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PDF-4+

The Powder Diffraction File Release 2006

PDF-4+

Index –
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 Fundamentals  Design and Purpose  Data sources and collaborations  Quantitative Analysis with PDF-4+  Material Data Sets (Entries) – Pattern Simulations – Molecular Display  Searches and Data Mining  Pattern Fitting  Combining Tools – Analyzing polymorphs
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PDF-4+

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 the capabilities in the database. The presentation focuses on the database and not on the capabilities of the database when combined with the world’s leading data analysis programs. The database itself contains over 500 pages of help file documentation. This includes definitions and terms of the classifications and calculations used in the database.
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PDF-4+ Fundamentals 4 .

I.PDF-4+ PDF-4+ Basic Capabilities  PDF-4+ contains 254.l and atomic parameters may contain dozens to hundreds of data points. h.k. only a few of which are described here. Display and search options can be combined and permuted using a JAVA interface. some fields such as d.873 entries.  Entries contain > 85 data fields. This results in nearly endless combinations for data display and analysis.  There are 65 different data display options. 5 .  There are 44 search options.

PDF-4+ Powder Diffraction File (PDF) PDF Databases are designed to work with most commercial diffraction analysis software packages. The ICDD works with software distributors so that the PDF seamlessly interfaces to their software. A list of compatible software and distributors can be found here. 6 . Many features in the database are specifically designed for distributor use.

PDF-4+ Release 2006). WinSearch32 PDF-2 Search Software Company MDI Overseas X-ray Oxford Instruments Oxford Cryosystems PANalytical Rigaku RMS Kempten Sine Theta STOE & Cie GmbH Tasker Applications Thermo Electron ZDS Software JADE. EVA Match. i. PolySNAP. RUBY ADM/PADS 2TdST WinX Pow TXRDWIN WinXRD SEARCH/MATCH. Topas DiffractPlus. jPOWD. 7 . QUANT Company Bede Bruker AXS Bruker AXS SAS (formerly Socabim) Crystal Impact Digital Data Corp EDAX GE Inspection GBC HKL Technology Inel WinFit ITAL Structures Kratos (Shimadzu) Please check with the vendor to match their software with the specific release of the PDF database (year and type.PDF-4+ Diffraction Analysis Software interfaced to PDF Databases Software Bede Search/Match EVA. jPOWD RIQAS. DiffractPlus. RIQAS.e. OIM Rayflex Search/Match Traces Flamenco WinDust32. RUBY PDF Plus Flamenco Crystallographica X’Pert Highscore Plus JADE. Endeavor MacPDF ACT.

PDF-4+ Design & Purpose 8 .

PDF-4+ 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. 9 .

structural and crystallographic classifications – using dozens of different searches.PDF-4+ Powder Diffraction File Rapid Material Identification with the PDF • The database is designed to use input data and match it to candidate reference materials. each classification can be searched. •There are many embedded indexes facilitating searches. •All data are converted to a standardized format for rapid search. properties. 10 . •Data are extensively classified by chemical and structural types. •Data entries are extensively cross referenced to other entries and to physical and chemical measurements. however it can also be done by chemistry. •Most matching is done by comparing sets of d-spacing and Intensities.

PDF-4+ Sources of Data 11 .

journals. scientific periodicals and theses 2) ICDD Grants for new materials (~60 annual grants) 3) Data collections donated by companies or individuals 4) Data from other Database organizations that they collect from scientific publications The Powder Diffraction File contains a compilation of data from 5 global databases.PDF-4+ The Powder Diffraction File PDF-4+ Database Data Sources for the Database 1) Publications. PDF-4+ uses 4 database sources. 12 .

This leads to improved accuracy in the database and the diffraction method of analysis. software and computational power as a function of time).  With time. optics. 13 . 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. data quality has steadily improved in both accuracy and precision. (Better hardware. The quality evaluations and standardization processes are also updated continually and the entire database gets reviewed each time.PDF-4+ 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.

Powder Diffraction File – Database Collaborators PDF-4+ Cambridge Structural Database (CSD) ICSD NIST 14 (LPF) Linus Pauling File .

355 Entries Release 2007 PDF-2 186. NIST.107 Entries ICDD. ICSD 15 . ICSD + LPF ICDD-organics + CSD ICDD.873 Entries PDF-4/ Organics 312.PDF-4+ Each PDF database contains data from several database sources PDF-4+ 254. NIST.

