2 Index – Use direct links to skip to the section FundamentalsDesign and PurposeData sources and collaborationsQuantitative Analysis with PDF-4+Material Data Sets (Entries)Pattern SimulationsMolecular DisplaySearches and Data MiningPattern FittingCombining Tools – Analyzing polymorphs
3 Notice This presentation gives an overview of features and capabilities found in the Powder Diffraction File (PDF),specifically PDF-4+ Release 2006.This presentation represents a small portion of thecapabilities in the database. The presentationfocuses on the database and not on the capabilitiesof the database when combined with the world’s leadingdata analysis programs.The database itself contains over 500 pages of helpfile documentation. This includes definitions and termsof the classifications and calculations used in the database.
5 PDF-4+ Basic Capabilities PDF-4+ contains 254,873 entries.Entries contain > 85 data fields, some fieldssuch as d, I, h,k,l and atomic parameters maycontain dozens to hundreds of data points.There are 65 different data display options.There are 44 search options.Display and search options can be combined and permutedusing a JAVA interface. This results in nearly endless combinationsfor data display and analysis, only a few of which are described here.
6 Powder Diffraction File (PDF) PDF Databases are designed to work with mostcommercial diffraction analysis software packages.The ICDD works with software distributors sothat the PDF seamlessly interfaces to their software.Many features in the database are specifically designedfor distributor use.A list of compatible software and distributors can be found here.
7 Diffraction Analysis Software interfaced to PDF Databases Company SoftwareBede Bede Search/MatchBruker AXS EVA, DiffractPlus,PolySNAP, TopasBruker AXS SAS DiffractPlus, EVA(formerly Socabim)Crystal Impact Match, EndeavorDigital Data Corp MacPDFEDAX ACT, OIMGE Inspection Rayflex Search/MatchGBC TracesHKL Technology FlamencoInel WinFitITAL Structures WinDust32, WinSearch32Kratos (Shimadzu) PDF-2 Search SoftwareCompany SoftwareMDI JADE, jPOWD RIQAS, RUBYOverseas X-ray PDF PlusOxford Instruments FlamencoOxford Cryosystems CrystallographicaPANalytical X’Pert Highscore PlusRigaku JADE, jPOWD, RIQAS, RUBYRMS Kempten ADM/PADSSine Theta 2TdSTSTOE & Cie GmbH WinX PowTasker Applications TXRDWINThermo Electron WinXRDZDS SEARCH/MATCH,QUANTPlease check with the vendor to match their software with the specific release of the PDF database (year and type, i.e. PDF-4+ Release 2006).
9 All PDF Databases are designed for rapid material identification All PDF Databases are designed for rapid material identification. This differentiates a PDF database from all other databases of crystallographic or physical property data. If you are working on a known material another database may be more appropriate for your work.
10 Powder Diffraction File Rapid Material Identification with the PDFThe database is designed to use input data and match it tocandidate reference materials.Most matching is done by comparing sets of d-spacing and Intensities,however it can also be done by chemistry, properties, structuraland crystallographic classifications – using dozens of differentsearches.All data are converted to a standardized format for rapid search.There are many embedded indexes facilitating searches.Data entries are extensively cross referenced to other entries and tophysical and chemical measurements.Data are extensively classified by chemical and structural types;each classification can be searched.
12 The Powder Diffraction File PDF-4+ Database Data Sources for the Database1) Publications, journals, scientific periodicals and theses2) ICDD Grants for new materials (~60 annual grants)3) Data collections donated by companies or individuals4) Data from other Database organizations that theycollect from scientific publicationsThe Powder Diffraction File contains a compilation of datafrom 5 global databases. PDF-4+ uses 4 database sources.
13 PDF Databases – Continuous growth and change Data on new materials are being constantly collected and published by laboratories around the world so the PDF database continually grows.With time, data quality has steadily improved in both accuracy and precision. (Better hardware, optics, software and computational power as a function of time). This leads to improved accuracy in the database and the diffraction method of analysis.A major function of the ICDD editorial system is to evaluate quality and standardize data that has been collected by global sources over decades of time. The quality evaluations and standardization processes are alsoupdated continually and the entire database gets reviewed each time.
