DRXWin2.0AGraphicalandAnalyticalToolforPowderXRDPatternsCopyright?VicentPrimoMartín1994-1998INDEXINTRODUCTION 1Setupandrequirements 2Files 3MainScreen 4SelectXRD 8Axis 12Peaks 13Patterns 14Tools 16PrintoutOptions 20PAGE20INTRODUCTIONDRXWin2.0isa32bitscomputerprogram(Windows95,NTorabove)whichletsyouworkwithXraydiffractionfilescomingfromseveraldiffractometers,andRietveldprogramslikeFullProfandRIET7.Themainperformancesare:Plotdiagrams(maximum9)inanoverlappedorsteppedway.Makezooms,addcommentsandgrids,changeaxisdivisions,etc.CustomiseXRDpatternscolourandwhiteorblackforthescreenbackgroundcolour.Automaticpeaksearchandtheabilitytoaddsymbolstopeaksforlabellingphases,etc.SavethepeakstoplotafterwardsasastickpatternandplotpatternsofthePDF-2database.Qualitativeanalysisbysearchingincustompatterndatabases.2qzerocorrection;backgroundcorrection;smoothing;peakareacalculation;deconvolutioninGaussian,LorentzianorPseudo-VoigtfunctionsallowingtocalculateFWHM;2qrangeremoving;combineXRDs(addandsubstract)andrescale.AbilitytoassociatefilestoDRXWinforloadingfileswithdouble-click.SavefilesinwindowsmetafileformattoeditormergeinanywordprocessorlikeMicrosoftWord,AmiPro,etc.ExcellentqualityforprintinggraphicsandextremelyeasytouseasitrunsintheMicrosoftWindowsenvironment.

SetupandRequirements TheprogrammustbeinstalledbyrunningSETUP.EXE. Thesupplieddonglehavetobeconnectedinanyparallelportofthecomputer:lptx(usuallylpt1). TheoptionofaddingsymbolstopeaksneedstheWingdingsfont(TrueType)whichcomeswithWindows. IfyourprinterdoesnotsupportTrueTypefontsyoumayhavesomeproblemsinprintoutand/oronthescreen(errormessage:InvalidPropertyValue).Youshouldupdateyourprinterdriver. Fromversion2.0DRXWinwillonlyrunin32bitsoperatingsystemslikeWindows95,WindowsNTandabove.Itisadvisabletohave16MbofRAMandSVGA(800x600).

FilesDRXWin2.0canreadfilesfromthefollowingdiffractometers:· SIEMENS(*.RAWand*.DAT).· RIGAKU(*.DAT)inbinaryformat.· PHILIPS(*.RD),(*.UDF);(*.DAT)Philips-PW1050/70(*.)andPhilips-PLV.· STOE(*.DAT).· SEIFERT(*.VAL). AlsoitcanreadASCIIfileswithextensionXY,withthefollowingformat:2Theta(blankspaceocomma)Intensity.The2Thetavaluesshouldhaveaconstantstep(it’sassumed). ThesefileswillbecalledSTANDARDXRD,anditwillbepossibletoworkwithupto9filesatthesametime. ThefilescomingfromRietveldprogramsarecalledRIETVELDXRD:· FULLPROF(*.PRF).Thesefileshavemoreinformationthantheotherones(theoreticandexperimentalpattern,hkl,etc.)sothatyouwillonlybeabletoworkwith1fileatatime,thuswhenyouopenaCompleteRietveldtheotherfileswillbedeletedfrommemory(soI'dsuggestthatyousavethembeforeopeningaRietveldXRDfile).ThebackgroundinformationforPRFfileswithPLOTPOWformatisincludedin.BACfileswhichmustbeinthesamedirectoryasthePRFfile.· RIET7(*.PLT).ThesefileshavethesameinformationasPRFfilesincludedbackgrounddata,buttheinformationisontwofiles(*.PLTand*.DAT)sothesetwofilesmustbeinthesamedirectory.· GSAS(*.DAT).Thesefilesonlyhavetheexperimentalpattern. Moreover,theprogramcreatessomefiles:inbinary(*.RXWand*.FLP)andASCII(*.ARX,*.AFTand*.DAT)formats.Thebinaryfilescanbeopenedstartinganewsession:· RXW:haveasession,sotheycanhaveupto9STANDARDXRDand/ortheoreticRIETVELDXRD.· FLP:haveasessiondoneonaCompleteRIETVELDXRD.OnlytheASCIIfileswith.DATextensioncanbeopenedbytheprogram:· ARX:haveasession,sotheyaresimilartoRXWbutobviouslytheydon'thavecomments,orpeaks,etc.Theyhaveonlyvaluesofintensityand2q.· AFT:havethetheoreticpatternofaRIETVELDXRD.· DAT:haveonlyoneXRDwithexactlythesameformatastheDATfileforFULLPROFprogram.

