HowtoAnalyzeMinerals

Fundamentals

Acknowledgement
Thistutorialwasmadepossiblebythemany contributionsofICDDmembersworkinginthe fieldsofmineralogyandgeology. Thedatashowninthispresentationwere contributedbyICDDmembersand/orclinic instructors

Overview
Thevastmajorityofmineralsarecrystallinesolids madeofperiodicarraysofatoms Crystallinesolids,whenexposedtomonochromatic Xrayswilldiffractaccordingtotheprinciplesof Braggslaw.Thisistheprinciplebehindsinglecrystal crystallographicanalysisandpowderdiffraction analysis Inpowderdiffractionanalysesarandomlyoriented, finelygroundpowderisrequiredformultiphase identificationandquantitation.

Diffraction BraggsLaw
IncidentcoherentXraybeam Xraysscatteredfrom thesecondplane traveltheextra distancedepictedby theyellowlines. Simplegeometry showsthisdistance= 2dsin

d
d=interplanarspacingofparallelplanesofatoms

Whenthisextradistanceisequaltoonewavelength,thexraysscatteredfromthe 2nd planeareinphasewithxraysscatteredfromthe1stplane(asarethosefromany successiveplane).Thisconstructiveinterferenceproducesadiffractionpeak maximumatthisangle.ThisisthebasisofBraggsLaw:

=2dsin

XRPDPatternforNaCl
=1.5406(CuK1) a=5.6404

Braggslawprescribesthe2 angularpositionforeach peakbasedonthe interplanardistanceforthe planesfromwhichitarises.

2 =2asin(/2d)

(111) d=3.256 2 =27.37

(200) d=2.820 2 =31.70

(220) d=1.994 2 =45.45

(311) d=1.701 2 =53.87

(222) d=1.628 2 =56.47

WhyItWorks
Eachcrystallinecomponentphase ofanunknownspecimenproduces itsown powderdiffractionpattern. Thesepatternsarisefromthe crystalstructuresofthecomponent phases Thepatternforamulticomponent mixtureconsistsoftheweighted sumoftheindividualpatternsfor eachcomponentinthemixture.
CaSO42H2O CaO Ca(OH)2 CaCO3

MaterialIdentification
PowderXRDiscalledafingerprinttechniquesince everyunknownneedstobecomparedtoareference. Inthediffractionpatternbelowaspecimenofoyster shell(topred)iscomparedtothereferencediffraction patternofcalciumcarbonate(bottomblue)fromthe PowderDiffractionFile.Thematchingofallmajorpeaks identifiestheoystershellasbeingcomposedof calciumcarbonate.

1Dvs 2Ddetectors
Diffractionfromapolycrystallinepowderwill Produceaseriesofrings(Debyerings)thatsatisfy Braggsequation.Ifa2Ddetectorisusedthenthe Fullringiscaptured.Aonedimensionaldetectorwill scanalongthethetaaxis(bluebox)andproduce Thediffractionpatternshownonthebottomright. Theringscanalsobeintegratedtoproduce1Dpatterns

Inthispresentationweshowdata fromboth1Dand2Ddetectors

2D

1D

PowderDiffractionBasics
Toanalyzemineralsbypowderdiffractionyouwillneedtohaveawellground specimenwheretheparticlesarerandomlyorientedinordertoproducea uniformintensity.Forreproducibleintensitiesdiffractionphysicsandparticle statisticsofthediffractionprocess*requirethattheparticlesshouldbebelow 10uminsizeandpreferably1uminsize. Improperspecimenpreparationisthesinglelargestsourceoferrorinthequantitative analysisofmineralsbypowderdiffraction Minimizingtheparticlesizealsodiminishesthesurfaceroughnessandoften helpspackingoftheparticlesintothespecimenholder.Properparticlesize reductioneliminatesorreducesmanyofthecommonerrorsassociatedwith mineralidentificationandanalysissuchasorientation,specimentransparency granularityandmicroabsorption.Ageneralruleofthumbistoregrindand analyzethedataagainifyouhaveagreatdealofdifficultywiththeinitialanalysis.

