ۥ- & % ç ͧ ק(,,BBBBBBB4v&* FARHAN A Qualitative and Quantitative PC program for X-ray powder diffraction Written by Dr. Khalid A. AL-Farhan Chemistry department College of Science King Saud University Riyadh 11451, P.O. Box 2455 Saudi Arabia. Fax: + (9661) 468315 1998 by Dr. Khalid A. AL-Farhan All Right Reserved Contents Chapter One 1.1- Introduction 2 2.1- General Comments 3 3.1- Demonstrating Example files 3 4.1- Measured (Sample) Data File (MDF) content and format (TEST.DI file) 4 5.1- Standard Data-base File (SDF) content 5 6.1- SDF distributed with the program and the Demo version for testing porepous 5 7.1- Program test 6 8.1- Disclaim liability 6 9.1- Installing FARHAN 6 10.1- Running FARHAN 6 11.1- Related References 7 Chapter Two Sample Data Manipulation 8 Chapter Three Standards Data-Base Manipulation 11 Chapter Four (Identification and Quantification) 1.4- Introduction 14 2.4- Identification Examples 15 1.2.4- Identification Example of Major and Minor phases 15 2.2.4- Identification Example of very Minor phases 20 3.4- Identification and Quantification Examples 23 1.3.4- Multiphase Quantification Example using multiline 23 2.3.4- Multiphase Quantification Example using multiline of sample containing amorphous phase 24 3.3.4- Multiphase Quantification Example using one line 26 4.3.4- Multiphase Quantification Example using one line of sample containing amorphous 27 5.3.4- General Comments on Quantification 29 Chapter Five 1.5- Search-Match-Identification (S-M-I) parameters 30 2.5- ASCII Peaks file which can be read by the program 31 Application Form for FARHAN 33 Chapter One 1.1- Introduction FARHAN program (1998) can efficiently provide precise qualitative and quantitative results from X-ray powder diffraction data of unknown sample comprises of several crystalline phases of any type, in one program run, even without user intervention. In favourite cases, the complete qualitative and quantitative results can be obtained by the following three steps: (1) Select the fully-automatic identification and quantification option. (2) Input the sample file name. (3) Input the standards file name. The program has special adjustable Search-Match-Identification (S-M-I) parameters for dealing with very problematic sample i.e. sample severely suffer of preferred orientation and/or solid solution. Furthermore, the author has implemented new powerful matching routine which uses variable Intensity Error Window (IEW) and a tuneable combined figure-of-merit (FOM), which makes the programs automatic identification procedure succeed in most cases. Whether automatic identification was successful or not the program provides the user with many FOMs and dynamic functions which helps him correctly selecting the present phases in the sample. However, for comparison with other Search-Match programs or for use in some special cases, matching routine with fixed IEW is also included in the program. The addition of quantitative analysis to the S-M-I procedure is new and of practical importance in many areas such as in materials quality control, mineralogical surveys, and in most research projects and analysis problems in which the XRPD is used as a primary tool. In FARHAN the most widely used and well-documented internal standard quantification method in its generalised form (via RIR) has been implemented. Thus, the analyst can use any diffraction line or multiple lines to quantify the found phases. The default programs quantification routine (APR) is based on the Adiabatic Principle method (Chung, 1974b). Where no internal standard needs to be added to the sample. However, in the cases where amorphous phase is expected to be presence or an unidentified or identified phase with unknown RIR is present, the programs Matrix-Flushing routine (MFR) (Chung, 1974a) should be used, where the amorphous content can be estimated. Phases quantification from XRPD data using FARHAN program has never been easier. Using APR the analyst dose not need to perform any especial action. While, with the MFR the analyst may need to advise the program which one of the found phases is the added standard, and its weight percent. Then, on the analysts request, the program calculates the weight percent concentration of the found phases either before or after the addition of the standard to the sample Also, included in the program many identification and education supporting routines such as internal-standard line positions correction routine, quantitative multiphase simulated diffractogram routine, 2symbol 113 \f "Symbol" \s 12-I or d-I diffractogram editing and manipulating routine, user data base creation and expansion routine, and other utility routines. At the strategically steps, special offered have been paid to allow the program to either performs a smart selection or protecting the user from inputting wrong value. The way in which the program has been developed allows the professional diffractionest to fully utilise his knowledge. While it can be easily and understandably used by inexperienced analyst and student as to helping them to master the identification subject. On the other hand, it can help the instructor to put examples and exercises to teach his students, in very efficient way, the different techniques used in tackling different frequently encountered identification problems caused by systematic errors, solid solution, preferred orientation, lines overlap in multiphase sample, etc. . The most important theoretical background of the program will be published in the Powder Diffraction (1998) 13.3 1-6 (journal). Thus, this user manual will be concerned with the practical use of the program. However, with the aid of the program easy structure and the included examples you will be able to grow very rapidly your experience in the programs subjects as will as in how to use the program efficiently. Before running the program, please read the general comments in the next title. The program can read the *.DIF and *.UDI files of Siemens and Philips difractometers respectively. And it can use (1) reformatted JCPDS-ICDD files such as Minerals, Metals and Alloys, Educational, (2) reformatted Hlzel file of Minerals (3) User created files, for identification and quantification. Finally, beside the above features, FARHAN is a portable program (about 500 KB). A feature which untie the user (who is interested in identification and quantification) from the diffractometer and the software (which it is not portable) on which he collected his diffractograms. So, the postgraduate students and researchers can carry with them their valuable data and database when they moved from lab. to another lab.. And also allows the community of special interest (zeolites, minerals,...,etc.) to exchange their data and database for purpose of phases identification and quantification. JCPDS: Joint Committee on Powder Diffraction Standards. ICDD: International Center for Diffraction Data, 12 campus Boulevard, Newtown Square, PA 19073, U.S.A. Hlzel: Alexander R. Hlzel, Systematik der Mineralogie, D-55270 Ober-Olm, Ulmenring 11, Germany. 2.1- General Comments 1) FARHAN runs on IBM or Compatible Personal Computer (PC) equipped with 286 or higher processor and Dos2.1 or higher. 2) The approach of this manual is to use demonstrating a step-by-step example and see the effects of each step on the computer screen. Indeed FARHAN was designed to be used without a manual. For this reason, instructive interactive coloured menus are used throughout the program. In these menus, option can be selected by pressing the option identifier, which is either a number or a capital letter, then the choice is confirmed by pressing the Enter key symbol 191 \f "Symbol" \s 12 . In the menu-bar one can moves between options by pressing symbol 172 \f "Symbol" \s 12 or symbol 174 \f "Symbol" \s 12 key. Where a function key (Fn) is used as options identifier, pressing that function key will selects that option. 3) The selected option in the menu-bar is the highlighted one. 4) Information inputted to the program can be either small or capital letters. In this manual capital letters are used. So it is recommended to press the Caps lock key immediately after switching on your PC. 5) In this manual user input is printed in italic font. 6) Always, follow the numbered steps in this manual when you run through the included example. 7) The program Demo version does not shows the full power and output of the program. 