MAINSCREENMAINELEMENTSTOOLBARS Therearetwotoolbars,atthetop(1)(Toolbar1)andright(2)(Toolbar2)ofthescreen

;andaninformationbar(3)atthebottomofthescreen.Inthefirstonethereare2qandIvalueswhichyoucanchangetosetzoomvalues,soyouwillbeabletodoazoomwiththesevaluesclickingthebutton(4).Thesecondhasthesebuttons

:· (5)openfiles.· (6)plottemporarylines(theyareneithersavedorprinted).· (7)showthetextbox(10)whereyoucanwritecommentsandchemistryformulas.· (8)deletetheactivetext(textsurroundedbyablackline).· (9)writethetextwrotein(10)withinthegraph.· (10)textboxwhereyoumustwritethetexttoprintonthegraph.· (11)dozoomwiththemouse.· (12)undothezoom.· (13)runtheXRDcommand.· (14)runtheAxiscommand.· (15)runthePrintcommand.· (16)savefiles.· (17)newsession.· (18)leavestheprogram.Intheinformationbar(3)youcansee:· (19)informationaboutthetoolsandelements.· (20)valuesof2q,dandIasthemousemovesoverthescreen.· (21)setwhichwavelengththeXRDwastakenwith(thisisneededtogeneratedvaluesfrom2qvalues).Itcanbechangedbydouble-clicking.Additionalelements· (22)usedinRietveldXRDstochangetheplacewherethedifferenceplotwillbeprinted.· (23)usedinRietveldXRDsafterusing(21)toshowthenewplot(replot).· (24)verticalscrollbarsofthezoom.· (25)horizontalscrollbarsofthezoom.· (26)zoominintensityaxisonly.Additionalwindows.Theycontain

:· (27)thehkllist· (28)thebackgroundlist.Fromhereispossiblemovethebackgroundmarksbyusingthescrollbars.· (29)themainparametersbelongingtothefunctionsfromapeaksdeconvolution.· (30)patternslist.· (31)toolsformanualpeaks.· (32)increaseordecreasethesteptosearchpeaksinamanualway.· (33)set/eraseapeakinthepositionwherethepeaksearchingcursorissituated.· (34)movethepeaksearchingcursortotheleft/right.· (35)legend.MENUSThereare9menus:· Files:fromhereyoucanstartanewsession,openandsavefiles;savemetafilefiles,printandsetupprinter,chooselanguage,andexit.· Edit:letsyoucopytheimageinbitmapormetafile(scalable)formattoclipboard.· Options:youcanselectfonts;showtheXRDlegend(35)andPatternlist(30);showthehkllist(27)ifyouareworkingwithaRietveldXRD;showthezoomscrollbars(24)-(26);thebackgroundlist(28);thedeconvolutionlist(29);andremovethetoolbars.· XRD:accesstothewindowoftheXRDplottingoptions.· Axis:accesstotheaxisformatwindow.· Peaks:accesstothepeaksearchingwindow.· Patterns:accesstothesearchingpatternswindow,andtore-scalethepatternstofittotheXRD.· Tools:menutousethedifferenttoolsavailablefromversion1.3.· Help:opensthehelpfile.TIP: BypressingthemouserightbuttoninwhateverlistofDRXWinyou'llseeafloatingmenuwithseveraloptions.