This data is added to inorganic materials data from ICDD.PDF-4+ PDF-4+ The PDF-4+ and its subset. are the only PDF databases that contains data from the Linus Pauling File (LPF). many with unique compositions. NIST and ICSD to form the comprehensive data collection in PDF-4+. PDF-4/Minerals. It is also a large source of data on inorganic materials. 16 . The LPF is currently the largest single global source of inorganic atomic coordinates and crystallographic parameters.

translated. edited and standardized 60 Years PDF-4/ Organics PDF-4+ 17 .000 Material Data Sets and Growing! PDF-4+ Data from global sources – collected.500.

PDF-4+ PDF-4+ More Data and New Data Distribution of data by number of elements. PDF-2 and PDF-4+ Unique Formula 18 .

For example PDF 04-005-4319 is the PDF number for an Fe3O4 entry that is sourced from the Linus Pauling File (04-LPF). 19 .PDF-4+ Database Codes The first two digits in any PDF number contains the database Code.

k. such as the one for Acetaminophen. PDF 00-039-1503.I and h. 20 Print display of a PDF entry .PDF-4+ Material Data Sets (Entries) Each entry contains Chemical information and nomenclature Experimental conditions Diffraction data including d. displayed on the left may contain thousands of alphanumeric data fields.l listings Journal reference and bibliographic citations Crystallographic data Individual entries.

shown below. Printed Form for Data 21 . is used to display the data in PDF-4+.Acetaminophen PDF 00-039-1503 PDF-4+ A multi-page nested display.

PDF-4+ Quantitative Analysis with PDF-4+ 22 .

23 . Quantitative analysis can be performed by any of three different methods and the database provides the properties required these analysis techniques.PDF-4+ PDF-4+ The PDF-4+ database is designed for rapid identification and quantitative analysis.

923 Entries with I/Ic 98.291 Structures with atomic parameters and unit cells 254.873 entries all with full digital patterns that can be modified for wavelength. electrons) instrumental and specimen effects 24 Method of Quantitation Reference Intensity Ratio Rietveld Analysis Full Pattern Analysis . radiation (x-rays.PDF-4+ Quantitative Analysis and PDF-4+ Database Quantity Required by the Method 165. neutrons.

PDF-4+ Full Pattern Analysis Digital patterns of ~150 A Cellulose II and Ib. 25 . Experimental data on a natural product tablet in blue. with crystalline stearic acid.

PDF-4+

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 software packages, including those of all major global instrument manufacturers. These software packages provide the required calculations and refinements for automated quantitation utilizing the data in PDF-4+. With modern software and databases this operation is seamless and can be often be done in minutes.
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PDF-4+

Features – The PDF Entry

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PDF-4+

The main entry page includes several display options 1 and data in nested display Pages. 2 These are activated by the “point” and “click” of a mouse.

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PDF-4+ 1 Display Options Pattern Simulations Electron Diffraction Simulation Electron Backscatter Pattern Digital Diffraction Pattern 29 .

PDF-4+ 1 Display Options Molecular Dimensions & Graphics Molecular Graphics Bond Angles & Distances 30 .

Crystallite size simulation 31 . instrument and specimen factors. wavelengths. Options for import/export and graphic display Calculations.PDF-4+ 1 Pattern Simulations Options for the addition of multiple phases.

32 . Fixed Slit Variable Slit Integrated I Note how the intensities changes as a function of optical configuration. resolution.PDF-4+ Display Options – d.I Listings Right click the mouse to Undock pattern listing and compare data with different instrument configurations.

2 PDF-4+ Data in Nested Display Print Forms 33 .

active link to atomic environment display Editors evaluation and database cross references 34 . formula. Pearson symbol and prototype assignment Structure. pattern cross references (active link). quality mark Subfile designations. atomic positions. symmetry.PDF-4+ 2 Data in Nested Display – Computer Display Experimental and Bibliographic reference Opening page – status.

PDF-4+ Display Fields in PDF-4+ Color Coding Key  Fields filled in >80% of the 254. consultant or volunteer editorial task team  Quality indicator measurements 35 .873 entries  Fields filled when the data is provided by the original source  Fields filled by an field expert editor.

