Introduction:

JADE software can be used to do a wide range of analysis on crystalline powders. Using WPF refinement
phase composition can be determined and using the FWHM (full width half max) JADE can apply
algorithms that can estimate crystallite size as long as the crystals are less than 500 nm in diameter.
However, it is very important to understand what is being measured and what is not.

Using the Scherrer formula, we can calculate an estimate of the grain (crystallite) diameters of the
powders by measuring the breadth of the most intense peak It is the grain size you are trying to
establish. B is full width of the peak at Imax. B must be converted from degrees to radians prior to
calculation of t. is wavelength of the X-ray.

Fig. 1 Patterns of one material obtained on two different X-ray diffractometers

Keep in mind that this is only an estimate, that there are a number of factors that contribute to peak
broadening, crystallite size is not particle size. Broadening can come from the instrument, from strain in
the crystal lattice and from temperature factors to name a few.

Sample Prep
If you havent done so already, make sure your powders are crushed and of a relatively uniform size. It
may be necessary to use the mortar and pestle. Powders with average particle size less than 45 um are
necessary for a good scan. Use the sieve to verify that the powder is ready.

Pack the powder into the sample holder and spread flat. The sample surface must be in the same plane
as the sample holder and there should not be powder anywhere on the sample holder except the well.
If the sample isnt smooth and flat and/or if the sample holder is at any angle in the sample stage then
the peaks will either not show up or they will be shifted.

The TA will supervise the lab and only students who have had some previous training should operate
the instrument. Operation procedures can be found on the class web page. In this lab measure the tin
samples with the following scan parameters. (If you are using a different material, follow the same
procedure with scans the TAs have indicated)

Using JADE for XRD Pattern Analysis

JADE is software developed for academic and industry analysis of XRD patterns. It was used to prepare
the patterns shown in this manual. The class will use JADE to open patterns, label the peaks, estimate
crystallite size, etc. The user manual for the software is very useful and can be found in the help menu
on the main window. For convenience there are a number of excerpts from the help manual in the lab
resource folder. What follows below is the most basic procedures for identifying peaks. For more in-
depth analysis individuals will need to spend some time investigating the features of the software on
their own.

After a pattern has been obtained, if it was saved properly, it will be available on the JADE computer
located in the room next to the XRD room. There is no internet access on either the XRD control
computer or the JADE computer. Only use USB thumb drives on the JADE computer. Do NOT use USB
drives or any other kind of secondary storage media on the XRD control computer.

Open MDI 9, (this is JADE). There will likely be a folder created for the class; go to this folder on the
shared drive and find the XRD pattern to be analyzed. Under the <edit> menu find <User Preferences>
and select <JuniorLab> .

Fig. 5 Primary JADE menu: The menu items most often used are shown.

Under the <Analyze> menu select <Find Peaks>. A dialog opens that allows one to choose what labels to
place on the pattern. In addition to the labels, all of the peak information can be saved as a text file.
 Fig. 6 Peak Search Results

Next, open the <PDF> menu and select <Chemistry> This will open a periodic table.

Fig. 7 Choose Elements

Select the elements of interest. Usually it is better not to select more than 3 or 4 elements at a time. If
the element button is selected once the element turns blue and JADE will search for all possible matches
involving that element. If the button is selected twice the element turns green and JADE will only search
for that element with the stoichiometry chosen. Select <OK> and a new dialog will open with a list of
possible matches. Scroll down the list to find the best match. To narrow the search, close the new
dialog and open the <Search/Match> menu. Choose the line based search. In the line based search
dialog select all data bases on the left hand side, and check the box to use the chemistry already chosen.
Then select the S/M button on the upper right hand corner. If a dialog opens suggesting that a
background can be done, select <No>; this will be done in a subsequent step. This is generally the
longest step. The more one knows about the material, the easier this step becomes.

