20-SEP-2005 Documentation for program BREADTH Copyright notice: This program is copyrighted by Davor Balzar (www.du.

edu/~balzar,
balzar@du.edu). It is free for noncommercial use, provided that the reference is made to the following publication: D. Balzar and H. Ledbetter, J. Appl. Cryst. 26 (1993) 97-103. For all other (commercial) use of the program or the method, a prior written permission from the author has to be obtained. Introduction The program calculates domain size and microstrain from input integral breadths of at least two 'pure' physically (specimen, structurally) broadened diffraction-line profiles. Beyond the classic so-called simplified integral-breadth methods (summarized in [1]), program calculates the root-mean-square strain (RMSS) and both area- and volume-weighted domain sizes according to the 'double-Voigt' method [2], which is equivalent to the Warren-Averbach approach. This method is treated more thoroughly in [3-6] and its application in [6-9]. Here are given basic formulas and the format of input and output files. All are ASCII text files read and written by formatted I/O. Calculations If the distortion coefficient is approximated by a harmonic term, the size and distortion integral breadths of Lorentz (Cauchy) (SC and DC) and Gauss (SG and DG) parts conform to relations [2]:

s 2 s0 2 2 2 2 G = SG + DG s 2 s0

C = SC + DC

(1) (2)

Here, s02 is taken for the first peak. To determine unknowns SC, DC, SG, and DG, data for at least two reflections must be available. If data for more than two peaks are present, unknowns are calculated by means of the linear least-squares fit. Area- and volume-weighted domain sizes follow directly:
< D >s = 1 2 SC ; < D >v = exp(k 2)

SG

erfc(k)

(3)

where k = SC/(1/2SG), the characteristic integral-breadth ratio of a Voigt function. Furthermore, the MSS is a function of the averaging distance L:
2 1 DG DC 1 < (L) > = 2 + 2 . s0 2 L 2

(4)

Comments - If input data are given by pseudo-Voigt or Pearson-VII functions, the FWHM and (m) parameters are transformed to C and G of the corresponding Voigt function according to the approximations given in [10-12]. Some of the algorithms give the exaggerated errors especially of G at the Lorentzian limit. - Unless data for only two peaks are present or at least one error of C and G is equal to zero, fit is weighted by the reciprocal of the variance. This regards the determination of 'doubleVoigt' parameters only. The fit for the evaluation of parameters from the simplified integralbreadth methods is not weighted at any circumstances, because of its low accuracy. - The minimum value of integral breadth or its error is set to 10-5 2 degrees. - The CuK1 wavelength (1.5405981 ) is assumed for all calculations unless a different wavelength is defined on line 2. - Warren [13] defined the parameter a3' (edge of orthorhombic cell, orthogonal to diffracting planes) to include all observable variation in the peak intensity. Program takes the smallest a3' of all peaks present. - Tails of the Voigt function (synthesized from the input Lorentz and Gauss integral breadths) are arbitrarily cut off at the 0.1% of the maximum peak intensity. - Up to the 1000 Fourier coefficients of the physically broadened line profile are generated. The behavior of the size coefficients is monitored by their first derivative. If it changes the sign (physically illogical because the column-length distribution function shouldn't be negative), all the coefficients are cut off at that harmonic number and the appropriate warning is issued. Also, all the subsequent coefficients are cut off prematurely, but without warning, if the size coefficients fall below value of about 10-30, in order to avoid the stack underflow with some FORTRAN compilers. This is to be expected for relatively small domain sizes and/or narrow size distributions, because all the coefficients approach zero for L 6 4. - Should K_SIZE (see Eq. 4) and R_SIZE (see Eq. 5) fall out of regular limits, the "hook" effect will occur. Then, domain sizes obtained by application of Eqs. 2 will differ from values obtained by numerical integration of corresponding column-length distribution functions, because all negative values of column-length distribution function are set to zero. In this case, both area-weighted (D(ARE) DF) and volume-weighted (D(VOL) DF) domain sizes are calculated from the corresponding distribution functions, too. Note that the strains averaged over (D(ARE) DF)/2 and (D(VOL) DF)/2 can be estimated from the table of 50 RMSS generated at the end of BREADTH.OUT. Input file Line Format 1 (A80) 2 3

4,5,..