3.1- Demonstrating Example files: The following seven sample data files are distributed with FARHAN program for the porepous of demonstrating who the program can be used and types of results it capable to produce: 1) TEST.DI: the sample mainly composed of four minerals (SiO2 (Quartz) & ZnS (Sphalerite) & PbS (Galena) & FeS2 (Pyrite)). XRF analysis indicate small amount of Gold and Copper (the most likely Cu-containing mineral in this sample is the Chalcopyrite CuFeS2). The data of this sample was used to test SANDMAN4 and symbol 109 \f "Symbol" \s 12PDSM6 programs, and also was used as one of the mineral exercises in the "Use of the Powder Diffraction File, An Educational Resource Package, 1996" of JCPDS-ICDD. This file will be used to demonstrates who phases in a multiphase sample can be automatically and interactively identified. 2) TEST.UNA: this file contains the two unassigned lines remain after identifying the first four phases in the previous sample. Remember that, XRF analysis indicate small amount of Gold and Copper (the most likely Cu-containing mineral in this sample is the Chalcopyrite CuFeS2). This file will be used in demonstrating how one can conduct identification based on use of few or one line. 3) Test6.DI: the sample composed of three organic compounds (m-Dinitrobenzene (40%) & 2,4-Dinitrophenol (40%) & 2,6-Dinitrophenol (20%)). The data of this sample was used to test PDSM3 program and the program of Huang and Parrish5. 4) Q16-3-1.DI: the sample composed of three inorganic compounds (ZnO Zincite (40%) & Al2O3 Corundum (20%) & CaF2 Fluorite (40%)). The chemical was taken off the shelf (i.e. they are not certified standards) carefully weighed, thoroughly mixed and ground using agate mortar and pestle. The XRPD data was collected by Siemans D5000 diffractometer (Cu target and Ni filter). Peak height was used to represent the peak intensity. This file will be used in demonstrating the type of quantitative results one may obtained when he used the programs automatic identification and quantification option. 5) Q17-4-1.DI: the sample composed of four phases (ZnO Zincite (15%) & Al2O3 Corundum (30%) & CaF2 Fluorite (35%) & SiO2 Gel (20%) (amorphous phase)). The above sample preparation and data collection procedure in (4) was used. This sample will be used in demonstrating who the program can helps the user detecting the presence of amorphous materials in the sample. Then how he can proceed quantifying the phases, including the amorphous content using multiline. 6) SAMPLE1.DI: the sample composed of four phases (ZnO (41.49%) & KCl (22.23%) & LiF (18.32%) & Al2O3 (17.96)). The data were taken from Chung (1974a) paper. This sample will be used in demonstrating who the quantitative analysis using one line can be performed, the type of quantitative results one may obtained, and one can compered the program results with the published values. 7) SAMPLE5.DI: the sample composed of four phases (ZnO (34.43%) & CaCo3 (28.00) & Al2O3 (21.44%) & SiO2 Gel (16.13%) (amorphous phase)). The data were taken from Chung (1974a) paper. This sample will be used in demonstrating who the program can helps the user detecting the presence of amorphous materials in the sample. Then how he can proceed quantifying the phases, including the amorphous content using one line. 4.1- Measured (Sample) Data File (MDF) content and format (TEST.DI file): E6-1-15 ; sampleID or phaseID SI ZN PB FE ; elements content of the sample Exercise 6.1.15 ; comments 27 1.5405 0 ; number of X-ray lines, symbol 108 \f "Symbol" \s 12, RIR (normally I/Ic) 4.26 20 ; d, I (d-spacing and Intensity of the first line) 3.423 7 3.344 100 3.125 54 3.037 2 2.965 9 2.704 5 2.454 6 2.423 3 2.349 1 2.281 5 2.236 4 2.209 1 2.126 5 2.097 4 1.979 3 1.915 28 1.817 9 1.789 2 1.713 1 1.671 3 1.658 1 1.632 17 1.562 1 1.541 6 1.501 1 1.484 1 5.1- Standard Data-base File (SDF) content: Each phase in this file has the same information as that in the sample data file. The phase chemical formula, chemical name and mineral name were written in the comments line. Also, each d-I line has an order parameter; which is equal 7 for the most intense line, 5 for the second, 3 for the third, and 0 for the other lines. 6.1- SDF distributed with the program and the Demo version for testing porepous: To makes the demonstrating examples representative, the top ranked standard phases results when matching the samples data against the whole undeleted phases in the mineral file of ICPDS-ICDD (4091 phases) or Hlzel minerals file (3800), are included in the FARHAN.DB file. The CHUNG74.DB SDF is also distributed with FARHAN program, for quantitative analyses using one line. 7.1- Program test: The program has been tested extensively using data published in the literature and using many samples of variety of sources and types, and was found to perform exceptionally good. It may be enough here to say that the program can automatically solve almost all the 15 examples in the "Use of the Powder Diffraction File, An Educational Resource Package, 1996" of the JCPDS-ICDD without using elemental information of the sample. In most cases, the user only doing the following steps: (1) Select the Fully-automatic Identification procedure. (2) Input the sample data file name. (3) Input the standard data base file name. 8.1- Disclaim liability: The author disclaims any responsibility for any loss or damage resulting from use of the program or its association. 9.1- Installing FARHAN: 1- Switch on your PC. 2- Press Caps lock key. 3- Make new F98 directory: C:\>MD F98 symbol 191 \f "Symbol" \s 12 4- Change to F98 directory: C:\>CD F98 symbol 191 \f "Symbol" \s 12 5- Copy all the files on the FARHAN diskette to F98 directory: C:\F98>COPY A:*.* symbol 191 \f "Symbol" \s 12 or COPY B:*.* symbol 191 \f "Symbol" \s 12 6- It is convenient to create a program shortcut using windows explorer. In this case it is advisable to select full window and close on exit from the screen option of the properties bottom. 10.1- Running FARHAN: While you are in the F98 directory type the program name: C:\F98>FARHAN symbol 191 \f "Symbol" \s 12 Screen1 is displayed. It shows the authors name and address, the version's year, the copyright sign, the copy serial number and the program tasks. 1- Sample Data Manipulation. 2- Standards Data-Base Manipulation. 3- Identification and Quantification. 4- Quite. The program uses the computer conventional memory. So if it fails to run (1) go to FARHAN.PAR file and reduce the value of Program Memory Control Parameter (the line before the last line in the file), or/and (2) use MemMaker to free more of the 640 kb conventional memory, or/and (3) remove memory-resident programs. 11.1- Related References: Identification and Quantification 1) Khalid A. Al-Farhan (1998) Powder Diffraction.13.3, 1-6. 2) Jenkins, R., and Snyder, R. (1996). Introduction to X-ray powder diffractometry (John Wiley and Sons, Inc.) Identification 3) Marquart, R.& Milne, G. & Heller, S. & Johnson, G. and Jenkins, R. (1979) J. Appl. Crys. 12, 629-634. 4) Schreiner, W & Surdukowski, C. and Jenkins, R. (1982). J. Appl. Crys.15, 513-523. 5) Huang, T. and Parrish, W. (1982). Adv. in X-ray Anal. 25, 213-219. 6) Marquart, R. (1986) Powder Diffraction 1, 34-39. Quantification 7) Chung, F.(1974a) J. Appl. Crys. 7, 519-525. 8) Chung, F. (1974b) J. Appl. Cryst. 7, 526-531. Chapter Two Sample Data Manipulation While you are at screen1 -Type 1 Screen2 is displayed. The menu-bar at the bottom of screen2 is: Input/Read Edit/Diffract (i-s) Correction Normalize Save Print Quit I- Input/Read option Allows you to input sample data from the keyboard or read sample data from a file. 1- T0 read data from file: 1.1- Select the Input/Read option Already selected 2.1- symbol 191 \f "Symbol" \s 12 Screen3 is displayed 3.1- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another MDF) 4.1- symbol 191 \f "Symbol" \s 12 Screen4 is displayed, which is labelled with "Set FARHAN98 program Parameters". The second line in screen4 shows the number of X-ray lines (27) read from the sample data file. This number can be controlled by changing values of d-Minimum, d-maximum and Sample Intensity Background parameters. If one of these values has been changed, Function key number 7 (F7) should be pressed. 5.1- Press Esc key Screen2 is displayed once again. You can now skip down to II (i-s) Edit/Diffract option. 