X-Ray Diffraction

X-Ray Diffraction
1. Introduction Solid matter can be described as: Amorphous: The atoms are arranged in a random way similar to the disorder we find in a liquid. Glasses are amorphous materials. Crystalline: The atoms are arranged in a regular pattern, and there is as smallest volume element that by repetition in three dimensions describes the crystal. This smallest volume element is called a unit cell. The dimensions of the unit cell are described by three axes: a, b, c and the angles between them alpha, beta, and gamma. About 95% of all solids can be described as crystalline. An electron in an alternating electromagnetic field will oscillate with the same frequency as the field. When an X-ray beam hits an atom, the electrons around the atom start to oscillate with the same frequency as the incoming beam. In almost all directions we will have destructive interference, that is, the combining waves are out of phase and there is no resultant energy leaving the solid sample. However the atoms in a crystal are arranged in a regular pattern, and in a very few directions we will have constructive interference. The waves will be in phase and there will be well defined X-ray beams leaving the sample at various directions. Hence, a diffracted beam may be described as a beam composed of a large number of scattered rays mutually reinforcing one another. We have two kinds of X-ray diffraction: single crystal X-ray diffraction and polycrystalline or powder X-ray diffraction. Single-crystal X-ray Diffraction is a non-destructive analytical technique which provides detailed information about the internal lattice of crystalline substances, including unit cell dimensions, bond-lengths, bond-angles, and details of site-ordering. Directly related is single-crystal refinement, where the data generated from the X-ray analysis is interpreted and refined to obtain the crystal structure.
1

X-Ray Diffraction
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analysed material is finely ground, homogenized, and average bulk composition is determined. It is very important to have a sample with a smooth plane surface. If possible, we normally grind the sample down to particles of about 0.002 mm to 0.005 mm cross section. The ideal sample is homogeneous and the crystallites are randomly distributed. The sample is pressed into a sample holder so that we have a smooth flat surface. 2. X-ray Powder Diffraction (XRD) Instrumentation X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an X-ray detector. X-rays are generated in a cathode ray tube by heating a filament to produce electrons, accelerating the electrons toward a target by applying a voltage, and bombarding the target material with electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target material, characteristic X-ray spectra are produced. The geometry of an X-ray diffractometer is such that the sample rotates in the path of the collimated X-ray beam at an angle while the X-ray detector is mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2. The instrument used to maintain the angle and rotate the sample is termed a goniometer. For typical powder patterns, data is collected at 2 from ~5 to 70. 3. Sample preparation We put our sample on a 2 mm thick plate with a 20 mm square hole in the center. We fix the sample with stickers. On two sides of the plate, there are two glass strips (one in black and the other with no colour) to protect the plate against the pins in the holder. To ensure that the sample has a flat surface, after placing it, we put a glass strip on two glass sides and push it (Fig 1). Then we can check the height of the sample with those for the glass strips. To place the sample in the instruments holder, place the plate under the pins in which the black glass places under two pins (at the back) and the
2

X-Ray Diffraction
other one under one pin (the front). While holding the plate with your hand, with the other hand bring the holder screw up until it reaches the plate. Close the window. Te remove your sample, there is a trigger beside the holder screw. Bring it forward to release the screw and then bring the screw downward while holding the plate with your other hand. Remove the plate.

Hole
Fig 1: Sample fixing on the plate Important: Sometimes the holder arm is not in the horizontal situation. To place the sample easily, you can bring it to the horizontal situation by entering this command to the control panel: Shift Circle 1:1 Enter (When the control panel shows circle, only enter the rest of the command). After placing your sample you should only check that the numbers on the arm have the same direction (1,1,0.2,1).

X-Ray Diffraction

Fig 2: Right position

Fig 3: Wrong position Important: The two lights in the instrument should be on all the times. Otherwise, call the trainer.

X-Ray Diffraction

Fig 4: Siemens D5000 X-Ray Diffractometer 4. Programming After placing the sample go to the computer desktop.
1. Open XRD Main screen folder. In this folder you can find several

icons. The main icons are: Edit Job: To define the condition and collecting the data Eva. : To view the data and evaluate them XCH: To change the format of data (transform from .RAW format to .txt format, etc.) STATUS: To watch the program in progress We start with the Edit Job. 1. Open Edit Job by double click. (Click Yes for the messages).

