Caglioti U V W parameters
Dear All, i am a little bit confused about the magnitudes of the U V W profile parameters of the caglioti function for instrumental broadening. Is it true, that U and W are always positiv (larger 0) and V is always smaller 0 (negativ)? Thanks for your hints and explanations. Best Regards, Stefan
Re: Caglioti U V W parameters
Stefan, Not really. You should care about full width at half maximum - that should not be negative in any case. As follows, negative W does not have much sense. Negative U is also suspicious because it means that at higher angles your peak width may stop increasing with the 2Theta increase, which is rarely the case. V, however, certainly can be positive. But only their combination (resulting FWHM) has a meaning, not individual parameters. with best regards, Yaroslav At 11:17 AM 6/25/2007, you wrote: Dear All, i am a little bit confused about the magnitudes of the U V W profile parameters of the caglioti function for instrumental broadening. Is it true, that U and W are always positiv (larger 0) and V is always smaller 0 (negativ)? Thanks for your hints and explanations. Best Regards, Stefan
RE: Caglioti U V W parameters
Dear Stefan ( all, I suppose), From the original formulation by Caglioti, et al. U0, V0 W0 for a nonfocusing neutron CW instrument and describes a parabolic curve with the minimum at roughly the 2-theta angle that matches the monochromator take-off (really 2-theta) angle. For a Bragg-Brentano powder diffractometer the curve is usually quite flat yielding very much smaller FWHM especially for the low angle portion rising only at high angles. I suppose the minimum is about the 2-theta for the analyser crystal. Thus, U, V W are usually quite small but the relationship of U0, W0 V0 still holds. They can be a bit hard to determine unless a very high quality pattern is used for the calibration. The expression using U, V W yields (FWHM)^2 so it REALLY can't ever have a negative result as Yaroslav noted in his message. Rietveld refinement codes will protect against the possibility of a negative square root in various ways (if not they can crash on a negative sqrt error). Bob Von Dreele R.B. Von Dreele IPNS Division Argonne National Laboratory Argonne, IL 60439-4814 -Original Message- From: Stefan Berger [mailto:[EMAIL PROTECTED] Sent: Monday, June 25, 2007 11:18 AM To: rietveld_l@ill.fr Subject: Caglioti U V W parameters Dear All, i am a little bit confused about the magnitudes of the U V W profile parameters of the caglioti function for instrumental broadening. Is it true, that U and W are always positiv (larger 0) and V is always smaller 0 (negativ)? Thanks for your hints and explanations. Best Regards, Stefan
AW: RE: Caglioti U V W parameters
Dear Yaroslav, Dear Bob and all, thanks for your hints. I don't have some difficulties with negative FWHM^2. I try to refine a pattern of LaB6 reference material with GSAS. Data were obtained with a Siemens D5000 diffractometer. So after refining background, zero, Lx, Ly and lattice dimensions i try to refine GU, GV and GW simultaneously (Lx, Ly, background, lattice dimensions and zero are flagged for refinement too). Starting values are GU=2, GV=-2, GW=5. After refining the plot looks better and CHI^2 is better too (nearly 1.6). THe FWHM^2 calculated by widplot is around 0.06°. GU and GW are positiv but the GV parameter is now positiv too (between 2 and 4). Is this trustable or should i change something in my refinement procedure (may be unflag Lx and Ly...)? Thanks in advance, Stefan -Ursprüngliche Nachricht- Von: Von Dreele, Robert B. [mailto:[EMAIL PROTECTED] Gesendet: Mo 6/25/2007 19:27 An: rietveld_l@ill.fr Betreff: RE: Caglioti U V W parameters Dear Stefan ( all, I suppose), From the original formulation by Caglioti, et al. U0, V0 W0 for a nonfocusing neutron CW instrument and describes a parabolic curve with the minimum at roughly the 2-theta angle that matches the monochromator take-off (really 2-theta) angle. For a Bragg-Brentano powder diffractometer the curve is usually quite flat yielding very much smaller FWHM especially for the low angle portion rising only at high angles. I suppose the minimum is about the 2-theta for the analyser crystal. Thus, U, V W are usually quite small but the relationship of U0, W0 V0 still holds. They can be a bit hard to determine unless a very high quality pattern is used for the calibration. The expression using U, V W yields (FWHM)^2 so it REALLY can't ever have a negative result as Yaroslav noted in his