Once one or more pattern matches have been found, close the search/match window. Under the
<Analysis> menu, select <Peak Profile> (see figures below). Like the Peak search, there are two dialog
boxes associated with this menu item and the second page is accessed with the same page icon. Be sure
to deselect the background curve. Check off <FWHM>, <Skew> and any other variables necessary for
the profile. It may also be helpful to check off K-beta peaks. It is possible to do the peak profile for all
the peaks at once. However, the results tend to be more accurate when done one at a time. Choose
the 3 5 most intense peaks. Use the peak whose area is 100% maximum to calculate the estimated
crystallite size.

Fig. 8 Peak fit

If the pattern is of a mixed phase material the phases present and their concentrations can be
determined. For this kind of analysis it is important to be sure what elements make up the material
before analysis. After the steps above have been completed, open the <Options> menu. At the bottom
is the <WPF> option. Once it loads there should be a dialog in the center that has the number of
reference patterns available. (these are the patterns chosen in the peak search and match). Double click
in the center of the dialog and JADE will run a check using those patterns. JADE returns a statistical
probability that the pattern being analyzed matches up with the reference patterns.

Fig. 9 WPF Refinement

The value R/E is a measure of the goodness of fit and would ideally be one (1). The refinement data and
the pattern can also be saved as a pdf, choose the print icon and select <Quantitative Results>. Please
read the reference, Refinement Displays and Results provided in the lab resource folder.

References:

MSE 311, 312, 313 2012

Callister, William D: Materials Science and Engineering: An Introduction, 6th Edition Wiley & Sons, 2003
Cullity, B.D.: Elements of X-Ray Diffraction 2nd edition, Addison-Wesley Publishing Company, Inc. 2001
Overview of WPF Refinement Page 1 of 3

Overview of WPF Refinement Dialog

With the WPF Refinement option in Jade, you can perform whole pattern fitting (WPF) of the observed data and
Rietveld refinement of crystal structures. The former, sometimes referred to as the Pawley method, can be
considered to be the foundation of the Rietveld method, and is also suitable for cases where crystal structures are
not known but a good reference pattern, complete with d's and I's as well as lattice constants, is available. In
either case, you fit a diffraction model to your measured pattern by non-linear least-square optimization in which
certain parameters are varied to improve the fit of your model to the observed data. Modeling parameters include
background, profile parameters, and lattice constants. For Rietveld refinement, a complete physics simulation is
generally used in which crystal structures of the phases are required. Since the physics of scattering is well
known, this method can be very exact and even allow adjustment of atomic coordinates, occupancies, and
thermal parameters. In Jade, you have access to these parameters but we recommend caution in this area
especially with data that obviously don't warrant such extensive fitting. The object is to stay on the right side of
the line differentiating 'Science' from 'Art' (curve fitting). For some problems you will combine both tools since
one or more phases in a mixture may only be known by a good reference pattern without a structure. In such
cases, we refer to the refinement as combining both 'structure' and 'structureless' models. Although these are
very sophisticated methods, you will find that Jade makes this process simple. The outcome of a successful
refinement would include the phase compositions along with the refined structure models.

An example of the refinement dialog is shown below, and the dialog is accessible from the 'Options | WPF
Refinement...' menu.

With original codes by MDI to implement advanced optimization algorithms and modeling options, its user-
friendly interface and rich features include:

Interactive dialogs designed to work with the XRD Simulation option for easy recall of structure phase data
from FIZ ICSD and user structure database. Therefore this option includes the XRD simulation package.

Integrated structure database manager with Boolean retrievals by structure data. Also utilize Jade's
search/match and PDF overlays with cross reference to structure databases for auto-loading of structure data.

Utilize structureless phase data in WPF refinement, complimenting nicely the model building in cases where a

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Overview of WPF Refinement Page 2 of 3

structure is unknown but a good single-phase pattern is available in the form of a d-I list with known lattice
constants.

Utilize scan data as pure phase patterns in WPF refinement, a useful provision to deal with phases such as
clays which have rather skewed peak profiles and strong preferred orientation.

Determine precise lattice constants with corrections of instrumental and experimental aberrations, and
with/out internal phase standard.

