PDF-4+

Report
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PDF-4+
The Powder Diffraction File
Release 2006
PDF-4+
Index –
Use direct links to skip to the section
 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
PDF-4+
PDF-4+ Basic Capabilities
 PDF-4+ contains 254,873 entries.
 Entries contain > 85 data fields, some fields
such as d, I, h,k,l and atomic parameters may
contain 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 permuted
using a JAVA interface. This results in nearly endless combinations
for data display and analysis, only a few of which are described here.
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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.
Many features in the database are specifically designed
for distributor use.
A list of compatible software and distributors can be found here.
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PDF-4+
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)
Diffraction Analysis Software
interfaced to PDF Databases
Software
Bede Search/Match
EVA, DiffractPlus,
PolySNAP, Topas
DiffractPlus, EVA
Match, Endeavor
MacPDF
ACT, OIM
Rayflex Search/Match
Traces
Flamenco
WinDust32, 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, jPOWD
RIQAS, RUBY
PDF Plus
Flamenco
Crystallographica
X’Pert Highscore Plus
JADE, jPOWD,
RIQAS, RUBY
ADM/PADS
2TdST
WinX Pow
TXRDWIN
WinXRD
SEARCH/MATCH,
QUANT
Please 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).
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PDF-4+
Design & Purpose
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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.
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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.
•Most matching is done by comparing sets of d-spacing and Intensities,
however it can also be done by chemistry, properties, structural
and crystallographic classifications – using dozens of different
searches.
•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 to
physical and chemical measurements.
•Data are extensively classified by chemical and structural types;
each classification can be searched.
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PDF-4+
Sources of Data
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PDF-4+
The Powder Diffraction File
PDF-4+ Database
Data Sources for the Database
1) Publications, 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+ uses 4 database sources.
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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.
 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 also
updated continually and the entire database gets reviewed each time.
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Powder Diffraction File – Database Collaborators
PDF-4+
Cambridge Structural
Database (CSD)
ICSD
NIST
14 (LPF)
Linus Pauling File
PDF-4+
Each PDF database contains data
from several database sources
PDF-4+
254,873 Entries
PDF-4/ Organics
312,355 Entries
Release 2007
PDF-2
186,107 Entries
ICDD, NIST, ICSD + LPF
ICDD-organics + CSD
ICDD, NIST, ICSD
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PDF-4+
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, many
with unique compositions. This data is added to inorganic
materials data from ICDD, NIST and ICSD to form the
comprehensive data collection in PDF-4+.
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500,000 Material Data Sets and Growing!
PDF-4+
Data from
global sources – collected, translated, edited and standardized
60 Years
PDF-4/
Organics
PDF-4+
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PDF-4+
PDF-4+
More Data and New Data
Distribution of data by number of
elements, PDF-2 and PDF-4+
Unique Formula
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PDF-4+
Database Codes
The first two digits in any PDF number contains the database
Code. For example PDF 04-005-4319 is the PDF number for
an Fe3O4 entry that is sourced from the Linus Pauling File
(04-LPF).
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PDF-4+
Material Data Sets (Entries)
Each entry contains
Chemical information and nomenclature
Experimental conditions
Diffraction data including d,I and h,k,l listings
Journal reference and bibliographic citations
Crystallographic data
Print display of a
PDF entry
Individual entries, such as the one for
Acetaminophen, PDF 00-039-1503, displayed
on the left may contain thousands of
alphanumeric data fields.
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Acetaminophen
PDF 00-039-1503
PDF-4+
A multi-page nested display,
shown below, is used to
display the data in PDF-4+.
Printed Form for Data
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PDF-4+
Quantitative Analysis
with PDF-4+
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PDF-4+
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.
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PDF-4+
Quantitative Analysis and
PDF-4+
Method
of Quantitation
Database Quantity Required by
the Method
Reference Intensity Ratio
165,923 Entries with I/Ic
Rietveld Analysis
98,291 Structures with atomic
parameters and unit cells
Full Pattern Analysis
254,873 entries all with full
digital patterns that can be
modified for wavelength,
radiation (x-rays, neutrons,
electrons) instrumental and
specimen effects
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PDF-4+
Full Pattern Analysis
Digital patterns of ~150 A Cellulose II and Ib, with crystalline
stearic acid. Experimental data on a natural product tablet in blue.