message. Rietveld refinement codes will protect against the possibility of a negative square root in various ways (if not they can crash on a negative sqrt error). Bob Von Dreele R.B. Von Dreele IPNS Division Argonne National Laboratory Argonne, IL 60439-4814 -Original Message- From: Stefan Berger [mailto:[EMAIL PROTECTED] Sent: Monday, June 25, 2007 11:18 AM To: rietveld_l@ill.fr Subject: Caglioti U V W parameters Dear All, i am a little bit confused about the magnitudes of the U V W profile parameters of the caglioti function for instrumental broadening. Is it true, that U and W are always positiv (larger 0) and V is always smaller 0 (negativ)? Thanks for your hints and explanations. Best Regards, Stefan winmail.dat
More Caglioti U V W parameters
To all: OBSERVATION: Most of the reported X-ray Rietveld analyses I've seen include refined values for U, V, W which are dependent on the particular sample of interest. As you say below regarding U, V, W: They can be a bit hard to determine unless a very high quality pattern is used for the calibration. Therefore, I am puzzled why it is current practice to allow U, V W to vary during Rietveld refinement. If U, V, W are really INSTRUMENT parameters, shouldn't they be determined independently using a very high quality [specimen to determine the] pattern [which] is used for the calibration -- and then FIXED FOR FUTURE ANALYSES? Can anyone explain why U, V, W are refined? Frank May Research Investigator Department of Chemistry and Biochemistry University of Missouri - St. Louis One University Boulevard St. Louis, Missouri 63121-4499 314-516-5098 [EMAIL PROTECTED] From: Von Dreele, Robert B. [mailto:[EMAIL PROTECTED] Sent: Mon 6/25/2007 12:27 PM To: rietveld_l@ill.fr Subject: RE: Caglioti U V W parameters Dear Stefan ( all, I suppose), From the original formulation by Caglioti, et al. U0, V0 W0 for a nonfocusing neutron CW instrument and describes a parabolic curve with the minimum at roughly the 2-theta angle that matches the monochromator take-off (really 2-theta) angle. For a Bragg-Brentano powder diffractometer the curve is usually quite flat yielding very much smaller FWHM especially for the low angle portion rising only at high angles. I suppose the minimum is about the 2-theta for the analyser crystal. Thus, U, V W are usually quite small but the relationship of U0, W0 V0 still holds. They can be a bit hard to determine unless a very high quality pattern is used for the calibration. The expression using U, V W yields (FWHM)^2 so it REALLY can't ever have a negative result as Yaroslav noted in his message. Rietveld refinement codes will protect against the possibility of a negative square root in various ways (if not they can crash on a negative sqrt error). Bob Von Dreele R.B. Von Dreele IPNS Division Argonne National Laboratory Argonne, IL 60439-4814 -Original Message- From: Stefan Berger [mailto:[EMAIL PROTECTED] Sent: Monday, June 25, 2007 11:18 AM To: rietveld_l@ill.fr Subject: Caglioti U V W parameters Dear All, i am a little bit confused about the magnitudes of the U V W profile parameters of the caglioti function for instrumental broadening. Is it true, that U and W are always positiv (larger 0) and V is always smaller 0 (negativ)? Thanks for your hints and explanations. Best Regards, Stefan winmail.dat
Gianluigi Marra/EC176101/EC-IT/ENICHEM/IT
Sarò assente dall'ufficio a partire dal 25/06/2007 e non tornerò fino al 09/07/2007. Risponderò al messaggio al mio ritorno.
Re: More Caglioti U V W parameters
In my opinion, the short answer (regarding use of Caglioti parameters) is
that their use is historic and somewhat convenient, but their usual
application is based on no theory whatsoever, and they can be quite
troublesome to apply.
They came from a paper (Nuc. Instrum. Methods, 1958) on the resolution
of a neutron powder diffractometer using mosaic crystals and S\{o}ller
(that's an umlaut over the o; please, not solar) collimators, which gives
precise expressions for U, V, and W in terms the various geometric
parameters of the diffractometer. If (as was true of most samples on
neutron powder diffractometers at the time) the instrument dominated the
peak shape, they give a good representation of the observed linewidth.
Maybe you could tweak them up a bit to account for sample broadening.
Accordingly, they were ideally suited to Rietveld's method which was first
developed for CW neutron powder diffractometers. Historically, they seem
to have overstayed their welcome, I mean their theoretical justification.