2- To input sample data from key board: (Not fully enabled in the Demo version) Repeat the above steps 1.1 to 3.1 (which will be considered here as steps 1.2 to 3.2) 4.2- type N symbol 191 \f "Symbol" \s 12 N tells the program that new sample data going to be inputted from the key board. Where the default character O tells the program to read old sample data from existent file. 5.2- Input number of X-ray lines symbol 191 \f "Symbol" \s 12 Then follow the screen output to input the sample data. The X-ray line positions can be inputted as d or symbol 113 \f "Symbol" \s 12 or 2symbol 113 \f "Symbol" \s 12 or sin2symbol 113 \f "Symbol" \s 12. Once the sample data has been read or inputted, the following options can be utilised. II- Edit/Diffract option Allows you to displayed, manipulate, edit and save 2symbol 113 \f "Symbol" \s 12-I or d-I diffractogram. - Select the Edit/Diffract option symbol 191 \f "Symbol" \s 12 screen5 is displayed showing the diffractogram. The menu-bar at the bottom of the screen5 is: 1: 2theta 2: d-space 3: Zoom 4: d-2theta 5: Plot 6: Shift Ins: Insert Del: Delete E: exit The symbol 172 \f "Symbol" \s 12 or symbol 174 \f "Symbol" \s 12 key Allows you to move to any diffraction line (the line is highlighted as yellow) as you move from line to line, the exact 2theta, d-spacing and intensity values of the highlighted line are displayed above the diffractogram. The 1 or F1 key Allows you to edit the 2theta and intensity values of the highlighted line. The 2 or F2 key Allows you to edit the d-spacing and intensity values of the highlighted line. The 3 or F3 or Z key Allows you to zoom in the 2theta or d-spaceing axis (the horizontal axis). The 4 or F4 key Allows you to switch between 2symbol 113 \f "Symbol" \s 12-I and d-I diffractogram. The 5 or F5 or P key Allows you to save the displayed plot in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. The 6 or F6 or S key Allows you to shift all the diffraction lines by a specific value of 2theta or d-spacing ( useful for correcting the diffractometer systematic error). The Ins or I key Allows you to insert new diffraction line. The Del or D key Allows you to delete the highlighted line. The H key Allows you to edit the phaseID (or the sampleID). The N key Allows you to edit the phase name (or the sample comment). The E key Allows you to edit the phase (the sample) elemental information. The L key Allows you to edit the lambda value. The Esc key Allows you to exit from the Edit/Diffract option and return to screen2. III- (i-s) Correction option Allows you to correct the sample line positions by Internal-Standard (i-s) method: 1- Select the (i-s) Correction option symbol 191 \f "Symbol" \s 12 2- Type 1 symbol 191 \f "Symbol" \s 12 3- Press Esc key 4- Type 1 5- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF) 6- Type 2.CB.100 symbol 191 \f "Symbol" \s 12 (The i-s phase ID) 7- Press any key 8- Type 1 or 2 or 3 symbol 191 \f "Symbol" \s 12 9- symbol 191 \f "Symbol" \s 12 or type in another file name to save the corrected data in it. Note that, the current data in the computer memory are the corrected sample data. IV- Normalize option Allows you to normalize the sample X-ray intensities (the most intense line scaled to100). V- Save option Allows you to save the current sample data in a file. VI- Print option Allows you to save sample data in a file in format suitable for archiving and printing. VII- Quit option Allows you to finish sample data manipulation task and return to screen1. Chapter Three Standards Data-Base Manipulation While you are at Screen1 -Type 2 Screen6 is displayed. The menu-bar at the bottom of Screen6 is: data-Base Read phase Edit/Diffract save As sample Print Simulate Quit I- data-Base option Allows you to: 1- Create standards data base file (SDF) from sample data file (MDF). 2- Append MDF to an existence SDF. II- Read phase option Allows you to read information of any standard phase stored in one of the SDFs: 1- Select the Read phase option symbol 191 \f "Symbol" \s 12 Screen4 is displayed. d-Minimum, d-Maximum and Standard Intensity Background parameters control how the program will read the X-ray data of the phase. If one of these values has been changed, Function key number 7 (F7 key) should be pressed. 2- Press Esc key 3- Type 1 4- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF) 5- Type 33-1161 symbol 191 \f "Symbol" \s 12 (Quartz SiO2 phaseID) Data of Quartz is now read. III- Edit/Diffract option Allows you to displayed, manipulate, edit and save 2symbol 113 \f "Symbol" \s 12-I or d-I diffractogram. - Select the Edit/Diffgract option symbol 191 \f "Symbol" \s 12 screen5 is displayed showing the diffractogram. The menu-bar at the bottom of the screen5 is: 1: 2theta 2: d-space 3: Zoom 4: d-2theta 5: Plot 6: Shift Ins: Insert Del: Delete Esc: exit The symbol 172 \f "Symbol" \s 12 or symbol 174 \f "Symbol" \s 12 key Allows you to move to any diffraction line (the line is highlighted as yellow) as you move from line to line the exact 2theta, d-spacing and intensity values of the highlighted line are displayed above the diffractogram. The 1 or F1 key Allows you to edit the 2theta and intensity values of the highlighted line. The 2 or F2 key Allows you to edit the d-spacing and intensity values of the highlighted line. The 3 or F3 or Z key Allows you to zoom in the 2theta or d-spacing axis (the horizontal axis). The 4 or F4 key Allows you to shift all the diffraction lines by a specific value of 2theta or d-spacing ( useful for correcting the diffractometer systematic error). The 5 or F5 or P key Allows you to save the displayed plot in a file in HPLG format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. The Ins or I key Allows you to insert new diffraction line. The Del or D key Allows you to delete the highlighted line. The H key Allows you to edit the phase ID (or the sample ID). The N key Allows you to edit the phase name (or the sample comment). The E key Allows you to edit the phase (the sample) elemental information. The L key Allows you to edit the lambda value. The Esc key Allows you to exit from the Edit/Diffract option and return to screen2. IV- save As sample option Allows you to save the data, already read by the program using Read phase or Simulate option (and may be has been edited), in MDF. So it can be used as an exercise for example. V- Print option Allows you to save sample data in a file in format suitable for archiving and printing. VI- Simulate option Allows you to simulate in quantitative way the diffraction data of a multiphase sample: 1- Select the Simulate option symbol 191 \f "Symbol" \s 12 Screen4 is displayed. d-Minimum, d-Maximum and Standard Intensity background parameters control how the program will read the x-ray data of the phases and the d-Error Window parameter controls the way in which the program treats the overlapped lines. 2- Press Esc key 3- Type 2 symbol 191 \f "Symbol" \s 12 To simulate the diffraction data of sample having 2 phases. 4- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF where your first phase is stored) 5- Type 2.CB.100 symbol 191 \f "Symbol" \s 12 (phaseID of Galena) 6- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF where your second phase is stored) 7- Type 33-1161 symbol 191 \f "Symbol" \s 12 (phaseID of Quartz) Simulate Powder Diffraction Screen is displayed. Now you can press F2 key to edit the ISF% values, or press F3 key to edit the RIR values, or press F4 key to edit wt% (weight%) values of each phase in the table. 6- Press F4 key 7- Type 50 symbol 191 \f "Symbol" \s 12 8- Type 50 symbol 191 \f "Symbol" \s 12 9- Press F5 key Note the ISF% of the second phase becomes 92.31. Examine the values in the table and if you are satisfied with them go to the next and final step. 10- Press F6 key Simulation is finished. You can now plot the simulated diffractogram, edit it, print it or save it in MDF. You can use such MDF to test the program or to examine your students or to compare it with similar experiment results. VI- Quit option Allows you to finish standards data base manipulation task and return to Screen1. Chapter Four Identification and Quantification 1.4- Introduction The program provide three level of phases identification and Quantification procedures: 1- Manual Identification and Quantification. 2- Semi-Automatic Identification and Quantification. 