X-Ray Diffraction

2. On the Default directory you have to define the file name that you

want to have the results to be stored. To change it go to the File menu, select Change default directory and replace the name you want. Make sure that the Definition for directory in ACCM XRD Lab should be the same as bellow: C:\userdata\name of your file\ (e.g. C:\userdata\tahereh\). The final \ is necessary. If you miss it, the data may be saved elsewhere. 3. On the toolbar (top of the window) click D icon. (Click Yes for the messages). Open a New file. Go to Measurement Set up and choose Qualitative Extended. A new window like bellow would be opened:

X-Ray Diffraction

Leave the Comment blank. Check that the Scantype and Scanmode are selected as locked coupled and continuous, respectively. Here, only the settings for 2Theta are active and you cannot change the settings for Theta. Enter 2.0000 and 90.0000 for the start and stop angels. These limits are the standard degrees of rotation when you have no idea of your sample characteristics. Enter 0.0200 and 1.0000 for the Step size and Time/step, as well. By defining these items, in the Scan time you can see the time which is needed to complete the process. The Def. Generator must show 40 kV and 30 mA. These are fixed by the trainer and only change them when a new different condition is needed. Click OK. Go to the File menu, select Save as and save the file in your defined directory (e. G. Tahereh) and name your file based upon your conditions (e. g. 2-90_0-02_1s_1hr13min). Save the file. Close the window.
7

X-Ray Diffraction
1. Return to the data file. In the table insert the name of your sample in the first row and in the RAW.File column. Go to the Parameter File and then click Browse. Choose the file that you made for the qualitative measurement (e. g. 2-90_002_1s_1hr13min). Open it and then its name should be observed in the table. Leave other cells blank. Click Execute Job. Click Yes for the messages. (At this time the No Active Job button at the bottom becomes green and Measurement starts). 1. To watch the program progress, Open Status icon by double click. Evaluation of Data
1. Open the Eva.exe file (storage data software).

X-Ray Diffraction
2. Open the File menu. Go to the Import, then Scan File, browse

for your directory and select the file (.RAW) and open it. Here, you can have a window split into two windows and a tool box window (if not, go to the view menu). Note: By double clicking on top of the smallest window, the whole picks will fit in the biggest window. 3. To figure out the match elements for the picks, from the toolbar, select Search Match.

4. In the Search/Match window, tick your sub file(s). Define the Max Results (e. g. 24). To specify the elements, tick the Toggle all, and then click on your desired element. Otherwise, the system will look for it automatically. (One click: Make the element in gray colour and the software will consider any combination of your selected elements.

X-Ray Diffraction
Double click: Make the element in green colour and the softwares look only for the selected combinations. It is common to click once and look for any combination.) Then click Search. In the database window you can watch the found results and if you click on them, the picks relevant to that item will be appeared on the main window. Besides them there are some signs. (D: Deleted database, Q: Questionable, *: New database). It is advisable to check all of the results to select the best that match your results. 5. To save the file, click Print Preview in the toolbar. Go to Set up and select Landscape, then click OK. Go to the View toolbox and set the title or change it. Click Move to clipboard. Go to WordPad (Start menu, Accessories, then WordPad). Paste the results. In the TXT file, go to File menu, click Save as and save the file in your defined directory (e. g. Tahereh). Change the format of files (XCH) 1. Go to XRD Main Screen. 2. 2. Double click XCH.

10

X-Ray Diffraction

3. Click Open, find your sample file with the .RAW suffix and open it. 4. From the toolbar, select UXD and the opened window change the format of the file from .RAW to .TXT (e.g. change the control.raw to control.txt) and save that .txt file. 5. After the above step, a purple icon will be appeared near the Open folder. If you open it, you can see the .txt file (The data in .txt file can be used in Excell or elsewhere).

Transferring Data to the server When you finish saving the files in your specific directory and also for having access to those data, you should transfer them to the IMAGELAB2 server. To do it:
1. Open the C:\userdata. 2. On the left side you can see a narrow column and on the right side

you have the files in userdata folder. From the left side find the IMAGELAB2 server and drag your directory file (e. g. Tahereh) to the Q-T folder (or any folder that your name belongs to).
11

X-Ray Diffraction
Access to your data from your desktop 1. Go to the address: http://sydney.edu.au/acmm/ 2. Click Accessing the ACMM. 3. Click Download my images. 4. Enter your username and password, click Submit. 5. Beside the Download your images from Imagelab2, click Click here. 6. Select your Group (e. g. Q-T) and save your folder or files on your desktop. Open the results of TXT file in Excel 1. 2. 3. 4. Open the .txt file relevant to your sample. Select the text part and delete all of them. Copy the result numbers. Open a new excel window and paste the copied numbers (if paste is not active, go to Data menu and click on Convert txt to columns).

Technical notes: In different instrument, for each element or compound, the intensity of the picks may vary but the angels are fixed (it is specific for each compound, like a fingerprint for humans!). If the result picks and those from database have a small shift (between 0.1 to 0.2 mm) it can be ignorable. This can happen when the surface of the sample is not completely flat in all regions.

12