Description TITLE Any 80 characters characterizing the specimen. (F12.6) WAVELENGTH in . It can be omitted, in which case it defaults to the CuK1 wavelength (1.5405981 ). (I2) IFUNCTION Characterizes the fitting function used: 1 - Voigt, 2 - pseudo-Voigt, 3 - Pearson VII (3I2,2X,F8.4,5X,4F8.5) At least 2 lines of line-profile data (in the order of increasing 2) as follows: 3I2 hkl Miller indices

F8.4 4F8.5

Position of the peak maximum in 2 degrees Two pairs of the fitting parameters with the associated errors, depending on the value of IFUNCTION: 1 - Voigt function (i) Lorentz (Cauchy) component of the Voigt function and its estimated standard deviation. (ii) Gauss component of the Voigt function and its estimated standard deviation (all in 2 degrees). 2 - pseudo-Voigt function (i) Full width at the half maximum (FWHM) in 2 degrees and its estimated standard deviation. (ii) The mixing parameter in the range 0 (Gauss) to 1 (Lorentz) and its estimated standard deviation. 3 - Pearson-VII function (i) Full width at the half maximum (FWHM) in 2 degrees and its estimated standard deviation. (ii) The shape factor (exponent) m in the range 1 (Lorentz) to 30 (approximates to Gauss limit) and its estimated standard deviation.

Output files File BREADTH.OUT Symbol 2T MAX 2T BEG 2T END s BETA_L BETA_G BETA

a3 (A) N(CUT) K_SIZE R_SIZE SIZE LORENTZ, SIZE GAUSS, Size and distortion integral breadth in -1 determined from STRAIN LORENTZ, the Equations (1) and (2) STRAIN GAUSS D(ARE) Area-weighted domain size in * D(ARE) DF Area-weighted domain size in , calculated as a mean of the areaweighted column-length distribution function D(VOL) Volume-weighted domain size in * D(VOL) DF Volume-weighted domain size in , calculated as a mean of the volume-weighted column-length distribution function EPS(Ds/2) RMSS averaged over the distance D(ARE)/2 EPS(Dv/2) RMSS averaged over the distance D(VOL)/2 _________________________________________________ * Optional parameter; its appearance depends on some preset condition.

Description Position of the peak maximum from the input list Peak cutoff at low angle (0.1% of the maximum intensity) Peak cutoff at high angle (0.1% of the maximum intensity) =2sin/=1/d, variable in reciprocal space Lorentz integral breadth of the Voigt function Gauss integral breadth of the Voigt function Integral breadth of the Voigt function computed from the BETA_L and BETA_G Parameter a3' in The last harmonic number of the Fourier coefficients used Characteristic integral-breadth ratio of a Voigt function Ratio of volume- to area-weighted domain size

EPS(a3) EPS(GAUSS) D (A) EPS N L (A) AS AD EPS(L)

RMSS averaged over the distance a3 RMSS averaged over the infinite distance (Gaussian limit) Volume-averaged domain size in from the simplified integral-breadth methods Upper limit of strain from the simplified integral-breadth methods Harmonic number =N*a3, column length (averaging distance in real space) in Size coefficients Distortion coefficients RMSS averaged over the distance L

Warnings Program may print the following warnings: - NEGATIVE OR IMAGINARY INTEGRAL BREADTHS SET TO ZERO !! CHECK SIZE & STRAIN / LORENTZ & GAUSS INTEGRAL BREADTHS Some of SC, DC, SG, and/or DG are found to be negative or imaginary, which is physically illogical. They are set to zero in the subsequent calculations. - SIZE PARAMETERS IRREGULAR !! CHECK K_SIZE & R_SIZE Characteristic integral-breadth ratio of the size-broadened Voigt profile k is required to change in range
1/ 2 k < .