3- Fully-Automatic Identification and Quantification. The third procedure is the most sophisticated one. It automatically found the candidate phases and select from them the most probable phases to be present in the sample, then quantify them. It also, allows the user to switch to the Search-Match (s-m) screen where all the functions and figure-of-merits he may need to examine the automatic identification results, or to restore one or more of the selected phases, then interactively identify the present phases, are available to him. In the second procedure the program automatically found the candidate phases then switches to the s-m screen. It is worth to note that, the automatic identification and quantification functions are also available in the s-m screen. This procedure gives the user more control in selecting the candidates when he searching large data base file and he need to use the continue search option. 2.4- Identification Examples TEST.DI file will be used. So, please, see page 3 for sample details. The weight% of the phases constituting the sample of this example is unknown. Thus we will concentrate here mainly on the identification technique. 1.2.4- Identification Example of Major and Minor phases While you are at Screen1 1- Press 3 (to select Identification and Quantification task) 2- Press 3 (to select Fully-Automatic Identification and Quantification procedure) Screen3 is displayed. 3- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another MDF) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) Pressing F1 key restore the field original entry. While pressing F2 key at any field restore the original Sample Major Element. It is highly recommended to include the sample major elements if you knew them. 8- Press Esc To start the Search-Match-Identification-Quantification procedure using the program default parameters and without using the sample elemental information. The Esc key allows you to interrupt the search-match. Screen7 is displayed. As you can see, the program found the correct phases (Quartz, Sphalerite, Galena and Pyrite) and quantify them using the Adiabatic principle method. The quantitative results are not correct because the RIRs of some identified phases is unknown. The screen contains a complete short report of the identification and quantification results. Which can be sent to the printer by pressing the Print Screen key. Searching the whole JCPDS-ICDD mineral file of 4091 undeleted phases (sets 1-45) takes about 7 seconds on IBM compatible PC equipped with Pentium 150 processor. And it takes about 6 seconds to search the whole hlzel file of minerals. Pressing F5 key takes you to the s-m screen. Identification and quantification task is completed here. The task is successful, as can be judge from the displayed General Matching Measured (GMM). Though, the values of the GMM have to be interpreted based on each sample nature. The following values usually indicate reliable and complete identification (major and minor phases) and quantification (if there is no non-crystalline phase or phase with unknown RIR) results have been obtained (see 5.3.4 for comments on quantification). However, the following steps are given to demonstrate some of the program functions and comment on them. Which they are useful in interactive identification and quantification. 9- Press Esc key Full qualitative and quantitative report is sent to TEST.OUT file. Concluding matching plot is displayed. So, the goodness of matches can be graphically estimated in a collective manner. Each line in the simulated (middle) graph has the same color of its phase ID which is shown at the bottom of the screen. Note also the proper treatment of the overlap lines. The top graph shows the position and intensity of the remaining lines (4 lines), two of them (violet) are unassigned (unmatched) lines and the other two (yellow) are residual lines (i.e. remain after subtracting the lines in the middle graph from the corresponding lines in the bottom graph). The graphs can be zoomed and/or saved in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. Pressing F1 or 1 or T key displays the s-m screen. Where pressing Esc key finishing the Fully-Automatic Identification procedure and returns you back to Screen1. 10- Press F1 or 1 or T key Search-Match (s-m) screen is displayed. 9 candidate phases sorted in ascending order of their agreement values and usually the top 10 ranked phases are displayed. The matching table reports the Agreement factor, ISF%, R%, mD-del (<|dm - ds|>), number of matching lines, number of missing lines, 3hp (which tells which of the three most intense lines of the standard is matched and which is missed), phaseID, and formula and name of each candidates. The s-m screen offer almost all the functions user need to identify the truly present phases from the candidates in very problematic sample. The Page Down key Allows you to display the next s-m table page. The Page Up key Allows you to display the previous s-m table page. The End key Allows you to display the last s-m table page. The Home key Allows you to display the first s-m table page. The symbol 175 \f "Symbol" \s 12 key Allows you to move to and select the next candidate phase. The symbol 173 \f "Symbol" \s 12 key Allows you to move to and select the previous candidate phase. The symbol 191 \f "Symbol" \s 12 (Enter) key Allows you to go to the matching graphical screen for visual inspection of the matching between the selected candidate and the sample. More matching measures are available in this screen. The values of ISF% and IEW can be adjusted. The graph can be zoomed and/or saved in HPGL format. The Ins key Allows you to insert (add) candidate phases to the s-m table. Ether by inputting their phaseID, or by commanding the program to search SDF and select the candidate phases based on the current S-M-I parameters. The Del key Allows you to delete a candidate phase from the s-m table. The F1 or I key Commands the program to automatically identify the most probably present phases. The F2 or Q key Commands the program to switch to the quantification procedure and quantify the found phases. The F3 or C key Allows you to display concluding matching plot. The F4 or R key Allows you to reject and restore data of one or all previously accepted (found) phases. The F5 or D key Allows you to sort the candidates in ascending order according to any of the matching table columns 2 to 8. Useful columns for this type of sorting are 2, 3, 6 or 8. The F6 or U key Allows you to sort the candidates in descending order according to any of the matching table columns 2 to 8. Useful columns for this type of sorting are 4, 5 or 7. The F7 or 1 key Allows you at any identification stage to match a particular candidate in the s-m table against the original sample data and displaying the results in the first line (1) of the white window near the bottom of the screen. Note that, after identifying one or more phases all the rematch operations are carried out against the remaining sample lines. The F8 or 2 key Allows you at any identification stage to match a particular candidate in the s-m table against the original sample data and displaying the results in the second line (2) of the white window near the bottom of the screen. The F7 and F8 functions are useful at the late stage of identification when you needs to know which of a particular two phases matches the original sample better. The F9 or G key Allows you at any identification stage to display the matching graphical screen (see step 10 below) which shows the detail matching results of a particular candidate in the matching table against the original sample data. The F10 or N key Allows you to rematch the candidates using their N intense lines. This is a useful function when you needs to compare the program matching results with the results of other search-match program, or with the results of hand search using search manual listing only N intense lines (usually N = 3, 5, 8 or 15) of the standard phases. The P key Allows you to display Screen4 and edit the program S-M-I parameters. By using F10 function you can rematch the candidates and see or explain the effects of the changed parameters on the matching results. So that you can tune the program to the problem, and also you can find the most suitable set of parameters for your type of samples. The S key Since pressing Esc key can interrupt the search, this function allows you to continue searching the remainder of the data base. Before you use continue search you should select up to seven phases (the program tries to select some good matched phases). So the program will keep their data and list them with the candidate phases found in the next search round. The Esc or E key Allows you to end phases examination and identification. 