This is especially so for high resolution x-ray powder diffractometers at
synchrotrons and elsewhere where the peak width is almost entirely from
the sample, not the instrument.
One problem with them is that for inappropriate choices of U, V, and W,
the linewidth can become an imaginary number over a certain range of
diffraction angles. This leads to some unpleasant instabilities in
refinement programs that use them.
The fundamental parameters approach would have you model the instrument
and the sample separately, and for any other kind of diffractometer, U, V,
and W are probably not a very good model of either. You can learn about
fundamental parameters e.g., from the Bruker Topas documentation, or from
Klug and Alexander, chapter 6.
If you are not going to try to separately model instrument and sample, you
can get a pretty good line through your data points and relative
intensities suitable for Rietveld analysis with U, V, and W (and some of
their extensions, such as Lorentzian X and Y in, e.g., GSAS) Toward that
end note that if you forget V, the (Gaussian) FWHM is $(U \tan^2 \theta +
W)^{1/2}$, which suggests that U is kind of like strain broadening and W
is kind of like size broadening, coming together in quadrature. I have
had generally OK luck leaving V set to zero and refining U and W. That
has the advantage of being more robust than refining the three (or more)
parameters. I guess once your refinement is pretty much under control,
you could let V vary to see if the fit improves. Just be careful not to
believe that the refined values of U, V, and W have any meaning in such a
refinement.
^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~^~
Peter W. Stephens
Professor, Department of Physics and Astronomy
Stony Brook University
Stony Brook, NY 11794-3800
fax 631-632-8176
Re: More Caglioti U V W parameters
Just to add more fat to the fire Have a look at Young, R. A. Desai, P. 1989, 'Crystallite Size and Microstrain Indicators in Rietveld Refinement', Archiwum Nauki o Materialach, vol. 10, no. 1-2, pp. 71-90. (I can send the PDF if needs be) They talk about the Thompson, Cox and Hastings model, which explicitly separates the gaussian and lorentzian components of a psuedo-Voight peak shape. FWHM(G)^2 = U tan^2(T) + V tan(T) + W FWHM(L) = X tan(T) + Y/cos(T) As Prof. Stephens pointed out (and is stated in Yound and Desai), the coefficients can be broken into instrumental and sample (size, strain) components. U = U_inst + U_strain V = V_inst W = W_inst X = X_inst + X_strain Y = Y_inst + Y_size You can fix the instrument components with your standard, and then refine the difference with your sample. If you want to stick with the straight UVW symbolism, Young and Desai also state that you can use the size broadening term FHWM(G)^2 = Z/cos^2(T), which yields: FWHM(G)^2 = Z/cos^2(T) + (U_inst + U_strain) tan^2(T) + V_inst tan(T) + W_inst which can be re-written as FWHM(G)^2 = (U_inst + U_strain + Z_size) tan^2(T) + V_inst tan(T) + (W_inst + Z_size) as long as you constrain the two Z_size's to be the same. The last equation is what Prof Stevens alludes to in his refinement of U and W, all of the sample related parameters are folded up there. Of course, your mileage may vary... Cheers Matthew Matthew Rowles CSIRO Minerals - Clayton Ph: +61 3 9545 8892 Fax: +61 3 9562 8919 (site) Email: [EMAIL PROTECTED]
Re: More Caglioti U V W parameters
Matthew, could I please get the PDF version of the paper? thanks, KLaus-Dieter. [EMAIL PROTECTED] wrote: Just to add more fat to the fire Have a look at Young, R. A. Desai, P. 1989, 'Crystallite Size and Microstrain Indicators in Rietveld Refinement', /Archiwum Nauki o Materialach,/ vol. 10, no. 1-2, pp. 71-90. (I can send the PDF if needs be) They talk about the Thompson, Cox and Hastings model, which explicitly separates the gaussian and lorentzian components of a psuedo-Voight peak shape. FWHM(G)^2 = U tan^2(T) + V tan(T) + W FWHM(L) = X tan(T) + Y/cos(T) As Prof. Stephens pointed out (and is stated in Yound and