15 Each PDF database contains data from several database sources 254,873 EntriesPDF-4/ Organics312,355 EntriesRelease 2007PDF-2186,107 EntriesICDD, NIST, ICSD + LPFICDD-organics + CSDICDD, NIST, ICSD
16 PDF-4+The PDF-4+ and its subset, PDF-4/Minerals, are the only PDF databases that contains data from the Linus Pauling File (LPF). The LPF is currently the largest single global source of inorganic atomic coordinates and crystallographic parameters.It is also a large source of data on inorganic materials, manywith unique compositions. This data is added to inorganic materials data from ICDD, NIST and ICSD to form the comprehensive data collection in PDF-4+.
17 500,000 Material Data Sets and Growing 500,000 Material Data Sets and Growing! Data from global sources – collected, translated, edited and standardizedPDF-4/Organics60 YearsPDF-4+
18 PDF-4+ More Data and New Data Distribution of data by number ofelements, PDF-2 and PDF-4+Unique Formula
19 Database CodesThe first two digits in any PDF number contains the databaseCode. For example PDF is the PDF number foran Fe3O4 entry that is sourced from the Linus Pauling File(04-LPF).
20 Material Data Sets (Entries) Each entry containsChemical information and nomenclatureExperimental conditionsDiffraction data including d,I and h,k,l listingsJournal reference and bibliographic citationsCrystallographic dataIndividual entries, such as the one forAcetaminophen, PDF , displayedon the left may contain thousands ofalphanumeric data fields.Print display of aPDF entry
21 AcetaminophenPDFA multi-page nested display, shown below, is used to display the data in PDF-4+.Printed Form for Data
23 PDF-4+ The PDF-4+ database is designed for rapid identification and quantitative analysis.Quantitative analysis can be performed by any of three different methods and the database provides the properties required these analysis techniques.
24 Quantitative Analysis and PDF-4+ Method Database Quantity Required byof Quantitation the MethodReference Intensity Ratio 165,923 Entries with I/IcRietveld Analysis 98,291 Structures with atomicparameters and unit cellsFull Pattern Analysis 254,873 entries all with fulldigital patterns that can bemodified for wavelength,radiation (x-rays, neutrons, electrons) instrumental and specimen effects
25 Full Pattern AnalysisDigital patterns of ~150 A Cellulose II and Ib, with crystallinestearic acid. Experimental data on a natural product tablet in blue.
26 Automated Quantitative Analysis by XRD PDF-4+ databases provide reference data, viewing software, critical physical properties and crystallographic properties required for quantitative analysis.The database is designed to work with many softwarepackages, including those of all major global instrumentmanufacturers. These software packages provide therequired calculations and refinements for automatedquantitation utilizing the data in PDF-4+. With modern software and databases this operation is seamless and can be often be done in minutes.
31 Pattern Simulations 1 Options for the addition of multiple phases, instrument and specimen factors, wavelengths.Options for import/export and graphic displayCalculations.Crystallite sizesimulation
32 Display Options – d,I Listings Right click the mouse to Undock pattern listing and compare datawith different instrument configurations.Fixed SlitVariable SlitIntegrated INote how the intensities changes asa function of optical configuration, resolution.
34 Data in Nested Display – Computer Display 2 Subfile designations, patterncross references (active link),Pearson symbol andprototype assignmentExperimental andBibliographic referenceOpening page – status,formula, quality markStructure, symmetry,atomic positions,active link to atomicenvironment displayEditors evaluationand database cross references
35 Display Fields in PDF-4+ Color Coding KeyFields filled in >80% of the 254,873 entriesFields filled when the data is provided by the original sourceFields filled by an field expert editor, consultant or volunteer editorial task teamQuality indicator measurements
36 Display Fields Accessible from the Main Entry page through nested page displays PDFPDF#StatusQuality MarkPressure/TemperatureChemical FormulaWeight %Atomic %ANXCompound NameMineral NameCommon NameExperimentalRadiationWavelengthFilterd-spacing typeCutoffIntensity typeI/IcCamera DiameterReferenceTitleAuthorCitationPhysicalSystemSpace GroupAspectAuthor CellVolumeReferenceD calcD measD structureSS/FOMMelting PtZR-FactorErrorCrystalSpace GroupZMWCrystal CellCrystal VolumeCrystal axial ratioReduced CellReduced Volume
37 Display Fields Accessible from the Main Entry page through nested page display Only in PDF-4+OpticalalphabetagammaSign2VReferenceStructureTF typeCoordinate TableAtomNumberWyckoff PositionSymmetryx,y,zSOF (Site Occupancy)ITF (Isothermal TF)AET (Atom Environment)Symmetry OperatorAnisotropic Temp FactorsMiscellaneousCAS #PDF Cross Referencesand statusPearson SymbolPrototype StructureLPF PrototypeMineral ClassificationZeolite ClassificationSubfilesEntry DateLast Modification DateEditorialEditors Commentsincludes commentsgenerated by statisticalanalysis of the dataUser CommentsShared Comments98,291 Structures in PDF-4+
38 Display Fields in PDF-4+ Expanded viewsof the d, I, h,k,llistingandstick figure.Both are interactivedisplays where theuser can expand,sort and scale thedata.
