and L.E. AlexanderWiley-Interscience, 1974, 2nd edition. Defects and Microstructure Analysis by Diffraction R.L. Snyder, J. Fiala and H.J. Bunge, IUCr Monographs onCrystallography, Vol 10, Oxford Science Publications, 1999. Diffraction Analysis of the Microstructure of Materials Diffraction Analysis of the Microstructure of Materials E. J. Mittemeijer, P. Scardi Springer (2004)On line resourceshttp://epswww.unm.edu/xrd/resources.htmA resource page for XRDhttp://www.ccp14.ac.uk/The collaborative computational projectshttp://www.icdd.com/International centre for diffraction data

Information from Xray PowderDiffractionpatternsParticle sizeand defectsPeak shapesPeak �Unit cellSymmetryand sizecbaDiffuse scattering,sample holder,matrix, amorphousphases, etc.40Atomicdistribution inthe unit cell

NOTEAb initio recognition and structural refinement ofcrystallogrphic structure of unknown phase(s) (i.e.:direct methods) is a hardly complex task**It is easier (and it is often the case) to refine thecrystallographic structure (and phase composition) of asample exploiting the a-priori knowledge you may haveabout your sample, that is: starting from models,hypothesis, patterns database, etc.** Ab initio structure determination from Powder diffraction data Harris, K.D.M., M. Tremayne, and M. Kariuki. Contemporary Advances in the Use of Powder X-RayDiffraction for Structure Determination, Angew. Chem. Int. Ed. 40 (2001) 1626-1651. Giacovazzo, C. Direct Methods and Powder Data: State of the Art and Perspectives, ActaCrystallogr. A52 (1996) 331-339. Scardi, P., et al. International Union of Crystallography Commission for Powder Diffraction.http://www.iucr.org/iucr-top/comm/cpd/

XRPD experiment has gone!We have data.And now?

www.fis.uniroma3.it/ meneghini/software.htmlDownload and install:XRD tutorial.exeXRPD tutorial.exeXRD tutorial 3.exeGSASCMPRVESTAgnuplotbinwgnuplot.exeY2O3 PCWY2O3 GSASAu GSAS

More information onGnuplot at:Firstly: get a look to the data!www.gnuplot.info25000'y2o3.dat' u 1:22000015000./data10000plo y2O3.plt500000gnuplot pl [:][:]20'y2o3.dat' ux-rangefileploty-range401:2usingx:ycolumns6080w lwithlines100120

Main peaks: aresymmetric? Arethere saturationeffects?1.Check the dataqualityIs the statistics goodenough also for weakerpeaks?Can youdistinguishdifferent peaks?Are theresolution, theangular step, etc.appropriate?

If the patterns are good.go aheadIf not.Note: Data collection on S.R. isdefinitively faster than in laboratorybut:6-12 months from proposalsubmission to experiment . . .!!!(if you are lucky) ! ! !.consider to recollect the XRPD patterns

SECOND: compare your data withmodels based on your a prioriknowledge on the sampleCompare your diffractograms with patterns expected forcompounds of similar compositionLook for the structure of know compounds on /webmineral.com/http://barns.ill.fr/Note:SR facilities have oftenaccess to private DataBaseclosed to your institution!

http://database.iem.ac.ru/mincryst/y2o3.dat

ICSD public versionhttp://barns.ill.fr

Your data25000They reasonablymatch!'y2o3.dat' u 1:2y2o3.dat20000150001000050000102030405060go ahead!databaseIf not. maybeyour sample iswrongLiterature Data

Go deeper into the datasave file: icsd 86815.celsave file: icsd 86815.cif

icsd 86815.cificsd 86815.cel

PowderCellPCWXRD tutorial InstallVESTAPCWpcw.exePowderCell is a simple to handleprogram allowing:-structural visualization,Y2O3 PCWY2O3 GSASAu GSASicsd 86815.cely2o3.x y-theoretical XRPD patterncalculation-Rietveld refinement- etc.http://users.omskreg.ru/ kolosov/bam/a v/v 1/powder/details/pcwindex.htm

generate thepatternPlay with the structurelook at the whole cellModify/Create the unit cellLoad structure file (.cel)patternrefinement

Load structure fileicsd 86815.cel

Provide here the informationabout the experiment, mainly:Wavelengthexperimental geometrydiffractedbeamincomingbeamθθ

. XRPD tutorial/datiy2o3.x yData and model patterns arereasonably similar,our model/hypothesis seems correct,now we can derive quantitativecrystallographic informationrefining the XRPD patterns!