11- Press F4 or R key (to activate the restoring function) 12- Press A (to restore all found phases) $ If one has chose the Semi-Automatic Identification procedure with the same input, the program will bring him to this s-m screen with the same results. $ If one has chose the Manual Identification procedure with the same input, the program will bring him to this s-m screen but with an empty s-m table. So that, he can manually insert into the s-m table his choice of candidate phases by inputting SDF and the candidate phaseID. If the field of the candidate phaseID is left empty, the program will search the SDF and select the candidate phases based on the current S-M-I parameters. 13- Press F1 or I key To let the program automatically identifying the four certainly present phases and displaying a concluding matching plot. As you can see the matching is quit good. 14- Press F1 or 1 or T or Esc key To return back to the s-m screen. 15- Press F2 or Q key To let the program automatically quantifying the four found phases. 16- Press F1 or 1 or T or Esc key To return back to the s-m screen. 17- Press F4 or R key (to activate the restoring function) 18- Press A (to restore all found phases) 19- Press Del key To delete the top ranked phase in the s-m table, the Quartz PhaseID = 33-1161*. 20- Press Y key To confirms the deletion. The delete function is useful when you would like to delete some candidate phases you knew that they can not be exist in the sample. 21- Press Ins key To insert the quartz back into the s-m table. The insert function is useful when there are some phases you expect them to present in the sample, but they are not listed in the s-m table. That may be because some of them are not in the searched database, or can not pass the current S-M-I parameters. 22- Type 1 23- Type FARHAN.DB symbol 191 \f "Symbol" \s 12 (the SDF where the data of quartz is stored) 24- Type 33-1161 symbol 191 \f "Symbol" \s 12 The Quartz is matched and inserted in the s-m table. In the following we will proceed in identification as a user who would like to use his knowledge and notices to select the present phases. I.e. we will not relay on the program in the identification, but we will utilise some of the programs functions to help me selecting the truly present phases. 25- Select the top ranked candidate phase. 26- symbol 191 \f "Symbol" \s 12 (for graphical inspection of the match) Matching graphical screen is displayed which allows you to examine whether the selected candidate phase present in the sample or not. If not, You can return to the s-m screen and examine the next candidate. In the standard graph (top) line has lower height than the matched sample line is displayed as white line, line possess higher height than the matched sample line is displayed as green line and missing line is displayed as red line. Matched standard and sample lines having the same color (cyan) are equal in height within the IEW. 27- Press F4 or C key (for insightful graphical inspection of the match) Notice that, the intensity matching is not excellent. You can improve it by inputting a better ISF% (the grid lines, symbol 172 \f "Symbol" \s 12 and symbol 174 \f "Symbol" \s 12 keys, and the displayed proposed values of ISF% will helping you finding the best value). If variable intensity window option is active you can also adjust the IEW. The plot can be zoomed, standard intensities can be scaled, and the plot can be saved in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. 28- Press symbol 174 \f "Symbol" \s 10 key once. 29- symbol 191 \f "Symbol" \s 12 (the current ISF% will be displayed) 30- Type 100 symbol 191 \f "Symbol" \s 12 (to improve the intensity matching using the proposed value of ISF%) 31- symbol 191 \f "Symbol" \s 12 (to accept the program estimated IEW) Select one of the following options: (1) Accept and Subtract the standard lines from the sample lines. This option is provided for proper treatment of overlap lines. (2) Accept and Delete the matched sample lines. This option is used when you have good explanation for the intensity miss match and you do not like to have any residual lines after subtraction. (3) Ignore. 32- Press F1 or 1 or S key The program will Subtract the standard lines. Then rematch the candidate phases against the remaining sample lines. The s-m screen is displayed. The found phase is listed below the s-m table at the right of the screen. 33- symbol 191 \f "Symbol" \s 12 (to examine the top ranked phase) Matching graphical screen is displayed. 34- Press F1 or 1 or S key To Accept and Subtract the standard lines from the sample lines. 35- symbol 191 \f "Symbol" \s 12 (to examine the top ranked phase) Matching graphical screen is displayed. Since matching results does not suggest presence of overlap lines, one should choose Accept and Delete option (2). 36- Press F2 or 2 or D key The s-m screen is displayed. As can be seen in the first line, the number of remaining lines is 5 and they representing 3.51% of the total sample intensity (second line) i.e. they are lines of minor phases. 37- Press F3 or C key Concluding matching plot is displayed. It confirms that the 5 remaining lines representing minor phases (they are of very low intensity). 38- Press F1 or 1 or T or Esc key s-m screen is displayed. One of the techniques offered by the program to identify minor phases is sorting the candidate phases in ascending order of their mD-del (<symbol 68 \f "Symbol" \s 12d>) values. 39- symbol 191 \f "Symbol" \s 12 (to examine the top ranked phase) Matching graphical screen is displayed. Since matching results does not suggest presence of overlap lines, one should choose Accept and Delete option (2). 40- Press F2 or 2 or D key The s-m screen is displayed. 41- Press F3 or C key Concluding matching plot is displayed. It confirms that the identification is correct and almost complete. 42- Press F1 or 1 or T or Esc key s-m screen is displayed. At this point, and because there are two unassigned lines, if you knew or suspect that some specific phases may be exist in the sample, you can use the insert function (Ins key) to insert these phases into the s-m table. Then examine how good they match the unassigned lines. 43- Press Esc (to end phases examination and identification) Screen6 is displayed, which shows summery of the Identification and quantification results. 44- Press Esc key Concluding matching plot is displayed, for final conformation. 45- Press Esc key Identify procedure is finished and you returned back to Screen1. Since the matching is very good, as can be judge from the GMM and concluding matching plot, one usually ended the identification task at this point. But since we have some information about the sample. It seems possible to pursue the identification further. Identification based on one line will be dealt with under the next title. 2.2.4- Identification Example of very Minor phases By very minor phases, I mean the phases which are represented in the samples XRPD data by one or two lines. The definite identification of these phases can not be based on the XRPD data alone, especially in the case of one line. In these cases, any identification program can only give a list of possible phases. Based on the sample chemistry, physical properties, and its source, it is possible select the truly present phases from the list. This example will show how the program is very helpful in these cases. Now, we will concern our selves with how to find the best phases matching the two unassigned lines remained after the last identification. To make this task simple, the program automatically creates two files at the end of every identification session. For example, the two files for the sample which its MDF is TEST.DI are: TEST.UNA, which is contain the sample information and the unassigned lines. TEST.REM, which is contain the sample information and both the unassigned and residual lines i.e. the remaining lines. Also, supplied with the program a parameters file FARHAN.QUN which contains parameters suitable for such cases and can be read by pressing F4 key in the parameters screen4. This is an ASCII file which user can edit to establish his most satisfactory default parameters for one line identification and quantification. While you are at Screen1 1- Press 3 (to select Identification and Quantification task) 2- Press 2 (to select Sime-Automatic Identification and Quantification procedure) Screen3 is displayed. 