*Referenceswithparticlestatistics analyses
IntroductiontoXRayPowderDiffractometry,RonJenkins,RobertL.Snyder, WileyInterscience Publisher,1996 XRayDiffractionProceduresforPolycrystallineandAmorphousMaterials, HaroldP.KlugandL.R.Alexander,WileyInterscience,1974

TheChallengeishowtogetarepresentativesamplethatwill producearepresentativespecimenforyourdiffractometer

Therock/mineralsamplewillneedto becrushedintosmallpiecesandthen ultimatelygroundintoafinepowder.

Ifthemineralissoftanagatemortarandpestle canbeusedtoproduceafinepowder.Ifthemineral ishardmechanicalgrindingmayberequired.

Courtesy of PANalytical

MacrotoMicro Mountainstomolehills
Macro
RiffleSplitters JawCrushers SampleThieves Pulverizer Mills(large) Slicers&Dicers Diamondsaws Coreborings TungstenCarbidedrills

Micro
Mortar&Pestle Ballmill(small) ParticleSieve Cryogrinder Attritionmill Micronizing mill

Thesemechanicaldevicesareusedtosampleminerals.Oftentimesmanyof thesedeviceswillbeusedinsuccessiontogofromtonsofsolidrocktoa finelypowderedspecimen.

Particlesize reduction
Anattritionormicronizingmillis becomingacommontoolusedin manylaboratoriesforparticle reduction.Thesetypesofmillshave beenshowntobeabletoreducethe particlesizeofmanyhardminerals withoutsignificantlydiminishingthe crystallinityorcontaminatingthe specimenwithmillingmedia.The mediausedinthemillingprocesscan varyfrompolyethylenetoalumina, agateortungsten.Ingeneral, matchingthemediahardnesswiththe specimenhardnessisusefulifone wanttoavoidsignificantdamageto thespecimenduringtheparticle reductionprocess. Onleft:Particlesievesof100,200and600mesh Onright:Micronizing chambersfromaMcCrone micronizing mill usingeitheragatemediaoraluminamedia(lightpink)

CavityMountfromICDDclinics, mountsbyPANalytical,Rigaku,BrukerAXS Examplesoffinelygroundpowdersreadyforanalysis

ZeroBackgroundHolders
offcutsiliconcrystal,offcutquartzalso used

Anessentialtoolformostmineralogistsistheuseofazero backgroundholder.Thisistypicallyanoffcutsinglepieceof quartzorsiliconthatwillnotproduceanybackgroundinthe pattern.Thisisveryusefulforsmallspecimensthatcanbecentered intheholder.Thisiscriticalifoneisanalyzingclaysoramorphous materialsthatareweaklyscattering.Standardglassandplastic holderscontributeamorphousscatterthatcaninterferewiththe determinationofclayoramorphousphases.

EffectsofaSmoothSurface
Havingasmallparticlesizeanda smoothsurfacecanalsoreducenoiselevels asdemonstratedinasystematicstudyby KlugandAlexander. Morerecentlysomescientistsareusingthis variation,withagammascantechniqueandtwo dimensionaldetectors,toprovideestimations ofparticlesizes.

Reproducedfrom KlugandAlexander, WileyPublishers1974

Diffractionpatternsin3Dspace
Ontheleftarethreeidealizedpatternsfrom asinglecrystal,largegrainsandanidealrandom powder Themiddlefigurebelowisfromatwodimensional detectorofaspecimenofsiliconandmannitol.The siliconwasfinelygroundpowderthatproduceda perfectDebyediffractionring,themannitol was assymmetric largeplatelets(leftphoto)that producedthespottedringsinthemiddlepattern andthemisshapenpeaksinthefarrightpattern.
Ifyourpeakslook likethis regrind thesample.Iftheshape isduetolargegrains Thenthepeakwilllook normalonregrinding. Ifthepeaksaredueto multiplephasesitwillnot changewithregrinding

Intensespotsfrom orientedlargegrains

Tip: Narrow or spotty peaks may be a sign of orientation, granularity and/or poor sampling statistics (small samples) Film
Courtesy Forensic Science Service