Desai), the coefficients can be broken into instrumental and sample (size, strain) components. U = U_inst + U_strain V = V_inst W = W_inst X = X_inst + X_strain Y = Y_inst + Y_size You can fix the instrument components with your standard, and then refine the difference with your sample. If you want to stick with the straight UVW symbolism, Young and Desai also state that you can use the size broadening term FHWM(G)^2 = Z/cos^2(T), which yields: FWHM(G)^2 = Z/cos^2(T) + (U_inst + U_strain) tan^2(T) + V_inst tan(T) + W_inst which can be re-written as FWHM(G)^2 = (U_inst + U_strain + Z_size) tan^2(T) + V_inst tan(T) + (W_inst + Z_size) as long as you constrain the two Z_size's to be the same. The last equation is what Prof Stevens alludes to in his refinement of U and W, all of the sample related parameters are folded up there. Of course, your mileage may vary... Cheers Matthew Matthew Rowles CSIRO Minerals - Clayton Ph: +61 3 9545 8892 Fax: +61 3 9562 8919 (site) Email: [EMAIL PROTECTED] -- Dr. Klaus-Dieter Liss Senior Research Fellow The Bragg Institute, ANSTO PMB 1, Menai, NSW 2234, Australia New Illawarra Road, Lucas Heights T: +61-2-9717+9479 F: +61-2-9717+3606 M: 0419 166 978 E: [EMAIL PROTECTED] http://www.ansto.gov.au/ansto/bragg/staff/s_liss.html private: http://liss.freeshell.org/
Re: More Caglioti U V W parameters
I´d like to read this paper too. So if you could send me a copy, Matthew, I´d be very pleased. Regards and thanks, Leandro From: Klaus-Dieter Liss [EMAIL PROTECTED] Reply-To: rietveld_l@ill.fr To: rietveld_l@ill.fr Subject: Re: More Caglioti U V W parameters Date: Tue, 26 Jun 2007 09:51:27 +1000 Matthew, could I please get the PDF version of the paper? thanks, KLaus-Dieter. [EMAIL PROTECTED] wrote: Just to add more fat to the fire Have a look at Young, R. A. Desai, P. 1989, 'Crystallite Size and Microstrain Indicators in Rietveld Refinement', /Archiwum Nauki o Materialach,/ vol. 10, no. 1-2, pp. 71-90. (I can send the PDF if needs be) They talk about the Thompson, Cox and Hastings model, which explicitly separates the gaussian and lorentzian components of a psuedo-Voight peak shape. FWHM(G)^2 = U tan^2(T) + V tan(T) + W FWHM(L) = X tan(T) + Y/cos(T) As Prof. Stephens pointed out (and is stated in Yound and Desai), the coefficients can be broken into instrumental and sample (size, strain) components. U = U_inst + U_strain V = V_inst W = W_inst X = X_inst + X_strain Y = Y_inst + Y_size You can fix the instrument components with your standard, and then refine the difference with your sample. If you want to stick with the straight UVW symbolism, Young and Desai also state that you can use the size broadening term FHWM(G)^2 = Z/cos^2(T), which yields: FWHM(G)^2 = Z/cos^2(T) + (U_inst + U_strain) tan^2(T) + V_inst tan(T) + W_inst which can be re-written as FWHM(G)^2 = (U_inst + U_strain + Z_size) tan^2(T) + V_inst tan(T) + (W_inst + Z_size) as long as you constrain the two Z_size's to be the same. The last equation is what Prof Stevens alludes to in his refinement of U and W, all of the sample related parameters are folded up there. Of course, your mileage may vary... Cheers Matthew Matthew Rowles CSIRO Minerals - Clayton Ph: +61 3 9545 8892 Fax: +61 3 9562 8919 (site) Email: [EMAIL PROTECTED] -- Dr. Klaus-Dieter Liss Senior Research Fellow The Bragg Institute, ANSTO PMB 1, Menai, NSW 2234, Australia New Illawarra Road, Lucas Heights T: +61-2-9717+9479 F: +61-2-9717+3606 M: 0419 166 978 E: [EMAIL PROTECTED] http://www.ansto.gov.au/ansto/bragg/staff/s_liss.html private: http://liss.freeshell.org/ _ Inscreva-se no novo Windows Live Mail beta e seja um dos primeiros a testar as novidades-grátis. Saiba mais: http://www.ideas.live.com/programpage.aspx?versionId=5d21c51a-b161-4314-9b0e-4911fb2b2e6d
Re: More Caglioti U V W parameters