SelectXRDThereare2types:· STANDARDXRD· RIETVELDXRD

STANDARDXRDInthelistontheleft(availableXRD)therearetheopenfiles,andintheright-handlisttherearetheXRDwhichwillbeplotted.Theleft-handlistcontainsthefollowinginformation:thefirst20charactersofXRD'stitle/commentplusfilename.Thelistontherightcontainsthesameinformationplus:· orderofRESCALING:ifvalueisequalto0thenXRDwillbeplottedwithitsrealintensityscale,andthereforetheXRDwillbeplottedinanoverlappedway;ifthevalueisbetween1and9,thiswillbethepositioninwhichtheXRDwillbeplotted,thereforetheywillappearinasteppedway.Youcanchangethevalueoftherescalingincrement,bydefaultitis110.· Thelinewidth:foreveryXRD.· Thelinestyle:differentstyleswithwidthhigherthan1arenotavailablebymostprinters.· Thelinecolour:byclickingthecolouritispossibletochooseanewone.· ThefactorofrescalingofeachXRDis100bydefault,butitcanbechanged(integervalues)toallowanyXRDbemore(orless)intensewhenperformingsteppedplots.IfyouwanttochangeanyoptionaboveyoumustpickanXRDintheright-handlistandthenchangethevalueinthelabelledcomboboxes.ItispossibletoseazerocorrectionforeveryXRD.Thisvaluewillbeaddedtothetheoreticalvalueof2qasaconstantfactor.TopassanXRDfromtheleftlisttotherightlistthereare3choices: 1.-doinga"doubleclick"ontheXRDyouwant 2.-dragginganddroppingontotherightlisttheselectedXRD.Ifyou drag-dropontothecolourlineyouwillgettheXRDinthatcolour. 3.-pressingthebutton"PassALL"TheXRDcanbedeletedfromthelistintwoways: 1.-dragginganddroppingtheselectedXRDontothepaperbin 2.-pressingthekey"Supr"youwilldeletetheselectedXRDWiththe"Resc.Aut."buttontheXRDswillberescaledinthesameorderastheyareinthelist.Withthefollowingoptionsyouwillget:· Fixaxisformat:holdconstanttheaxisformat.· Deletetext:thetextwillbedeletedwhenanewplotisdone.· Black(White):gettochangethecolourlineoftheallXRDstoblack(ifthebackgroundcolouriswhite)orwhite(ifthebackgroundcolouriswhite).· BackgroundColour:Black:changesthecolourofthebackgroundtoblack.

RIETVELDXRDAllowsyoutochoosewhichpartofthefileisgoingtobeplotted:· Experimental:youcanchooseline(blue)orpoints(black)· Theoretic:alwaysappearsinablackline· Difference:plotsthedifference(greenline)betweenexperimentalXRDandtheoretic.· Reflections:plotsthereflectionsofeveryphase.· Background:plotsthecalculatedbackground.Onlyavailablein.PLT;and.PRFfileswiththerightbackgroundfileinthesamedirectory.· Excluderegions:toenabletheexcludedregions.Onlyavailablefor.PRFfiles.· Asabove(andasalwaysinthisprogram)theWidthappliesonlytotheprintout.It’spossibletochangethecolouroftheexperimental,theoretic,differenceandbackgroundbyclickingeachcolour.Withthefollowingoptionsyouwillget:· Fixaxisformat:holdconstanttheaxisformat.· Deletetext:thetextwillbedeletedwhenitisdoneanewplot.

Axis Fromhereyoucanchangethenumberofdivisionsofaxis,valueofdivisions,addgrids,etc. Pressingthebutton"confirm"youcanfindoutifallvaluesarecorrects,forinstance,itcannothave7intervalsindiv.ppal.between0and60in2qalongwithavalueof5ofthediv.ppal.Thepredominantvalueistheoneyouinputlast. TheDiv.ppal.linesandDiv.sec.linesoptionssetagridin2qaxis.