3- TEST.UNA symbol 191 \f "Symbol" \s 12 (to input the MDF containing the unassigned two lines) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- symbol 191 \f "Symbol" \s 12 (to accept the displayed file FARHAN.DB. Or input another SDF) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) 8- Press F4 key This will let the program read the parameters file FARHAN.QUN which contains values suitable for identification and quantification based on one or two lines (this automatically done in the Demo version). The program default S-M-I parameters which will be re-tuned are the following five: 3-Highest Peaks (3hp) Treatment (0 To 3) : 1 Min. No. of Matched Lines : 1 d-Maximum : 1000 (so, all the phases in the SDF will be examine) Weights of Quant. and Qual. Int. Matching in the AG FOM : 0 1 Min. No. of Remaining Lines to Stop AUTO Identification : 0 It is some times important to reduce the value of Min. AG FOM for Candidate Phases parameter. If you would like to match only the standard most intense line, use Standard Intensity Background: 90. Although, the last change seems very logical, it is not recommended, because it will disable some rejection criterias. Accordingly, if you do not use the samples elemental information and very narrow d-window, depending on your data base, the number of candidates may be large. 9- Press Esc key To start Search-Match-Identification procedure using the current S-M-I parameters and without using the sample elemental information. As you can see, Chalcopyrite is listed at the top of the most possible phases and Gold is third (if one used the JCPDS-ICDD Minerals subfile, will end with almost the same results, concerning Chalcopyrite and Gold which are the correct phases) 10- symbol 191 \f "Symbol" \s 12 (for graphical inspection of the top ranked phase) 11- Press F4 or C key (for insightful graphical inspection of the match) As you can see the most intense Chalcopyrite lines (3hp=100) is matching the sample line at 29.3839 (2theta). 12- symbol 191 \f "Symbol" \s 12 (the current ISF% will be displayed) 13- symbol 191 \f "Symbol" \s 12 (to accept the program estimated ISF%) 14- symbol 191 \f "Symbol" \s 12 (to accept the program estimated IEW) 15- Press F1 or 1 or T or Esc key To return back to the s-m screen. In the same way, examination of the second phase will shows that, this phase is matching the same line 29.3839 (2theta) with less probability comparing to the Chalcopyrite. So that it can be excluded. Examination of the third phase (Gold) will reveals that, it is matching the other line which is at 38.2834 (2theta). 16- Press F1 or I key To let the program automatically identify the most probable phases according to its philosophy. As you can see the program has selected what expert analyst will select. 17- Press F1 or 1 or T or Esc key To return back to the s-m screen. 18- Press Esc (to end phases examination and identification) Screen6 is displayed, which shows summery of the Identification and quantification results. 19- Press Esc key Concluding matching plot is displayed, for final conformation. 20- Press Esc key Identify procedure is finished and you return back to Screen1. 3.4- Identification and Quantification Examples The use of the identification procedure in general case has been given in the previous examples. So, here we will concern our selves mainly with obtaining and presenting the quantitative results. 1.3.4- Multiphase Quantification Example using multiline Q16-3-1.DI file will be used. So, please see page 4 for samples details. While you are at Screen1 1 1- Press 3 (to select Identification and Quantification task) 2- Press 3 (to select Fully-Automatic Identification procedure) Screen3 is displayed. 3- Type Q16-3-1.DI symbol 191 \f "Symbol" \s 12 (to input the MDF) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- symbol 191 \f "Symbol" \s 12 (to accept the displayed file. Or input another SDF) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) Pressing F1 key restore the field original entry. While pressing F2 key at any field restore the original Sample Major Element. 8- Press Esc key To start Search-Match-Identification-Quantification procedure using the program default parameters and without using the sample elemental information. The Esc key allows you to interrupt the search-match. Screen7 is displayed. As you can see, the program found the correct phases and quantify them using the Adiabatic principle method. Searching the whole JCPDS-ICDD minerals file of 4091 undeleted phases (sets 1-45) takes about 7 seconds on IBM compatible PC equipped with Pentium 150 processor. And it takes about 6 seconds to search the whole hlzel file of minerals. The screen contains a complete short report of the identification and quantification results. Which can be sent to the printer by pressing the Print Screen key. The values of the RIR can be edited. If any of them has been changed, F2 key have to be pressed, so the program can use the new values to calculate the phases weight percent concentration using the Adiabatic principle method. Pressing F5 key takes you to the s-m screen. The quantitative results of the found phases in the flushed sample are displayed: SN PhaseID Formula and Name found wt% known wt% symbol 68 \f "Symbol" \s 12 1 Q3-1-1 ZnO / Zincite 39.87 40.00 -.13 2 Q12-1-1 Al2O3 / Corundum 19.99 20.00 -.01 3 Q6-1-1 CaF2 / Fluorite 40.14 40.00 +.14 9- Press Esc key Full qualitative and quantitative report is sent to Q16-3-1.OUT file. Concluding matching plot is displayed. So, the goodness of matches can be graphically estimated in a collective manner. Each line in the simulated (middle) graph has the same color of its phaseID which is shown at the bottom of the screen. The top graph show the positions and intensities of the remaining lines (7 lines), one of them (violet) is unassigned (unmatched) lines and the other six (yellow) are residual lines (i.e. remain after subtracting the lines in the middle graph from the corresponding lines in the bottom graph). The graphs can be zoomed and/or saved in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. Pressing F1 or 1 or T key takes you to the s-m screen. Where pressing Esc key finishing the Fully-Automatic Identification procedure and returns you back to Screen1. 10- Press Esc key (to finish the task and returns back to Screen1) 2.3.4- Multiphase Quantification Example using multiline of sample containing amorphous phase Q17-4-1.DI file will be used. So, please see page 4 for samples details. While you are at Screen1 2 1- Press 3 (to select Identification and Quantification task) 2- Press 3 (to select Fully-Automatic Identification procedure) Screen3 is displayed. 3- Type Q17-4-1.DI symbol 191 \f "Symbol" \s 12 (to input the MDF) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- Type CHUNG74.DB symbol 191 \f "Symbol" \s 12 (to input SDF. It is automatically selected in the Demo version) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) Pressing F1 key restore the field original entry. While pressing F2 key at any field restore the original Sample Major Element. 8- Press Esc key To start Search-Match-Identification-Quantification procedure using the program default parameters and without using the sample elemental information. The Esc key allows you to interrupt the search-match. Screen7 is displayed. As you can see, the program found the correct phases and quantify them using the Adiabatic Principle method. But, the wt% of the internal standard is more than 10% of its true value. This, with the displayed general matching measures (complete and successful identification of crystalline phases) are indicating the presence of amorphous phase. To obtain correct quantification results, the matrix-flushing method (using either F3 or F4 key) should be used. 9- Press F3 key (to initiate the matrix-flushing routine to calculate the phases wt% in the flushed sample) 10- symbol 191 \f "Symbol" \s 12 (to accept the program automatic selection of the internal standard) 11- Type 30 symbol 191 \f "Symbol" \s 12 (the wt% of the internal standard) The quantitative results of the found phases and the amorphous in the flushed sample are displayed: SN PhaseID Formula and Name found wt% known wt% symbol 68 \f "Symbol" \s 12 1 Q3-1-1 ZnO / Zincite 14.78 15.00 -.22 2 Q12-1-1 Al2O3 / Corundum 30.00 30.00 0.00 3 Q6-1-1 CaF2 / Fluorite 35.27 35.00 +.27 amorphous material 19.95 20.00 -.05 If one used the Minerals file of JCPDS-ICDD, the quantitative results of the found phases and the amorphous in the flushed sample will be: SN PhaseID Formula and Name found wt% known wt% symbol 68 \f "Symbol" \s 12 1 36-1451* ZnO / Zincite 15.22 15.00 +.22 2 10-0173I Al2O3 / Corundum 30.00 30.00 0.00 3 35-0816* CaF2 / Fluorite 35.53 35.00 +.53 amorphous material 19.25 20.00 -.75 12- Press F4 key (to initiate the