PDF-4+ Display Fields Accessible from the Main Entry page through nested page displays Experimental Radiation Wavelength Filter d-spacing type Cutoff Intensity type I/Ic Camera Diameter Reference Title Author Citation PDF PDF# Status Quality Mark Pressure/Temperature Chemical Formula Weight % Atomic % ANX Compound Name Mineral Name Common Name Physical System Space Group Aspect Author Cell Volume Reference D calc D meas D structure SS/FOM Melting Pt Z R-Factor Error Crystal Space Group Z MW Crystal Cell Crystal Volume Crystal axial ratio Reduced Cell Reduced Volume 36 .

y.PDF-4+ Display Fields Accessible from the Main Entry page through nested page display Only in PDF-4+ Structure Optical Miscellaneous CAS # PDF Cross References and status Pearson Symbol Prototype Structure LPF Prototype Mineral Classification Zeolite Classification Subfiles Entry Date Last Modification Date Editorial Editors Comments -includes comments generated by statistical analysis of the data alpha TF type beta Coordinate Table gamma Atom Sign Number 2V Wyckoff Position Reference Symmetry x.z SOF (Site Occupancy) ITF (Isothermal TF) AET (Atom Environment) Symmetry Operator Anisotropic Temp Factors User Comments Shared Comments 98.291 Structures in PDF-4+ 37 .

k.PDF-4+ Display Fields in PDF-4+ Expanded views of the d. 38 . Both are interactive displays where the user can expand.l listing and stick figure. I. h. sort and scale the data.

PDF-4+ Searches and Data Mining 39 .

PDF-4+ Searches and Data Mining  ICDD problem solving software – Completely re-written in Java – Powerful search and retrieval – Numerous display options – Flexible user-interface – Features based on our extensive RDB knowledge and user feedback 40 .

Every PDF-4+ database has this program.PDF-4+ Searching Search Icon “Point and Click” Opening screen menu Main Search Page Searches are performed by using the search option on the program DDView+. This program is embedded in the database. 41 . If you use vendor display software you may have to start the program “ICDD PDF-4+ 2006” from your program menu to see the options described here. (It is an option for PDF-2).

PDF-4+ Search  Central input form (Main Search Page)  45 unique criteria in 7 categories  Multiple input methods: – Lists – Text – Numeric • Estimated Standard Deviation (ESD) • Ranges – Periodic Table – Composition Table  Logical Boolean operators  Powerful cumulative searches  Criteria selection awareness 42 .

43 . ambient data for Si and O were activated. Multiple fields can be active. primary. star quality. In this example search fields for LPF.PDF-4+ Searches are activated by point and click operations or alphanumeric entry. Activated fields become highlighted in red.

Input element composition analysis with error limits 44 .PDF-4+ This search activated an empirical formula combined an elemental composition analysis with a specific space group and compound name.

817 entries in PDF-4+ 1 The search criteria are given in the search description.Results 2 The criteria matched 1.PDF-4+ Search Display .817 entries search results can be accessed through the scroll bar. 3 All 1. 45 .

46 . drop and change the display order.User Preferences Click on the “Preferences” Icon or Use the Fields drop down menu User selection of the display fields can be done by point and click interfaces or a drop down menu. The menu above allows the user to add.PDF-4+ Search Results .

Quality mark. Reduced cell parameters. Pearson symbol and chemical formula. 47 . Minerals sorted Alphabetically.PDF-4+ Search Results Same search criteria as before but now the user defined order preferences are displayed: Mineral name. Reverse order by clicking on the Header.

48 .PDF-4+ Search Results – Display Algorithms & Calculations  Sorting algorithms: – Alphabetical – Alphabetical Formula Index – Numerical – Proprietary  Calculations: – Mean – Median – ESD Calculations Displayed Same search. the user can highlight any numerical field and obtain a mean. median and ESD for the entries.

PDF-4+ Application Example 1: Phase Identification  From research we obtain the following data: – Pattern is cubic – Lattice parameter a=12.010) Å – Pattern density is ρ=4.348(. 49 .9(.1) g/cm³ – Pattern color is red – Pattern melting point is 677(5) °C  We then input these user data into DDView+ and look for possible solution(s).

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One entry is from the experimental collection (PDF 00). the other from the LPF collection (PDF 04).PDF-4+ Problem 1 – Results (Answer) With the given input data there are only 2 search hits out of 254. 51 .873 entries in the database.

640 Å. what is the likely concentration of Zn in the alloy? 52 .PDF-4+ Application: Problem 2  From research we obtain the following data: – Powder Pattern Space Group is Fm-3m – Pattern only contains elements Cu and Zn  Input user data into DDView+  Additionally: – If we measure the lattice parameter: – a=3.