40 Searches and Data Mining ICDD problem solving softwareCompletely re-written in JavaPowerful search and retrievalNumerous display optionsFlexible user-interfaceFeatures based on our extensive RDB knowledge and user feedbackJavaFaster database accessPortable code for Web (WebStart)Cross-platform (Linux/Unix)User feedbackCustomersMembersEmployees
41 Searching Opening screen menu Main Search Page Search Icon “Point and Click”Opening screen menuMain Search PageSearches are performed byusing the search option on theprogram DDView+. Thisprogram is embedded in thedatabase. If you use vendordisplay software you may haveto start the program “ICDDPDF ” from yourprogram menu to see the optionsdescribed here. Every PDF-4+database has this program. (It isan option for PDF-2).
42 Search Central input form (Main Search Page) 45 unique criteria in 7 categoriesMultiple input methods:ListsTextNumericEstimated Standard Deviation (ESD)RangesPeriodic TableComposition TableLogical Boolean operatorsPowerful cumulative searchesCriteria selection awarenessCriteria ExamplesSubfileEmpirical formulaCompositionReference dataCell axis/volume (author, crystal, reduced)Space groupLong/Strong linesCategoriesSubfiles/Database FiltersPeriodic TableElementsNamesReferencesStructuresMiscellaneous
43 Searches are activated by point and click operationsor alphanumeric entry. Activatedfields become highlighted in red.Multiple fields can be active.In this examplesearch fields for LPF,star quality, primary,ambient data for Si and Owere activated.
44 This search activated an empirical formula combined an elemental composition analysiswith a specific space groupand compound name.Input element compositionanalysis with error limits
45 Search Display - Results 2The criteriamatched 1,817entries in PDF-4+Alphabetical Formula Index sort: Formulae are sorted on 1 commonFormulae are sorted by elements alphabetically starting with the sort element.If 2 formulae elements are alphabetically equal and contain 2 or 3 elements, they are sorted by the ratio of the second-to-last divided by the last atomic weight from largest to smallest.If formulae elements are alphabetically equivalent and higher than a ternary system, atomic weights are sorted alphabetically.Quality Mark (proprietary sort): Star, Indexed, Blank, Low-Precision, Calculated, Prototyping, Rietveld, HypotheticalAll 1,817 entriessearch results canbe accessed throughthe scroll bar.31The search criteria are given inthe search description.
46 Search Results - User Preferences Click on the“Preferences”IconorUse the Fieldsdrop down menuUser selection of the display fields can bedone by point and click interfaces or a dropdown menu. The menu above allows the userto add, drop and change the display order.
47 Search Results Same search criteria as before but now the user defined order preferences aredisplayed:Mineral name,Quality mark,Reduced cellparameters,Pearson symboland chemicalformula.Minerals sortedAlphabetically.Reverse order byclicking on theHeader.
48 Search Results – Display Algorithms & Calculations Sorting algorithms:AlphabeticalAlphabetical Formula IndexNumericalProprietaryCalculations:MeanMedianESDCalculationsDisplayedSame search, the user can highlightany numerical field and obtain amean, median and ESD for the entries.