matrix-flushing routine to calculate the phases wt% in the original sample) 13- symbol 191 \f "Symbol" \s 12 (to accept the program automatic selection of the internal standard) 14- symbol 191 \f "Symbol" \s 12 (to accept the displayed wt% of the internal standard) The quantitative results of the found phases and the amorphous in the original sample are displayed: SN PhaseID Formula and Name found wt% known wt% symbol 68 \f "Symbol" \s 12 1 Q3-1-1 ZnO / Zincite 21.11 21.43 -.32 2 Q12-1-1 Al2O3 / Corundum 00.00 00.00 0.00 3 Q6-1-1 CaF2 / Fluorite 50.39 50.00 +.39 amorphous material 28.50 28.57 -.07 15- Press Esc key Full qualitative and quantitative report is sent to Q17-4-1.OUT file. Concluding matching plot is displayed. So, the goodness of matches can be graphically estimated in a collective manner. Each line in the simulated (middle) graph has the same color of its phaseID which is shown at the bottom of the screen. The top graph show the positions and intensities of the remaining lines (6 lines), none of them (violet) is unassigned (unmatched) lines, so the six (yellow) are residual lines (i.e. remain after subtracting the lines in the middle graph from the corresponding lines in the bottom graph). The graphs can be zoomed and/or saved in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. Pressing F1 or 1 or T key displays the s-m screen. 16- Press Esc key (to finish the task and returns back to Screen1) 3.3.4- Multiphase Quantification Example using one line SAMPLE1.DI file will be used. So, please see page 4 for samples details. While you are at Screen1 1- Press 3 (to select Identification and Quantification task) 2- Press 3 (to select Fully-Automatic Identification and Quantification procedure) Screen3 is displayed. 3- SAMPLE1.DI symbol 191 \f "Symbol" \s 12 (to input the MDF) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- Type CHUNG74.DB symbol 191 \f "Symbol" \s 12 (to input the SDF. It is automatically selected in the Demo version) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) 8- Press F4 key This will let the program reads the parameters file FARHAN.QUN which contains values suitable for identification and quantification based on one or two lines (this automatically done in the Demo version). The program default S-M-I parameters which will be re-tuned are the following five: 3-Highest Peaks (3hp) Treatment (0 To 3) : 1 Min. No. of Matched Lines : 1 d-Maximum : 1000 (so, all the phases in the SDF will be examine) Weights of Quant. and Qual. Int. Matching in the AG FOM : 0 1 Min. No. of Remaining Lines to Stop AUTO Identification : 0 It is some times important to reduce the value of Min. AG FOM for Candidate Phases parameter. If you would like to match only the standard most intense line, then use Standard Intensity Background: 90. Although, the last change seems very logical, it is not recommended, because it will disable some rejection criterias. Accordingly, if you do not use the samples elemental information and very narrow d-window, depending on your data base, the number of candidates may be large. 9- Press Esc key To start Search-Match-Identification-Quantification procedure using the current S-M-I parameters and without using the sample elemental information. As you can see, the program found the correct phases and quantify them using the Adiabatic principle method. The results are in agreement with the published values. 10- Press Esc key Full qualitative and quantitative report is sent to SAMPLE1.OUT file. Concluding matching plot is displayed. So, the goodness of matches can be graphically estimated in a collective manner. Each line in the simulated (middle) graph has the same color of its phaseID which is shown at the bottom of the screen. The graphs can be zoomed and/or saved in a file in HPGL format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. Pressing F1 or 1 or T key displays the s-m screen. 11- Press Esc key (to finish the task and returns back to Screen1) 4.3.4- Multiphase Quantification Example using one line of sample containing amorphous SAMPLE5.DI file will be used. So, please see page 6 for samples details. While you are at Screen1 1- Press 3 (to select Identification and Quantification task) 2- Press 3 (to select Fully-Automatic Identification and Quantification procedure) Screen3 is displayed. 3- SAMPLE5.DI symbol 191 \f "Symbol" \s 12 (to input the MDF) 4- symbol 191 \f "Symbol" \s 12 (to accept the default option (o). The sample is old, so its data is saved in a file) 5- Type CHUNG74.DB symbol 191 \f "Symbol" \s 12 (to input the SDF. It is automatically selected in the Demo version) Screen4 is displayed. 6- symbol 191 \f "Symbol" \s 12 or press Tab or symbol 175 \f "Symbol" \s 12 key (to move to Sample Major Element field) 7- Press space bar key (to delete the elements) 8- Press F4 key This will let the program read the parameters file FARHAN.QUN which contains values suitable for identification and quantification based on one or two lines (this automatically done in the Demo version). The program default S-M-I parameters which will be re-tuned are the following five: 3-Highest Peaks (3hp) Treatment (0 To 3) : 1 Min. No. of Matched Lines : 1 d-Maximum : 1000 (so, all the phases in the SDF will be examine) Weights of Quant. and Qual. Int. Matching in the AG FOM : 0 1 Min. No. of Remaining Lines to Stop AUTO Identification: 0 It is some times important to reduce the value of Min. AG FOM for Candidate Phases parameter. If you would like to match only the standard most intense line, then use Standard Intensity Background: 90. Although, the last change seems very logical, it is not recommended, because it will disable some rejection criterias. Accordingly, if you do not use the samples elemental information and very narrow d-window, depending on your data base, the number of candidates may be large. 9- Press Esc key As you can see, the program found the correct phases and quantify them using the Adiabatic principle method. But, the wt% of the internal standard is more than 10% of its true value. This, with the displayed general matching measures (complete and successful identification of crystalline phases) are indicating the presence of amorphous phase. To obtain correct quantification results, the matrix-flushing method (using either F3 or F4 key) should be used. 10- Press F3 key (to initiate the matrix-flushing routine to calculate the phases wt% in the flushed sample) 11- symbol 191 \f "Symbol" \s 12 (to accept the program automatic selection of the internal standard) 12- Type 21.44 (the wt% of the internal standard) The quantitative results of the found phases and the amorphous in the flushed sample are displayed. The results are in agreement with the published values. 13- Press Esc key Full qualitative and quantitative report is sent to SAMPLE5.OUT file. Concluding matching plot is displayed. So, the goodness of matches can be graphically estimated in a collective manner. Each line in the simulated (middle) graph has the same color of its phase ID which is shown at the bottom of the screen. The graphs can be zoomed and/or saved in HPLG format. So that, hard copy can be plotted by HP plotter or compatible one. The HPGL file can be read by shareware programs (such as PRINTGLD program) which are converting the HPGL format to a wide variety of printer and plotter format. Pressing F1 or 1 or T key displays the s-m screen. 14- Press Esc key (to finish the task and returns back to Screen1) 5.3.4- General Comments on Quantification: The default programs quantification routine (APR), which is based on the adiabatic principle method, Chung (1974b), does not needs internal standard to be added to the sample, is usually capable to give good quantitative results. However when ever it is practical, addition of internal standard is recommended, because it allow: 1) Checking over the accuracy of the quantitative results. 2) Obtaining quantitative results when the identification is not complete. 3) Checking the presence and quantifying the amorphous material. 