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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
1
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
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PDF-4+
1
Display Options
Molecular Dimensions &
Graphics
Molecular Graphics
Bond Angles & Distances
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PDF-4+
1
Pattern Simulations
Options for the addition of multiple phases,
instrument and specimen factors, wavelengths.
Options for import/export and graphic display
Calculations.
Crystallite size
simulation
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PDF-4+
Display Options – d,I Listings
Right click the mouse to Undock pattern listing and compare data
with different instrument configurations.
Fixed Slit
Variable Slit
Integrated I
Note how the intensities changes as
a function of optical configuration, resolution.
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2
Data in Nested Display
PDF-4+
Print Forms
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PDF-4+
2
Experimental and
Bibliographic reference
Structure, symmetry,
atomic positions,
active link to atomic
environment display
Data in Nested Display – Computer Display
Opening page – status,
formula, quality mark
Subfile designations, pattern
cross references (active link),
Pearson symbol and
prototype assignment
Editors evaluation
and database cross references
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PDF-4+
Display Fields in PDF-4+
Color Coding Key
 Fields filled in >80% of the 254,873 entries
 Fields filled when the data is provided by
the original source
 Fields filled by an field expert editor,
consultant or volunteer editorial task team
 Quality indicator measurements
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PDF-4+
Display Fields Accessible from the Main
Entry page through nested page displays
PDF
Experimental
Physical
Crystal
PDF#
Status
Quality Mark
Pressure/Temperature
Chemical Formula
Weight %
Atomic %
ANX
Compound Name
Mineral Name
Common Name
Radiation
Wavelength
Filter
d-spacing type
Cutoff
Intensity type
I/Ic
Camera Diameter
Reference
Title
Author
Citation
System
Space Group
Aspect
Author Cell
Volume
Reference
D calc
D meas
D structure
SS/FOM
Melting Pt
Z
R-Factor
Error
Space Group
Z
MW
Crystal Cell
Crystal Volume
Crystal axial ratio
Reduced Cell
Reduced Volume
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PDF-4+
Optical
Display Fields Accessible from the Main
Entry page through nested page display
Only in PDF-4+
Structure
alpha
TF type
beta
Coordinate Table
gamma
Atom
Sign
Number
2V
Wyckoff Position
Reference Symmetry
x,y,z
SOF (Site Occupancy)
ITF (Isothermal TF)
AET (Atom Environment)
Symmetry Operator
Anisotropic Temp Factors
Miscellaneous
Editorial
CAS #
PDF Cross References
and status
Pearson Symbol
Prototype Structure
LPF Prototype
Mineral Classification
Zeolite Classification
Subfiles
Entry Date
Last Modification Date
Editors Comments
98,291 Structures in PDF-4+
-includes comments
generated by statistical
analysis of the data
User Comments
Shared Comments
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PDF-4+
Display Fields in PDF-4+
Expanded views
of the d, I, h,k,l
listing
and
stick figure.
Both are interactive
displays where the
user can expand,
sort and scale the
data.
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PDF-4+
Searches and Data Mining
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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
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Searching
PDF-4+
Search Icon
“Point and Click”
Opening screen menu
Searches are performed by
using the search option on the
program DDView+. This
program is embedded in the
database. 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. Every PDF-4+
database has this program. (It is
an option for PDF-2).
Main Search Page
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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
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PDF-4+
Searches are activated
by point and click operations
or alphanumeric entry. Activated
fields become highlighted in red.
Multiple fields can be active.
In this example
search fields for LPF,
star quality, primary,
ambient data for Si and O
were activated.
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PDF-4+
This search activated an
empirical formula combined
an elemental composition analysis
with a specific space group
and compound name.
Input element composition
analysis with error limits
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Search Display - Results
PDF-4+
2
The criteria
matched 1,817
entries in PDF-4+
1
The search criteria are given in
the search description.
3
All 1,817 entries
search results can
be accessed through
the scroll bar.
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PDF-4+
Search Results
- 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, drop and change the display order.
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PDF-4+
Search Results
Same search criteria
as before but now
the user defined order
preferences are
displayed:
Mineral name,
Quality mark,
Reduced cell
parameters,
Pearson symbol
and chemical
formula.
Minerals sorted
Alphabetically.
Reverse order by
clicking on the
Header.
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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.