Quantitative analysis with/out internal wt% standard, amorphous content, absorption and preferred orientation
corrections using both March and spherical harmonics function.

Refinement of structure models with intelligent constraints on atomic coordinates and site occupancy.

Unique constraint models for profile FWHM, shape and asymmetry, and allow individual FWHMs.

Allow for refinement of individual FWHM's (for anisotropic broadening), and I% values of structureless d-I list.

Le Bail extraction of reflection intensities (i.e. F(o)) for ab-initio structure solver and Fourier synthesis.

Support user/fixed and polynomial background models. Allow excluded data regions in refinement.

Support multiple powder diffraction geometries: Bragg-Brentano, Seemann-Bohlin, Guinier, Flat ImagePlate.

Allow automatic increment of upper limit in data region to handle refinement of imprecise lattices.

Support 'batch mode' refinement of multiple observed patterns with setup control files and macros.

Totally integrated into Jade with graphical displays of refinement progress and results.

Monitor atomic shifts in 3D structure viewer during refinement and compare before-and-after structure
models.

Extensive output options with refinement logs, presentation printouts and reports.

Handy tooltips identify the interface elements and controls in a compact but efficient dialog.

With all the folders and layers of interface controls, this dialog may appear rather complex to a new user. But
there is logic and purpose to this compact design. For example, modeless dialog makes it easy to setup a
refinement with structure and structureless data using other modeless dialogs in Jade. Being modeless also
makes it possible to interact with the zoom window to view the progress and results during a refinement, hence
justifying a compact design to avoid moving the dialog window. Nevertheless, you can switch it to the tile-view to
utilize larger screen area with the button on the dialog. In this tile-layout, you can toggle between full and
half width by right-clicking at the button, and between full and half height by left-clicking at the button.
Following topics provide detailed descriptions of refinement functions and applications:

Add Phase Data to Refinement

Global Parameters for Refinement
Phase Parameters for Refinement
Global Refinement Controls
Phase Refinement Controls
Refinement Displays and Results
Use Scan Patterns as Phase Data

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Overview of WPF Refinement Page 3 of 3

Phase Screening by WPF

Note: WPF refinement dialogs consume substantial amount of system resources (not physical memory) and
should thus be run on a Win-XP or Vista pc to avoid possible 'out of memory' problem.

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 XRD Intensity calculations : NaCl
Intensity = (Structure factor)(Polarization-Lorentz factor)(Multiplicity factor)
Note: Temperature and Absorption factors= constant for normal analysis

(1) Structure factor for NaCl If h+k+l=even #, Fhkl = 4( f Cl + f Na + )

If h+k+l=odd #, Fhkl = 4( f Cl f Na + )

Planes to be diffracted are: (111), (200), (220), (311), (222), (400)

f(Na+) and f(Cl-) are found from Atomic Scattering Data.

(2) Lorentz-Polarization (L-P) factor =

(3) Multiplicity factor for cubic

NaCl lattice parameter = 5.65 angstrom. Used CuK ray for XRD.

hkl d 2 sin/ f(Na+) f(Cl-) |F|^2 p p-L 1*2*3 Int%

111 3.262 13.65 27.31 0.1532 9 13 256 8 33.02 67641.07 6.9528
200 2.825 15.82 31.64 0.1769 8.5 12 6724 6 24.11 972862.3 100
220 1.997 22.68 45.36 0.2503 7.5 10 4900 12 10.88 640232.8 65.809
311 1.703 26.88 53.76 0.2935 6.8 9.4 108.16 24 7.400 19210.2 1.9746
222 1.631 28.18 56.36 0.3065 6.7 9.2 4044.96 8 6.647 215121.4 22.112
400 1.412 33.04 66.09 0.3539 5.8 8.5 3271.84 6 4.670 91693.07 9.4251

Predicted XRD pattern for NaCl under the CuK ray.

120
(200)
100

80
(220)
a.u

60

40
(222) (400)
20 (111)
(311)
0
10 20 30 40 50 60 70 80
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