4) In the worse, it may be needed to correct the line positions of the XRPD pattern. Although any pure, stable, having fine particles and can homogeneously mixed with the sample can be used as internal standard. It is by far better to use Al2O3 (Corundum) of fine particles (r<10 symbol 109 \f "Symbol" \s 12m). The accuracy desired in quantitative analysis is dependent on the sample preparation and on the intensity measurement and the data treatment implied. Although, the examples we have used in this manual showed that peak height gave satisfactory quantitative results, the peak intensity definitely gave better results. One of the merit of RIR quantitative method is that, one can use the published measured or calculated RIR. However, for more accurate results one should determine the RIRs using his set of experimental conditions. This can be done by accurately measuring the intensities (or the peak heights) of the most intense lines Isymbol 98 \f "Symbol" \s 12 and Isymbol 97 \f "Symbol" \s 12 of the standard symbol 98 \f "Symbol" \s 12 and the phase symbol 97 \f "Symbol" \s 12 respectively in a 50:50 wt% mixture. Then, the RIRsymbol 97 \f "Symbol" \s 12,symbol 98 \f "Symbol" \s 12 = Isymbol 97 \f "Symbol" \s 12/ Isymbol 98 \f "Symbol" \s 12 . If corundum is used as standard, then the determined RIRsymbol 97 \f "Symbol" \s 12,symbol 98 \f "Symbol" \s 12 is the I/Ic . Although, using multiple peaks in phase quantification is preferable, still there are many diffractionist whom using one line. This is because, it is more economical to measure accurately the intensity of a few peaks than scanning the whole pattern. But, if some lines are overlapped, quantification of the overlapped phases is not possible. For this reason, it is advisable to build your data base using two or more lines. However, for those whom would like to use one line for quantification, the parameters file (FARHAN.QUN) is suitable for this type of analysis and it can be read by pressing F4 key in the parameters screen4. In this case the data base is very simple. It contains the phase information and the d and I of one diffraction line, this usually the most intense one. The I value of this line is equal to 100 and its d value can be take from literatures or as usually obtained during the course of determining the RIR. For testing the quantification based on one line, we include with the program two example files (SAMPLE1.DI and SAMPLE5.DI) and the corresponding data base (CHUNG74.DB). These data were taken from Chung (1974a) paper (note, the intensities are normalised). By default, the programs quantification routines are using multiple lines. However, one can based his quantification on one selected line. This is usually but not necessarily, the most intense line of the phase. The selection is possible in matching graphical screen using scale option. This usually needed when the most intense line which is not overlapped nor bias is not included in the quantification calculation, that when its colour is either white or green in the matching graphical screen. Chapter Five 1.5- Search-Match-Identification (S-M-I) parameters Two general ASCII parameters files can be read by the program. These are: 1- FARHAN.PAR 2- FARHAN.QUN FARHAN.PAR file is automatically reads by the program. So it should contains the default S-M-I parameters. The parameters, which affect who the program will reads the sample or standard data or who the program, will performs the Search-Match or the identification task, can be edited within the program in the parameter screen4. The parameters shipped with the program are found suitable for wide type of problems, but they can not be considered universal. So if the user found him self always need to change a parameter or certain parameters to specific values. He should consider permanently changing these parameters by changing their values in FARHAN.PAR, using any ASCII (Text) editor program. So that he will not need to edit these parameters within the program. For example if one usually use the Minerals file of the ICDD, which he call it MINERALS.DB, to identify the phases in his samples. Then, he should edit the Standards Data File : FARHAN.DB (the last line in the file) by replacing the FARHAN.DB with MINERALS.DB. FARHAN.QUN file contains parameters suitable for phases identification and/or quantification using one line (or few lines). The program can read this file upon pressing F4 key in the parameters screen4. Again the user can customize the parameters in this file. FARHAN.PAR file formats and default parameters: 3-Highest Peaks (3hp) Treatment (0 To 3) : 3 d-Error Window : .025 Min. Intensity for Missing Line : 10 Min. (Matched/Observed) Lines % : 70 Min. No. of Matched Lines : 3 Weight of d Matching in the AG FOM : .975 Weights of Quant. and Qual. Int. Matching in the AG FOM : 1 1 Weights of Matched and Missing lines in the AG FOM : 1 1 Min. AG FOM for Candidate Phases : 2 Max. No. of Uesd Best Candidate Phases : 70 Min. No. of Remaining Lines to Stop AUTO Identification : 2 Intensity-Error-Window = (0) Varible (1) Fixed Weighted : 0 Fixed Intensity-Error-Window : 10 d-Minimum : 0 d-Maximum : 1000 Sample Intensity Background : .5 Standard Intensity Background : .5 No. of Plotter Pens : 8 Maximum Number of Reflection Lines : 180 Program Memory Control Parameter : 650 Standards Data File : FARHAN.DB 2.5- ASCII Peaks file which can be read by the program All modern X-ray powder diffractometers are provided with peaks finder program. At the present, FARHAN can read the ASCII peak files produced by: 1- Siemens D5000-Diffract/At V1.0. 2- Pillips-Wp 3710. 3- Any file has the similar format to the abov. For example, the ASCII peaks file produced by Siemens D5000-Diffract/At V1.0 has .DIF extension and format similar to that given below, can be read directly by the program as sample file. The .DIF file extension directs the program to read the file which expected to has the below format, and then the program saves the data in MDF with the same file name and .DI extension. DIFFRAC / AT -- PRINTDIF V1.0 *** 10-Nov-1996 13:40:22 Dump of file: C:\USERDATA\Q16-3-1.DIF (10-Nov-1996 12:53:42) Sample name : Q16-3-1 (01-Nov-1996 11:49:38) D5MEAS - Program:S.DQL Wavelength 1: 1.54056 Wavelength 2: 1.54439 Range # 1 Raw data measured from 2 theta = 5.000 to 75.000 Step size : 0.020 Time/step : 1.0 Peak width: 1.000 Threshold : 1.0 -N- 2 theta ---d--- ---Cps--- ---%--- 4 25.562 3.4819 57.52 5.28 1 28.264 3.1548 200.56 18.39 13 31.740 2.8168 692.22 63.49 2 32.618 2.7430 25.67 2.35 5 34.401 2.6048 544.93 49.98 6 35.120 2.5531 110.37 10.12 7 36.239 2.4768 1090.35 100.00 8 37.741 2.3816 44.42 4.07 9 43.319 2.0870 110.17 10.10 10 47.000 1.9317 197.91 18.15 11 47.518 1.9119 268.03 24.58 12 52.520 1.7410 47.69 4.37 3 55.744 1.6477 52.75 4.84 14 56.580 1.6253 330.85 30.34 15 57.480 1.6020 103.75 9.52 16 62.840 1.4776 290.23 26.62 18 66.340 1.4079 48.46 4.44 17 66.500 1.4049 52.12 4.78 19 67.940 1.3786 233.25 21.39 20 69.080 1.3586 114.24 10.48 21 72.560 1.3017 25.86 2.37 The program read these data regardless on which column they have been sorted. Also, the program can read ASCII peaks file with .TTI extension. The format of this file should be similar to the MDF with .DI extension (see section 4.1) except that the diffraction line is represented by its 2symbol 113 \f "Symbol" \s 12 and I. Usually, any ASCII peaks file can easily converted to either of .DI or .TTI file format using any text editor program. However, the academic or profit-making user can send the ASCII peaks file produced by their diffractometer to the author. Then, they will be provided with a new copy of the program which can directly read their diffractometer peaks file. Please, send the ASCII peaks file on 3.5 inch disk and specify the diffractometer type, its software name and the software version. Application Form for FARHAN A Qualitative and Quantitative PC program for X-ray powder diffraction Please tick the appropriate option: [ ] Please add my name to your mailing list for updates. I am interested in phases identification and quantification of [ ] Minerals. [ ] Metals and Alloys. [ ] Inorganic. [ ] Organic. I am going to use the program for [ ] education. [ ] academic researches. [ ] profit-making. My details: Name, title: Address: Fax : e-mail: Signature: Date : / / . Please Note: 1- The program will be provided on the understanding that, the author is not responsible about any damage result from the use of the program. 2- The copy of the program provided with this form should only be used on one computer at any given time by the registered user or his/her student. 3- Your copy serial number: ____________________________________________________________________ Send the form to: Dr. Khalid A. AL-Farhan Chemistry department College of Science King Saud University Riyadh 11451, P.O. Box 2455 Saudi Arabia. Fax: + (9661) 4683815 page 21 vx}.A+-)W7X=O~{wokc_D D D D D D D D $8D #~&QRnpCUBJfgi !mo{wokc_D D @ D D D D D $ '!(!D!F!J!K!g!i!!! 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