Re: Misconduct

[Le Bail Armel]

Good new from PubPeer:Virgil OptasanuHi. I am one of the co-authors. Thanks for these warnings. It does indeed appear that there are problems with this image with an intention to manipulate data. Whatever the reason for this manipulation, it is completely unacceptable. I will investigate to find the origin of this problem and ask the editors to possibly remove the article. Greetings.envoyé : 12 janvier 2024 à 12:57de : Le Bail Armel à : Rietveld_L objet : MisconductHi,A good candidate for the "worst Rietveld refinement of the year" award :https://pubpeer.com/publications/12069A6AD9D5D34F26031F34705D06Even the difference pattern is totally fabricated.BestArmel ++ Please do NOT attach files to the whole list Send commands to eg: HELP as the subject with no body text The Rietveld_L list archive is on http://www.mail-archive.com/rietveld_l@ill.fr/ ++   
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Re: Misconduct

[Alan W Hewat]

I sympathise with Luca. There is no generally accepted name for this kind
of profile refinement, as there is for Pawley or Le Bail refinement, terms
that are well understood. I would simply call it *Profile Refinement*, as
Rietveld did, specifying *Quantitative Phase Analysis* where that is
appropriate. It's true that you can refine the atomic coordinates for the
different phases (to reduce the R-factor :-) but it would be better
"conduct" to fix atomic coordinates as determined from well prepared
mono-phase samples, refining only particle size, preferred orientation etc
for each phase. So "Rietveld Refinement" would be restricted to cases where
the atomic coordinates were refined to fit the profile. I don't think this
was the case here.

On Sat, 13 Jan 2024 at 09:39, Luca Lutterotti 
wrote:

> You are both true in a certain sense. It is true that this is not the core
> of the Rietveld refinement per se, but we don’t have an “official” term to
> call a refinement of a powder pattern using crystallographic parameters.
> Hence I tried to call it Rietveld-like or extended Rietveld.
> The alternatives are full pattern fitting, but this is usually referring
> to an unconstrained refinement, Pawley like. In XRF they use the term
> Fundamental Parameters approach, but I am afraid in diffraction was already
> used (first Cohere, am I remembering right?) for fitting profiles using
> physical models for the instrumental broadening.
> The Rietveld community never defined a generally accepted term for this
> kind of refinement, so people outside it what can they use?
>
> I am amused how Armel can spot such articles and especially notice the
> trick they did. I would not call the worse Rietveld refinement but for sure
> a bad misconduct case. Were they removing some peaks they could not explain
> or put down an amorphous halo at low angle? I am sad they used Maud in the
> first place and then manipulate the image. I notice that they report the
> intensity as (linear) counts, but it is not, they replaced also the labels
> as from the noise, residual and peaks intensity I am sure it was in square
> root of the intensity. Background was removed too. But I think there was no
> review at all, as the figure caption contains errors even for the chemical
> formula (Fe -> F).
>
> Best regards,
> 
> [image: logo_unitrento_firma.png]
>
>
> *Luca Lutterotti*
> Dipartimento di Ingegneria Industriale
> Università di Trento
> via Sommarive, 9 - 38123 Trento (Italy)
> tel. +39 0461 2824-14 (Office), -34 (X-Ray lab)
>
> [image: ico_fb_32x32.png][image: ico_twitter_32x32.png][image:
> ico_insta_32x32.png][image: ico_linkedin_32x32.png][image:
> ico_youtube_32x32.png]
>
> Maud: http://maud.radiographema.com 
>
>
>
> On 13 Jan 2024, at 07:39, Alan W Hewat 
> wrote:
>
> The core of Rietveld refinement is REFINING the crystallographic
> parameters to fit the pattern. That was the great innovation. Is that done
> here ? To calculate various patterns to refine phase composition you
> necessarily need models of the crystal structures. But all refinements of
> powder patterns are not Rietveld Refinement. Quantitative analysis of
> powder samples is an important technique, and to attribute that to Rietveld
> is wrong. Same goes for Pair Distribution Function analysis. Calling
> everything "Rietveld Refinement" is not helpful, and actually hides the
> fundamental contribution of this technique to crystallography.
>
> 
> Dr Alan Hewat, NeutronOptics
> Grenoble, FRANCE (from phone)
> alan.he...@neutronoptics.com
> +33.476984168 VAT:FR79499450856
> http://NeutronOptics.com/hewat 
> ___
>
>
> On Sat, 13 Jan 2024, 07:00 Matthew Rowles,  wrote:
>
>> Hard disagree here.
>>
>> You're using crystallographic parameters to calculate the (intensities
>> and positions of the) pattern.
>>
>> To me, that's the core of Rietveld refinement.
>>
>> You need to apply a peak shape model. Why not apply a model from which
>> you can extract crystallite parameters?
>>
>> QPA can then be done on the output of a refinement, eg application of the
>> internal standard method using the Hill /Howard algorithm.
>>
>> Its still a Rietveld refinement, I'm not just fitting peaks willy nilly;
>> they're constrained by a crystal model.
>>
>>
>> Matthew
>>
>> On Sat, 13 Jan 2024, 01:48 Alan W Hewat, 
>> wrote:
>>
>>> Apart from the record number of atoms, phases, parameters, citations etc
>>> used to describe just 3 broad peaks, I object to this kind of refinement
>>> being called "Rietveld refinement". Luca called it "Rietveld-like" in MAUD,
>>> which was used here, but even that is wrong. The term "Rietveld refinement"
>>> should be restricted to the refinement of crystallographic parameters -
>>> cell dimensions, atom coordinates etc. and not applied to quantitative
>>> analysis of phases, particle size etc. Fitting peaks in powder patterns 