Peaks· Search: Auto:youmakeapeaksearchaccordingtotheconditionsatthebottom.Iminmeanstheminimumintensitytodetectanypeak;2qminandmax.settheintervalin2qforsearching;andSlopesetstheminimumslopeofthepeaks. Manual:allowsyoutosearchpeaksinamanualwayusingthetools(12),(13)and(14)inthemainscreen;orbyusingthemousebydoubleclickingonthepeaksandthenpressingtherightbuttonofthemouse.· Options:twosubmenus Peaksas:setsthewayDRXWinwillplotthepeaks Numbers:putsanumberaboveeverypeak Symbols:plotsasymbolabovethepeaks 2Theta:putsaboveeverypeakits2Thetavalue d:putsaboveeverypeakitsdvalue Changesymbols: Assignedtopeaks:toquicklychangesymbolsbetweentheavailablepeaksfromthegloballist.Thereisanextrasymbol(J)touseitasadummyifitisneededintheprocessofchangesymbols. Fromthegloballist:toaddanewpeaknotincludedinthegloballistortochangethesizeorboldconditionofthepeaks.· Plot:therearechancestoplotonlythepeaksofthosebelongingtothechosenXRDorofallXRDyouhaveplottedinthemainscreen.· Delete:youcanerasethepeaksoftheactiveXRDorofallXRD. TheactiveXRDissetinthelisttitled"ActiveXRD:".ToachieveapeaksearchofvariousXRDatthesametimeitisadvisablethattheyarerescaled. Peaksaredeletedifyouselectthemanddrag-dropinthepaperbinorbypressingthekey"Supr". Inordertoaddsymbolstothefoundpeaksyoumustselectthepeakorthepeaksyouwantanddrag-droponthesymbolandthenthesymbolwillappearattheleftofthepeaklist.Ifyouwanttoaddmorethanonesymboltoonepeakyouhavetograg-dropontotheDUPplace,soyouduplicatethepeakandyoucanaddanothersymbol.Thesymbolsareerasedifyoupicktheplacewheretheyareanddrag-droptothepaperbin. PressingthebuttonwhichhasadisketteandanarrowyouwillbeabletosavethepeaksinASCII(.PAT)orbinary(.XRP)format.Thesefiles(.XRP)canbeputinadatabaseofpatternsusingtheprogramCreaFitwithextensionDTB. ThemaximumnumberofpeaksforaXRDis200.

Patterns Itispossibletoplotstickpatternsfrom*.DTBfiles.ThesedatabasefilescancontainpatternscomingfromDRXWin(*.XRP;*.PAT)orPDF-2database,andarecreatedintheCreaFitprogram.· OpenDTB:firstyouhavetoopenadatabasefile(*.DTB).Theprogramsearchfora\drxwin\dtb\directorytofindpatternfiles,soitisadvisableyoumakeadirectorylikethatandsavetherethe*.DTBfiles.· Search: 1.-byPDFcard 2.-byformula Withthesecommandsyouwillgetapartialdatabase(SubDTB). 3.-showall:openthecompletedatabaseagain.ItisusedwhenyouhaveaSubDTByyouwanttohaveallpatternsonthelistagain.· Options: 1.-qualitativeanalysis:firstofallyouhavetoperformapeaksearchandthenonthebasistothesepeakstheprogramwillgiveyoualistofpossiblephasesthatexistintheXRD.Therearetwoconditionsofsearch:thefirstanalysesifthereareatleast70%ofthetotalintensitywiththefoundpeaks(showingthe%found),andifitisnottruethenthesecondsearchesforthe2or3mostintenselines.Ifsomepeakwithintensityhigherthan50%isnotfoundthenCreaFitwilltrythesecondalgorithm. 2.-Error=0.15:setstheerrorvaluewhencomparingpeakstopatternsin2qunits. 3.-Fastplot