(5)

This condition gives a lower and upper limit for the ratio of volume- to area- weighted domain size

1.31 2 e erfc(1/ 2) D(VOL) /D(ARE) < 2 .

(6)

If K_SIZE and R_SIZE are found to be out of these intervals, a warning is issued. - SIZE COEFFICIENTS OSCILLATE !! CHECK N(CUT) Normally, 1000 Fourier coefficients are generated. If the first derivative of size coefficients changes the sign, all the coefficients are cut off after N(CUT). - PHI LESS THAN THE LORENTZ LIMIT SET TO 2/PI and PHI GREATER THAN THE GAUSS LIMIT SET TO 2 SQRT(LN(2)/PI) The ratio FWHM/ of the Voigt function must fall between the Lorentz and Gauss limits:

2/ 2 ln 2 / .
These warnings are in effect only if input data are given with either pseudo-Voigt or Pearson-VII functions.

File AS.DAT AS is a function of L in the first column. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 AS File AD.DAT AD is a function of L in the first column. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 AD File EPS.DAT EPS(L) is a function of L in the first column. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 EPS(L) File EPSSQ.DAT EPS(L)^2 is a function of L in the first column. It may be used for plotting <2(L)> as a function of 1/L. Column Format Description 1 1X,F10.5 1000/L (A) 2 1X,F10.4 EPS(L)^2 @ 106 File DISFUNS.DAT PS is a function of L in the first column. It is normalized on unit area. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 PS Area-weighted column-length distribution function File DISFUNV.DAT PV is a function of L in the first column. It is normalized on unit area. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 PV Volume-weighted column-length distribution function File BREADTH.DAT AS, AD, PS, PV are all functions of L in the first column. Column Format Description 1 1X,F8.2 L (A) 2 1X,F10.7 AS 3 1X,F10.7 AD 4 1X,F10.7 PS 5 1X,F10.7 PV ________________________________________________________

References:
1. H. P. Klug and L. E. Alexander, X-ray Diffraction Procedures, 2nd edition (John Wiley, New York, 1974). 2. D. Balzar and H. Ledbetter, J. Appl. Cryst. 26 (1993) 97-103. 3. D. Balzar, Voigt-Function Model in Diffraction Line-Broadening Analysis, in Defect and Microstructure Analysis by Diffraction, edited by R.L. Snyder, H.J. Bunge, and J. Fiala, International Union of Crystallography Monographs on Crystallography No. 10 (Oxford University Press, New York, 1999) pp. 94-126. 4. D. Balzar, H. Ledbetter, Accurate Modeling of Size and Strain Broadening in the Rietveld Refinement: the "Double-Voigt" Approach, Advances in X-ray Analysis 38 (1995) 397-404. 5. D. Balzar, BREADTH -- a Program for Analyzing Diffraction Line Broadening, Journal of Applied Crystallography 28 (1995) 244-245. 6. D. Balzar, J. Res. Natl. Inst. Stand. Technol. 98 (1993) 321-353. 7. D. Balzar, J. Appl. Cryst. 25 (1992) 559-570. 8. D. Balzar and H. Ledbetter, J. Mater. Sci. Lett. 11 (1992) 1419-1420. 9. D. Balzar, H. Ledbetter, and A. Roshko, Pow. Diffr. 8 (1993) 2-6. 10. J. I. Langford, Accuracy in Powder Diffraction II, NIST Special Publication 846 (U.S. Government Printing Office, Washington, D.C., 1992) p. 110-126. 11. Th. H. de Keijser, J. I. Langford, E. J. Mittemeijer, and A. B. P. Vogels, J. Appl. Cryst. 15 (1982) 308-314. 12. Th. H. de Keijser, E. J. Mittemeijer, and H. C. F. Rozendaal, J. Appl. Cryst. 16 (1983) 309-316. 13. B. E. Warren, X-ray Diffraction (Addison Wesley, Reading, MA, 1969).