Re: Misconduct

[Luca Lutterotti]

You are both true in a certain sense. It is true that this is not the core of 
the Rietveld refinement per se, but we don’t have an “official” term to call a 
refinement of a powder pattern using crystallographic parameters. Hence I tried 
to call it Rietveld-like or extended Rietveld.
The alternatives are full pattern fitting, but this is usually referring to an 
unconstrained refinement, Pawley like. In XRF they use the term Fundamental 
Parameters approach, but I am afraid in diffraction was already used (first 
Cohere, am I remembering right?) for fitting profiles using physical models for 
the instrumental broadening.
The Rietveld community never defined a generally accepted term for this kind of 
refinement, so people outside it what can they use?

I am amused how Armel can spot such articles and especially notice the trick 
they did. I would not call the worse Rietveld refinement but for sure a bad 
misconduct case. Were they removing some peaks they could not explain or put 
down an amorphous halo at low angle? I am sad they used Maud in the first place 
and then manipulate the image. I notice that they report the intensity as 
(linear) counts, but it is not, they replaced also the labels as from the 
noise, residual and peaks intensity I am sure it was in square root of the 
intensity. Background was removed too. But I think there was no review at all, 
as the figure caption contains errors even for the chemical formula (Fe -> F).

Best regards,
 

Luca Lutterotti
Dipartimento di Ingegneria Industriale
Università di Trento
via Sommarive, 9 - 38123 Trento (Italy)
tel. +39 0461 2824-14 (Office), -34 (X-Ray lab)




Maud: http://maud.radiographema.com 


> On 13 Jan 2024, at 07:39, Alan W Hewat  wrote:
> 
> The core of Rietveld refinement is REFINING the crystallographic parameters 
> to fit the pattern. That was the great innovation. Is that done here ? To 
> calculate various patterns to refine phase composition you necessarily need 
> models of the crystal structures. But all refinements of powder patterns are 
> not Rietveld Refinement. Quantitative analysis of powder samples is an 
> important technique, and to attribute that to Rietveld is wrong. Same goes 
> for Pair Distribution Function analysis. Calling everything "Rietveld 
> Refinement" is not helpful, and actually hides the fundamental contribution 
> of this technique to crystallography.
> 
> 
> Dr Alan Hewat, NeutronOptics
> Grenoble, FRANCE (from phone)
> alan.he...@neutronoptics.com
> +33.476984168 VAT:FR79499450856
> http://NeutronOptics.com/hewat 
> ___
>
> 
> On Sat, 13 Jan 2024, 07:00 Matthew Rowles,  > wrote:
>> Hard disagree here.
>> 
>> You're using crystallographic parameters to calculate the (intensities and 
>> positions of the) pattern.
>> 
>> To me, that's the core of Rietveld refinement.
>> 
>> You need to apply a peak shape model. Why not apply a model from which you 
>> can extract crystallite parameters? 
>> 
>> QPA can then be done on the output of a refinement, eg application of the 
>> internal standard method using the Hill /Howard algorithm. 
>> 
>> Its still a Rietveld refinement, I'm not just fitting peaks willy nilly; 
>> they're constrained by a crystal model.
>> 
>> 
>> Matthew
>> 
>> On Sat, 13 Jan 2024, 01:48 Alan W Hewat, > > wrote:
>>> Apart from the record number of atoms, phases, parameters, citations etc 
>>> used to describe just 3 broad peaks, I object to this kind of refinement 
>>> being called "Rietveld refinement". Luca called it "Rietveld-like" in MAUD, 
>>> which was used here, but even that is wrong. The term "Rietveld refinement" 
>>> should be restricted to the refinement of crystallographic parameters - 
>>> cell dimensions, atom coordinates etc. and not applied to quantitative 
>>> analysis of phases, particle size etc. Fitting peaks in powder patterns was 
>>> done before Rietveld, who must be turning in his grave to see his name 
>>> associated with this kind of thing. 
>>> 
>>> 
>>> Dr Alan Hewat, NeutronOptics
>>> Grenoble, FRANCE (from phone)
>>> alan.he...@neutronoptics.com
>>> +33.476984168 VAT:FR79499450856
>>> http://NeutronOptics.com/hewat 
>>> ___
>>>
>>> 
>>> On Fri, 12 Jan 2024, 12:57 Le Bail Armel, >> > wrote:
 Hi,
 
 A good candidate for the "worst Rietveld refinement of the year" award :
 
 https://pubpeer.com/publications/12069A6AD9D5D34F26031F34705D06
 
 Even the difference pattern is totally fabricated.
 
 Best
 
 Armel
 
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