1 PDF-4+ 2 3 2 Search input 1 provide search criteria with results 3 displayed 53 .

(Composition plot not done by the database) 54 .PDF-4+ Problem 2 – Results (Answer) 4 (Obeys Vegard’s Law) The data from the Non-ideal solution behavior search form 3 were exported and plotted to identify the composition based on lattice parameter.

PDF-4+ Application Problem 3 – Answer shown.01 4 3. * Specific temperature given in the comments section of the entry.98 3. 4) Compare cell parameter with temperature*.02 LATTICE PARAMETER (A) 4. sequence described FERRO-PARA ELECTRIC TRANSITION IN BaTiO3 BaTiO3 4. 5) Plot the results.97 A(0) C(0) 250 300 350 T(K) 400 450 Sequence of 1) Search by composition 2) Search by temperature 3) Display results. so you would need to display the comment section. 55 .99 3.

PDF-4+ Pattern Fitting and Simulations 56 .

PDF-4+ Pattern Simulations Point & Click Click on this icon brings up the “Preferences” menu options for display features 57 .

PDF-4+ Diffraction Pattern Options • X-Ray Diffraction • Neutron Diffraction • Electron Diffraction  Radiation Settings – Anodes – Types • • • • • • Kα1 Kα2 Kβ Kα(avg) Kα1+2 Kα1+2+Kβ 58 – Custom wavelength .

PDF-4+ Diffraction Pattern Options  Geometry Settings – Bragg-Brentano – Debye Scherrer 59 .

hit return and then click apply.PDF-4+ Diffraction Pattern Options  Profile settings – pseudo-Voigt – Modified Thompson-CoxHastings pseudo-Voigt – Gaussian – Lorentzian – Particle Size To change to a user defined crystallite size enter a value. 60 .

provides data input and pattern options. 3 . each pattern can be 61 adjusted separately. 2 Crystallite size series Data input console. scale input other ref.PDF-4+ Graph Icon 1 Click once 1 Get digital pattern 2 Click again Add. patterns or experimental data. subtract.

PDF-4+ Application Example 1 Pattern simulation of complex mixtures using PDF-4+. ICSD – single crystal. LPF. DDView+ Data input console.single crystal 62 . goes to pattern options Raw Data 6 Phase solution used data from 3 different databases ICDD-powder.

mixed crystallite sizes Digital patterns of ~150 A Cellulose II and Ib.PDF-4+ Application Example 2 Full pattern analysis. with crystalline stearic acid. Experimental data on a natural product tablet in blue. 63 .

PDF-4+ Combining Tools – Analyzing Polymorphs 64 .

star quality. 65 2 elements.Primary patterns. formula SiO2 .PDF-4+ Example – Examining the Polymorphs of SiO2 1 1 Execute a Search . ambient conditions.

PDF-4+ Display the results 2 37 star quality. primary patterns Search Summary 66 .

customize the display by selecting preferences.PDF-4+ Customize the results Why are there so many primary star patterns for SiO2? To study this. 3 67 .

68 . Space Groups.PDF-4+ Customized results 4 SiO2 polymorphs – differences in Mineral Name. Pearson Symbols. Common Names. Unit Cell Volumes.

5 From the menu. then right click to provide a menu of options. CTRL and Shift Key can both be used to highlight user specific entries.PDF-4+ Analyze SiO2 polymorphs 4 Highlight a selection of data entries in the results. diffraction pattern is selected 69 .

The data clearly show that these are polymorphic materials with different characteristic diffraction patterns for each polymorph. 70 .PDF-4+ Polymorphs of SiO2 All eight highlighted entries are simultaneously plotted.

Three entries for Stishovite .why? 71 . Pearson symbol and reduced cell volume. use the prior results (37 SiO2 primary star patterns) and look at entries with the same space group.PDF-4+ Customize the results Why are there multiple primary star quality patterns for same polymorph? To study this.

chemists may prefer high purity synthetic or single crystal – if different in source or properties 72 ICDD editors will keep all entries. I/Ic High quality data on three different specimens taken by three different Laboratories.PDF-4+ Three entries for Stishovite why? Examine the Comments! Single Crystal Synthetic Powder Mineral Examine properties Slight difference in density. . Mineralogists typically prefer known minerals.

73 Answer . powder or single crystal. due to calcination). a primary pattern is selected for each different polymorphic form (~24 different polymorphs). for example mineral or synthetic. Different physical properties – the same polymorph may have slightly different physical properties or chemistry (i.PDF-4+ SiO2 Why are there 37 primary. star patterns? Polymorphs. Difference source. This is especially common in minerals from different geographic localities.e.