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PDF-4+
Application Example 1:
Phase Identification
 From research we obtain the following data:
– Pattern is cubic
– Lattice parameter a=12.348(.010) Å
– Pattern density is ρ=4.9(.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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PDF-4+
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PDF-4+
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).
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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=3.640 Å, what is the likely concentration of
Zn in the alloy?
52
1
PDF-4+
2
3
2
Search input 1
provide search criteria
with results
3
displayed
53
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.
(Composition plot not done by the database)
54
Application Problem 3 –
Answer shown, sequence described
PDF-4+
FERRO-PARA ELECTRIC TRANSITION
IN BaTiO3
BaTiO3
LATTICE PARAMETER (A)
4.02
A(0)
C(0)
4.01
4
3.99
3.98
3.97
250
300
350
T(K)
400
450
Sequence of 1) Search by composition 2) Search by temperature
3) Display results, 4) Compare cell parameter with temperature*,
5) Plot the results.
* Specific temperature given in the comments section of the entry, so you
would need to display the comment section.
55
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
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Diffraction
Pattern Options
PDF-4+
 Radiation Settings
– Anodes
• X-Ray Diffraction
• Neutron Diffraction
• Electron Diffraction
– Types
•
•
•
•
•
•
Kα1
Kα2
Kβ
Kα(avg)
Kα1+2
Kα1+2+Kβ
– Custom wavelength
58
PDF-4+
Diffraction
Pattern Options
 Geometry Settings
– Bragg-Brentano
– Debye Scherrer
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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, hit return
and then click apply.
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PDF-4+
Graph Icon
Click once
1
Get digital pattern
2
Click again
Add, subtract, scale
input other ref. patterns
or experimental data.
1
2
Crystallite size series
3
Data input
console, provides
data input and
pattern options,
each pattern can be
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adjusted separately.
Application Example 1
Pattern simulation
of complex mixtures
using PDF-4+, DDView+
PDF-4+
Data input
console, goes
to pattern options
Raw Data
6 Phase solution used data from 3 different databases
ICDD-powder, ICSD – single crystal, LPF- single crystal
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PDF-4+
Application Example 2
Full pattern analysis, mixed crystallite
sizes
Digital patterns of ~150 A Cellulose II and Ib, with crystalline
stearic acid. Experimental data on a natural product tablet in blue.
63
PDF-4+
Combining Tools –
Analyzing Polymorphs
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PDF-4+
Example – Examining the
Polymorphs of SiO2
1
1
Execute a Search - Primary patterns, star quality, ambient conditions,
65
2 elements, formula SiO2
PDF-4+
Display the results
2
37 star
quality,
primary
patterns
Search Summary
66
PDF-4+
Customize the results
Why are there so many primary star patterns for SiO2?
To study this, customize the display by selecting preferences.
3
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PDF-4+
Customized results
4
SiO2 polymorphs – differences in Mineral Name, Common Names,
Space Groups, Unit Cell Volumes, Pearson Symbols.
68
PDF-4+
Analyze SiO2 polymorphs
4
Highlight a selection
of data entries in the
results, then right click to
provide a menu of options.
CTRL and Shift Key can
both be used to highlight
user specific entries.
5
From the menu, diffraction pattern is
selected
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PDF-4+
Polymorphs of SiO2
All eight highlighted entries are simultaneously plotted. The data
clearly show that these are polymorphic materials with different
characteristic diffraction patterns for each polymorph.
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PDF-4+
Customize the results
Why are there multiple primary star quality patterns
for same polymorph?
To study this, use the prior results (37 SiO2 primary star patterns) and
look at entries with the same space group, Pearson symbol and
reduced cell volume.
Three entries for Stishovite - why?
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PDF-4+
Three entries for Stishovite why?
Examine the Comments!
Single Crystal
Synthetic Powder
Mineral
Examine properties
Slight difference
in density, I/Ic
High quality data on three different
specimens taken by three different
Laboratories. Mineralogists typically
prefer known minerals, chemists may
prefer high purity synthetic or single
crystal – if different in source or properties
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ICDD editors will keep all entries.
SiO2
Why are there 37 primary, star
patterns?
PDF-4+
Answer
Polymorphs, a primary pattern is selected for each different
polymorphic form (~24 different polymorphs).
Different physical properties – the same polymorph may
have slightly different physical properties or chemistry
(i.e. due to calcination). This is especially
common in minerals from different geographic localities.
Difference source, for example mineral or synthetic, powder
or single crystal.
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