49 Application Example 1: Phase Identification From research we obtain the following data:Pattern is cubicLattice parameter a=12.348(.010) ÅPattern density is ρ=4.9(.1) g/cm³Pattern color is redPattern melting point is 677(5) °CWe then input these user data into DDView+ and look for possible solution(s).Author’s Cell Axis: Cubic, a: (.01) ÅDensity: 4.9(.1) g/cm³Color: RedMelting Point: 677(5) °C
51 Problem 1 – Results (Answer) With the given input data there are only 2 search hits out of 254,873 entries in the database.One entry is from the experimental collection (PDF 00); the other from the LPF collection (PDF 04).
52 Application: Problem 2 From research we obtain the following data: Powder Pattern Space Group is Fm-3mPattern only contains elements Cu and ZnInput user data into DDView+Additionally:If we measure the lattice parameter:a=3.640 Å, what is the likely concentration of Zn in the alloy?Space Group: Fm-3mPeriodic Table: Only (Cu, Zn)
54 Problem 2 – Results (Answer) 4(Obeys Vegard’s Law)Answer: Estimated Zn weight concentration is 15%The data from thesearch formwere exported andplotted to identify the composition based on lattice parameter.(Composition plot not done by the database)Non-ideal solution behavior3
55 Application Problem 3 – Answer shown, sequence described FERRO-PARA ELECTRIC TRANSITION IN BaTiO3Sequence of 1) Search by composition 2) Search by temperature3) Display results, 4) Compare cell parameter with temperature*,5) Plot the results.* Specific temperature given in the comments section of the entry, so youwould need to display the comment section.
60 Diffraction Pattern Options Profile settingspseudo-VoigtModified Thompson-Cox-Hastings pseudo-VoigtGaussianLorentzianParticle SizeTo change to a userdefined crystallite sizeenter a value, hit returnand then click apply.
61 Graph Icon 1 Click once 1 Get digital pattern Click again Add, subtract, scaleinput other ref. patternsor experimental data.1223Crystallite size seriesData inputconsole, providesdata input andpattern options,each pattern can beadjusted separately.
62 Application Example 1 Pattern simulation of complex mixtures using PDF-4+, DDView+Data inputconsole, goesto pattern optionsRaw Data6 Phase solution used data from 3 different databasesICDD-powder, ICSD – single crystal, LPF- single crystal
63 Application Example 2 Full pattern analysis, mixed crystallite sizes Digital patterns of ~150 A Cellulose II and Ib, with crystallinestearic acid. Experimental data on a natural product tablet in blue.
65 Example – Examining the Polymorphs of SiO2 11Execute a Search - Primary patterns, star quality, ambient conditions,2 elements, formula SiO2
66 Display the results237 starquality,primarypatternsSearch Summary
67 Customize the resultsWhy are there so many primary star patterns for SiO2?To study this, customize the display by selecting preferences.3
68 Customized results4SiO2 polymorphs – differences in Mineral Name, Common Names,Space Groups, Unit Cell Volumes, Pearson Symbols.
69 Analyze SiO2 polymorphs 4Highlight a selectionof data entries in theresults, then right click toprovide a menu of options.CTRL and Shift Key can both be used to highlight user specific entries.From the menu, diffraction pattern isselected5
70 Polymorphs of SiO2All eight highlighted entries are simultaneously plotted. The dataclearly show that these are polymorphic materials with differentcharacteristic diffraction patterns for each polymorph.
71 Customize the resultsWhy are there multiple primary star quality patternsfor same polymorph?To study this, use the prior results (37 SiO2 primary star patterns) andlook at entries with the same space group, Pearson symbol andreduced cell volume.Three entries for Stishovite - why?
72 Three entries for Stishovite - why? Examine the Comments! Single CrystalSynthetic PowderMineralHigh quality data on three differentspecimens taken by three differentLaboratories. Mineralogists typicallyprefer known minerals, chemists mayprefer high purity synthetic or singlecrystal – if different in source or propertiesICDD editors will keep all entries.Examine propertiesSlight differencein density, I/Ic
73 SiO2 Why are there 37 primary, star patterns? AnswerPolymorphs, a primary pattern is selected for each differentpolymorphic form (~24 different polymorphs).Different physical properties – the same polymorph mayhave slightly different physical properties or chemistry(i.e. due to calcination). This is especiallycommon in minerals from different geographic localities.Difference source, for example mineral or synthetic, powderor single crystal.