Rietveld methodIcalc Ibck SbackgroundScalefactorStructureSymmetryΣhkl Chkl (θθ) F2hkl (θθ) etryset-upStructurefactorAtomic positions,site occupancy& thermalfactorsProfilefunctionparticle size,stress-strain,texture Experimentalresolution

ntSamplezeroshift

Icalc Ibck SΣhkl Chkl (θθ) F2hkl (θθ) Phkl(θθ)

Refinement of y2o3.x y 12/10/2005 12.58.11 R-valuesRp 18.08 Rwp 24.85 Rexp 2.012 iterations of 6parameteroldnewicsd 86815 PsVoigt2U:V:W:overall obal parameters zero shift:-0.1475-0.1997displacement:backgr. polynom :coeff.0.00001313a0 :4515.86306590.1070a1 :-841.4-1060a2 :68.7475.86a3 :-2.669-2.745a4 :0.052470.0522a5 :-0.0004457-0.0004386a6 :-6.29E-7-5.966E-7a7 :3.161E-83.121E-8a8 :-3.797E-12-8.06E-12a9 :-1.953E-12-1.947E-12a10 :2.97E-166.361E-1a11 :1.251E-161.261E-1a12 :-6.315E-19-6.571E-1a13 :8.173E-228.861E-2

Getting some other information from your dataCMPRXRPD tutorialProgramsGnuplotPCWDataGSASCMPRInstall CMPRprogram on the PC(defaults options)Analysis

Informations and tutorials for CMPRRepository: ling CMP on W7 maybe difficult, use the cmpr.zip file for start

Expand the cmpr.zipClick on AAA startCMPR.bat

read severaldata fileformats

export ASCIIfiles

select the data fileyou want to playingwith

You can combinedifferent data setsto simulatemultiphase systems

(multi-) peak fitting routines1

To Select diffraction peaks1) Move the mouse on the peakmaximum and2) pres the p key

Check box to refine orfix the parameters

For advanced users:Search for the possible symmetry usingITO, TREOR or DICVOL algorithms

GSASXRPD tutorialProgramsGnuplotCreate a newdirectory in thepath:PCWAnalysisDataGSASUTIL(XP)gsas expgui.exeC:\gsas\MyWorkY2O3 PCWCopy into thenew folderY2O3 GSASOther XRDAu GSASy2o3.gs,inst xry.prmObtaining GSAShttp://www.ccp14.ac.uk/solution/gsas/gsas with expgui install.html

Move to your newdirectoryChoose a filename for yourexperiment

Use theicsd 86815.celfile

Icalc Ibck SΣhkl Chkl (θθ) F2hkl (θθ) Phkl(θθ)

peak breadth Gaussian: σ2 GU tan2θ GV tan θ GW GP/cos2 θsample shift:GaussianSherrerbroadenings - π R shft / 3600sample absorption: µeff - 9000 / (ππ R Asym)peak breadth Lorentzian : γ (LX - ptec cos φ)/cosθ (LY - stec cos φ)φφ tan θLorentzianSherrerbroadening(particle y(stacking faults)

Gaussian Breadth:σ2 GU tan2θ GV tan θ GW GP/cos2 θLorentzian Breadth:γ (LX - ptec cos φ)/cosθ (LY - stec cos φ)φφ tan θStrain: S d/dGaussian contrib.S sqrt[8 ln 2 (GU- Ui)] (ππ/18000) · 100%InstrumentalcontributionLorentzian contrib.S (LY –Yi ) (ππ/18000) · 100%Particle size: PP (18000/ π) K λ / LXScherrerconstantInstrumentalcontribution

2Mp Σ w (Iexp-Icalc)2Rp Σ (Iexp-Icalc) / Σ IexpwRp sqrt[ Mp / Σ I2exp ]χ2 Mp / (Nobs - Nvar )143

GSASSNLS – XRPD gsas expgui.exec:\gsas\mywork Y2O3 PCWY2O3 GSASother XRDAu GSAS

m3m λ 0.688011Au 0. 0. 0.a 4.0782GOLDSFAu nanosized particles supported on waxwide broad peaks on intensestructured background!Ps 50 ÅToo structured background maypartially masks true peaks andintroduce artifacts and errors in yourstructural parameters

Now. you can (must) try!Use files in XRD DATAdirectoryFor comments, suggestions, support request etc.contacts:Dr Carlo Meneghinie-mail:meneghini@fis.uniroma3.itaddress: Dip. di Fisica, Univ. RomaTrevia della vasca navale 84,I-00146 Roma, Italia

Information from X-ray Powder Diffraction patterns. NOTE Ab initio recognition and structural refinement of crystallogrphic structure of unknown phase(s) (i.e.: direct methods) is a hardly complex tas