:allowsinafastwaytoplotthepatternsontheXRDs. 4.-Information

:showinformationofapattern

:chemistryformula,crystallographicdata,hesamewayastheCreaFitprogram.IMPORTANT:ThephaseswillbesearchedONLYonthepatternswhichareinthelist(ifyouhaveaSubDTBinthelistyouhavelesspatternsthaninthe*.DTBfile). PerformingtheQualitativeAnalysisondatabasesversionsearlytoCreaFit1.2theprogramwilltellyouthatupdatethedatabase(youonlyhavetoopenthefileinCreaFitandthensaveit). Whenyouopendatabasefiles(.DTB),thepatternsareshowninthelistoftheabovefigure,ifyoupickonthislistandpressthemouserightbuttonyouwillobtaininformationabouttheselectedpattern.Toplotapatternyouhavetomakeadouble-clickonthelistandthepatternwillappearinthepatternslistofthemainscreen.Inthislistyoucanputupto9patternsatthesametime.Inordertoplotthemyouhavetopickthepatternanddrag-dropontheXRDyouwant. Todeleteapatternonthescreenyouhavetoselectoneandthenpressthekey"Supr".Todeleteapatternofthepatternlistyoumustselectit/themandpressthekey"Supr"asabove. Adouble-clickinthemainscreenselectsastickpatternbyputtingblackspotsonthetopofthelines,moreoverinthepatternlistthepatternwillbeshadowedaswell.Youcanalsofindoutwhatpatternisplottedbydouble-clickingonthepatternlist.

TOOLSItispossibletofindinaninteractiveway(noautomatic)thebackgroundprofileofanXRD;toperformasmoothingbyaveragingtheintensitiesofthepeaks;tocalculatetheareaofthepeaks;deconvolutionofthepeaksusingseveralfunctions;removerangeoftheXRDs;combine(addorsubtract)andrescaleXRDs.ToperformthedifferentoperationsusethefollowingcommandsinToolsmenu:Background· Setbackground:themousepointerbecomeanarrowandyouwillbeabletosetthepointswhichwillbedefinethebackground.Thispointswillbesurroundedbyasmallsquareboxandyouwillbeabletomovethemalongthetwoaxisinitsallowedvalues(youwillbeunabletomovethemto2qvaluesnotallowedby2qmin,2qmaxorstep-sizeforexample).· Calculatebackground:inversion1.3itispossibletocalculatethefullprofilebyusing3methods:linearinterpolation,cubicsplines,andapolynomial(polynomial1)as:· Subtractbackground:thecalculatedbackgroundcanbesubtractedintwoways: Partial:theminimumintensityischosenasareferencetosubtractit. Total:zerointensityischosenasareferencetosubtractit. AnUNDOcanbedonefromEditionmenuwithUndoBackgroundcommand.Withthefollowingcommandsyouwillget:· Removemarks:removereferencebackgroundmarksfromthescreen.· Erasebackground:erasethebackgroundline. ThepointsselectedtodefinethebackgroundcanbeseeninthelistthatyoucanshowwiththecommandBackgroundListfromthemenuOptions.FromthiswindowbyusingthecorrespondingiconsitispossibletosavethepointsinASCIIformatandopenafilelikethattoplotthem.Smoothing ItisonlypossibletoperformsuchaoperationonaXRDnore-scaled.Youcanperformseveraltimesthesmoothingprocess.AnUNDOcanbedoneinthesamewayasabove.Area Firstofallyouhavetosetthelimitsoftheareatocalculatewiththeleftandrightbuttonofthemouse.ThenwithCalculatetheprogramwillcalculatetheareashadowedofthepeak.Deconvolution AsaboveyouhavetosetthelimitsoftheregionoftheXRDwheretoperformtheoperationwiththeleftandrightmousebuttons.Afterwardsyouhavetochooseonefunctionfromthefollowings: Gaussian Lorentzian Pseudo-Voigt:A,W,X0andgarerefinableparameters.Wisthehalfoffullwidthatmediumheight:W=(FWHM/2).X0isthe2qvaluewherethefunctioniscentred.gistheLorentziancontributiontothefunction.YoucansetseveralConstraintslike: FWMHequalorlesstosomevalue. FWMHforka1equaltoFWMHforka2. Lorentziancontribution,g,whenusingPseudo-Voigtfunctions. gforka1equaltogforka2. Changewavelenghtsofka1andka2.Ifforka2itisequalto0itwillnotcalculatetheka1-ka2splitting. Holdthetheoreticalrelationforka2-ka1intensities.If-1thisvaluewillberefined. SettheminimumvalueforRp,definedasfollows: SettheminimumvalueforRp,definedasfollows

: Moreover,itispossibletorefineeveryparameterofthefunctionsiftheyhavea-1downit,butiftheyhavea0theywillnotrefined.TheparameterthatbelongstothebaselineitiscalledBL. Ifyouwanttoconsidermorethanonereflectioninthatregionyoumustsettheminthesamewayaswhenamanu