Counter - Courtesy ORNL

2D Detector
- Courtesy Bruker-AXS

FirstdatafromMars
Thefirstpowderdiffractiondatadirectly fromMartiansoil(linkbelow). NoticetheniceuniformDebyeringswithonly asmallamountofgranularity ThiswasachievedontheMarsroverbyusinga grindingmillandthenplacingthesamplein anovelpiezoelectricspecimenholderwhichvibrates thesoil,randomizingtheparticles.Theholderand particlevibrationfromalaboratorydemonstration areshowninthelinkedmovie. Vibratingparticles http://www.icdd.com/resources/tutorials/files/xrdvibratingholder.mov Martiansoil http://www.nasa.gov/mission_pages/msl/multimedia/pia16217.html

Every time you prepare a sample you change it !

Make sure the sample prep technique is not destroying, altering or masking the original problem (tip - analyze before and after preparation steps)
-Grinding can destroy soft materials -Binders can mask or dilute phases - Temperature and humidity can change phase chemistry - Sieving may separate phases as well as separating particle size
Materialcanbeovergrounddestroyingcrystallinity. Hardmaterialslikequartzwilloftenselfgrindsoftermaterials.

Datacollection
Datashouldbecollectedfrom2to70 degreesforphaseidentificationand2to 100degreesforquantitativeanalysis withastepsizeof0.02degrees.(Cu radiation) Mineralsshowawidediversityin diffractionpatternswhicharearesultof theirdiversityincrystalandmolecular structure.Theplotatthetopshowsthe maximumdspacingfor39,406minerals andmineralrelatedmaterials(i.e. synthetics,gems)..Manymineralshave characteristicpeaksatveryhighd spacings (lowangles)asshownbythe insertofthetopgraphandbythe referencedataformontmorillonite showninthemiddlegraph.Alternatively fluoritehasadmaxataverylowd spacing(highangle)asshowninthe bottomgraph.Thisvarietydictatesa wideanalysisrangewhenanalyzing mineralunknowns.

dmax=17.10 5.162

dmax=1.931 47.002

MaterialIdentificationProcess
Preparethespecimen(wellgroundsmallparticle sizepowder) Collectthedata Treatthedata removebackground Inmanysearch/match smoothdataifneeded programsthesesteps arebatchedprocessed findpeaks soasingleuseroperation doesallthedatatreatment identifypeakheightsandareas normalizeallintensities Comparemineraldatatoreferencedata

DataTreatment
(graphicsinterfacewithICDDsSieve+program)
BackgroundRemoved DataSmoothed

RawData

PeaksFound

Normalized dspacings and intensites

SearchthePDF4+database

SearchMatchefficiencyisgreatlyimprovedbyusingamineralsandrelatedmaterial subfile.Thisreducesthesearchto39,406entriesinRelease2012.Thisisthelargest mineralentrycollectionintheworldfordiffractiondata.

Thesearchmatchesdspacings andimmediatelyfound quartzandazuriteinthisspecimen.

Match

Thematchofthecompletepatternscanbe comparedgraphically,above,orbyalineby linedspacingcomparisonontheright. Alldspacings inblueindicateamatch andthedspacinginblackarenotidentified. Thefirstcolumnisthedspacings ofthe unknownandtheothercolumnsaretheds and Isofreferencematerials.

Thirdphase Ba (Pb)SO4

Quartz

Azurite

MoreMatchesby analyzingtheremaining unidentifiedpeaks

Remainingresidualdspacings 9.856 dmaxofMuscovite 5.942 Malachite 3.145 CaF2 1.929 dmaxofCaF2 1.645 CaF2

Byexaminingtheresidualdspacings andsearching mineralsinthedatabase,additionalmineralscanbe found.

Usingadditionalinformationsuchasmicroscopicexaminationand elementalanalysesanothertwophasescanbeidentified tenorite andcopper.Themajorpeaksofthesephases areinareasofheavypeakoverlapwhichmakesidentification ofthesetwophasesdifficultwithoutthesupplementaldata. ThisparticularspecimenwasalsoanalyzedbyXrayFluorescencewhich confirmedthephasesidentified,includingtheleadinthePb doped Barite.