Matthew and Others: One has to be careful with the Gaussian parameters, as they add as squares. There is a newer publication that deals with this problem: Size-Strain Line-Broadening Analysis of the Ceria Round-Robin Sample, Journal of Applied Crystallography 37 (2004) 911-924. The reprint can be downloaded from http://www.du.edu/~balzar/s-s_rr.htm. Paragraph 3.3 gives a detailed procedure how to obtain size/strain data from Rietveld refinement of the U,V,W,X,Y parameters. Davor * Dr. Davor Balzar University of Denver 303-871-2137 www.du.edu/~balzar * - Original Message - From: [EMAIL PROTECTED] Date: Monday, June 25, 2007 6:28 pm Subject: Re: More Caglioti U V W parameters To: rietveld_l@ill.fr Just to add more fat to the fire Have a look at Young, R. A. Desai, P. 1989, 'Crystallite Size and Microstrain Indicators in Rietveld Refinement', Archiwum Nauki o Materialach, vol. 10, no. 1-2, pp. 71-90. (I can send the PDF if needs be) They talk about the Thompson, Cox and Hastings model, which explicitly separates the gaussian and lorentzian components of a psuedo-Voight peak shape. FWHM(G)^2 = U tan^2(T) + V tan(T) + W FWHM(L) = X tan(T) + Y/cos(T) As Prof. Stephens pointed out (and is stated in Yound and Desai), the coefficients can be broken into instrumental and sample (size, strain) components. U = U_inst + U_strain V = V_inst W = W_inst X = X_inst + X_strain Y = Y_inst + Y_size You can fix the instrument components with your standard, and then refine the difference with your sample. If you want to stick with the straight UVW symbolism, Young and Desai also state that you can use the size broadening term FHWM(G)^2 = Z/cos^2(T), which yields: FWHM(G)^2 = Z/cos^2(T) + (U_inst + U_strain) tan^2(T) + V_inst tan(T) + W_inst which can be re-written as FWHM(G)^2 = (U_inst + U_strain + Z_size) tan^2(T) + V_inst tan(T) + (W_inst + Z_size) as long as you constrain the two Z_size's to be the same. The last equation is what Prof Stevens alludes to in his refinement of U and W, all of the sample related parameters are folded up there. Of course, your mileage may vary... Cheers Matthew Matthew Rowles CSIRO Minerals - Clayton Ph: +61 3 9545 8892 Fax: +61 3 9562 8919 (site) Email: [EMAIL PROTECTED]
Instrumental broadening
Dear all, In the book The Rietveld Method edited by young, (Page 114 chapter 7, part 7.2.3) five instrumental contributions were discussed. Broadening due to: 1) Source 2) Flat specimen 3) Axial divergence 4) Speciment transparency 5) Receiving slit I`m looking for a reference that has a figure showing the effect of each contribution on a peak. The explanation in the book is suffuciant but it would be better to see an image if there is any. Vahit
Dislocation density Measurement
Dear All, How can I get a dislocation density from the X-Ray diffraction analysis after the Rietveld Refinement, or any other method to calculate the Dislocation density from the powder X-ray data, please give me your suggestions and notes, Thanks in advance With warm reagrds S.Murugesan
RE: Instrumental broadening
Vahit This could be what you're after: Volume 109, Number 1, January-February 2004 Journal of Research of the National Institute of Standards and Technology Fundamental Parameters Line Profile Fitting in Laboratory Diffractometers R.W. Cheary, A.A. Coehlo J.P. Cline Have a look at papers by Cheary and Coehlo. They've done quite a bit of work on instrumental broadening (particularly on axial divergence) for their fundamental parameters approach. Cheers Matthew Matthew Rowles CSIRO Minerals - Clayton Ph: ᄉ 3 9545 8892 Fax: ᄉ 3 9562 8919 (site) Email: [EMAIL PROTECTED] -Original Message- From: Vahit Atakan [mailto:[EMAIL PROTECTED] Sent: Tue 26/06/2007 12:22 To: rietveld_l@ill.fr Cc: Subject: Instrumental broadening Dear all, In the book The Rietveld Method edited by young, (Page 114 chapter 7, part 7.2.3) five instrumental contributions were discussed. Broadening due to: 1) Source 2) Flat specimen 3) Axial divergence 4) Speciment transparency 5) Receiving slit I`m looking for a reference that has a figure showing the effect of each contribution on a peak. The explanation in the book is suffuciant but it would be better to see an image if there is any. Vahit winmail.dat