Canwedoaquantitativeanalysis?
FortheReferenceIntensityRatiomethodoneneedsanI/Ic value foreachmineral
InPDF4+Release2012andPDF4/Minerals28,542outof39,406entries(72.4%) haveanI/Ic

FortheRietveld methodoneneedsatomiccoordinatesforeach mineralstructure

InPDF4+Release2012andPDF4/Minerals27,649outof39,406entries(70.1%) haveatomiccoordinatesorarecrossreferencedtoatomiccoordinates

Forpatternfittingmethodsdigitalpatternswouldberequiredfor allphases
InPDF4+Release2012andPDF4/Mineralsall39,406mineralandrelatedmineral entriescanbeexpressedaseitheranexperimentalorcalculateddigitalpattern (100%).Patternfittingmethodsmaybethepreferredmethodofanalysisifoneis dealingwithnoncrystallinecomponents.

RIRMethod

TheRIRmethodcalculatesanestimatedconcentrationbasedonscalingalldata totheintensityofcorundum(I/Ic).WithICDDssoftwarethisworkedwellforthe majorphasesshownhere,buthadtroublewithautoscaling theminorphasesdueto thepeakoverlapissues.Thesimulation(black)shownbelowwasbasedontheautomatic RIRscaling

PatternFitting

Patternfittingwassomewhatmoresuccessfulsincescaling canbemanuallyadjustedandminorphasesincluded. InICDDsoftwarethepatternscanbesummed(black)andcomparedto theexperimentaldata(red). OthervendorsoftwaresuchasFULLPATcanshiftandadjustpatterns toaresidual

Quantitation byPatternFitting
Phase Quartz Azurite Muscovite CopperOxide Flourite Ba(Pb)SO4 Malachite Copper Pattern IntegratedArea 116.7 12.9 2.0 2.0 9.6 9.4 5.0 2.0 I/Ic 3.1 1.9 0.4 2.8 3.84 2.85 1.74 8.86 N 37.64 6.78 5.00 0.71 2.50 3.29 2.87 0.22 59.01 wt% RIR Rietveld 71% 14% 5% 3.7% 2.5% 2% 1.5% 0.3% 64% 68% 11.5 23% 8.5 4% 1.2 4.2 5.65% 4.9 0.4

I/Ics foreachphasewereobtainedfromthePDFdatabaseandused toscalethefittedpatternsandnormalizethedata.

Rietveld Analysis Rietveld Analysiswasperformedbythe programHighScore Plususingatomic coordinatesfromthePDF4+database. Rietveld offerstheadvantageofrefiningeach phaseandpeakshape

Azurite Quartz Muscovite CopperOxide Flourite Ba(Pb)SO4 Malachite Copper

14% 71% 5% 3.7% 2.5% 2 % 1.5% 0.3%

Quantitativeresults
Intheprevious4slidesthreedifferentmethodswereusedfor quantitativeresultsbuttheywerenotequivalentmethods. Allthreemethodsidentifiedthemajorphases.TheautomatedRIRmethod hadsomedifficultywithminorphasesbecauseofpeakoverlap whereastheothertwomethodsweresomewhatmorerobust sincetheybothusedfullpatterndata.TheRietveldtechnique wasmorerigorousthanpatternfittingsincethedatawerefitand refined. Theintentwastodemonstratethatthereferencedatabasescansupport variousquantitativemethodsofanalysis.

Referenceonquantitativemethods: Madsen,I.C.,Scarlett,N.V.Y.,andKern,A.(2011), Descriptionandsurveyofmethodologies forthedeterminationofamorphouscontentviaXraypowderdiffraction,Z.Krist., 226,pp.944955.

Summary
Becauseofthedifficultiesinobtainingandpreparing samplesmineralanalysescanoftenbedifficult Specimenpreparationiskeytoobtaininggood results Thereisanarrayofdatabaseandpatternfitting softwaretoolsthatcanhelpanalyzecomplex multiphasemineralspecimensbothqualitativelyand quantitatively.