@Lawrence Margulies nice.

I think you might want to mean 'X-ray techniques (or SAXS to be specific!)' rather than 'XRD( as this is another well establish experimental technique with purpose of its own)'. Thank you for the heads up though :). Do share some software for SAXS data analysis for the benefit of the reader. But you must see that people are still confused with the sizes- that of particle, grain and crystallite.

And Raj kumar, to the best of my knowledge:

The fundamental size in any ordered crystalline solids is the 'crystallite size'. It is a measure of coherent diffracting domain - i.e., it is small single crystal in itself. The size that is estimated through XRD after implementing appropriate instrumental and micro-strain corrections are the average crystallites size of crystallites with a particular orientation. Grains are agglomerates of ordered solids with distinct boundaries. It can consist of a single crystalline orientation and sometimes multiple crystalline orientation. It can be seen by a microscope (conditioning maybe required). SEM and AFM are common techniques for that. A TEM can be used to probe if a grain further contain multiple crystalline orientation or not. Particle size is the biggest of them all. A particle can be anywhere from a single crystal to multi-granular agglomerate. I think it is meaningful to talk about it when u have some agglomerate of various size disperse in a medium like liquid or simply air (eg. powder, plz note that earlier i want to mean grain size, it stand corrected now. But remember, powder itself can be a single crystal).

So for your sample (and original question) , your bulk surely has some fundamental crystallites within. And unless those crystallites (crystal order) breaks down further upon your synthesis or conditioning, then there is every reason to believe that your synthesized materials still retain the same crystallographic order in the same range (same broadening). And good luck, I work with thin films where I am interested in crystallites and grains. Particles et al has little meaning in thin films.

As a general case the broadening of XRD peaks in nanocrystals is common. However you have to be careful because the broadening can also occur due to strain in the crystal. Peak broadening is normally seen in crystallites smaller than 100 nm. If the full-width at half maximum is If consistent for each peak then you can rest assured that broadening is due to the smaller crystallite size.

This paper may be of help:

https://www.researchgate.net/publication/230824264_On_the_modelling_of_the_powder_pattern_from_a_nanocrystalline_material

And many useful references are there...

Article On the modelling of the powder pattern from a nanocrystalline material

Insufficient information for a reasonable answer. What is raw? Is it bulk powder? Cross check the size of the crystallites in your raw and so called nano-particle. Remember particle size is not equal to powder size is not equal to crystallite size. And XRD measures only the crystallite size.

thank you joy deep dutta and Roman Nikolaevich,

Ch. Kishan Singh raw means bulk material. can u explain the difference between particles size, powder size and crystalline size ? and how to measure these different sizes of sample, please explain in detail

Particle size is sometimes called the primary particle size. It means that these are tightly bound agglomerates of crystallites (supposing you have a polycrystalline material, then a few crystals would be in each particle). Often a group of particles for agglomerates which determine the powder size. You could de-agglomerate these using surfactants for example in a colloidal suspension, which you cannot do to the primary particle. Very often the size goes as Powder (or aggregate size)> primary particle> crystallite size. I hope this clears up your doubts.

Once again i have remind everyone that particle size can be meazured by xrd. In fact it is the most accurate method and gives particle shape and distributions as well. Of course grain size can also be determined as well as ordering or clustering at all length scales betwedn 1nm and 10 microns simultaneously. I hope i dont have to keep correcting this misunderstanding.

@Lawrence Margulies nice.

I think you might want to mean 'X-ray techniques (or SAXS to be specific!)' rather than 'XRD( as this is another well establish experimental technique with purpose of its own)'. Thank you for the heads up though :). Do share some software for SAXS data analysis for the benefit of the reader. But you must see that people are still confused with the sizes- that of particle, grain and crystallite.

And Raj kumar, to the best of my knowledge:

The fundamental size in any ordered crystalline solids is the 'crystallite size'. It is a measure of coherent diffracting domain - i.e., it is small single crystal in itself. The size that is estimated through XRD after implementing appropriate instrumental and micro-strain corrections are the average crystallites size of crystallites with a particular orientation. Grains are agglomerates of ordered solids with distinct boundaries. It can consist of a single crystalline orientation and sometimes multiple crystalline orientation. It can be seen by a microscope (conditioning maybe required). SEM and AFM are common techniques for that. A TEM can be used to probe if a grain further contain multiple crystalline orientation or not. Particle size is the biggest of them all. A particle can be anywhere from a single crystal to multi-granular agglomerate. I think it is meaningful to talk about it when u have some agglomerate of various size disperse in a medium like liquid or simply air (eg. powder, plz note that earlier i want to mean grain size, it stand corrected now. But remember, powder itself can be a single crystal).

So for your sample (and original question) , your bulk surely has some fundamental crystallites within. And unless those crystallites (crystal order) breaks down further upon your synthesis or conditioning, then there is every reason to believe that your synthesized materials still retain the same crystallographic order in the same range (same broadening). And good luck, I work with thin films where I am interested in crystallites and grains. Particles et al has little meaning in thin films.

Broadening of XRD peak (due to particle size) is generally observed for particle size less than 200 nm and is more pronounced when size < 50 nm.

For proper calculation, other aspects such as the broadening due to strain in the sample should be considered. Therefore, the crystallite sizes determined from XRD must be compared with those derived from the transmission electron microscopy (TEM) analysis.

In practice, we should not rely on any single technique as for as particle size in concerned.

In order to be better sure about the actual particle size of "ÿour nanoparticle", try to do TEM analysis of your sample (diluted and well-dispersed by sonication) to get an idea of primary particle size. Also Doing TEM in dark field (DF) mode can give you an idea of whether you have poly-crystalline sample (you will see small crystallites shining brightly in DF TEM Images as shown in TEM image attached, for example). In most case, it is possible to measure the size of these small crysytallites (making up an aggregate or particle).

Then by comparing your XRD average crystalite Size with TEM particle size/crystallite size, you have a better idea of the size of "your nanoparticles". Your TEM size may be the same as the XRD size or a roughly a multiple of XRD size if various crystallites go to make up the particle you observe in TEM image).

The other participants have now perfectly explained the theoretical background and the important factors associated with your question.

From my perspective the Scherrer analysis works quite well and gives helpful hints at crystallite sizes in the range smaller than 50 nm, let the effects discussed above be in the range of +/- 20 %, basically the information obtained reflects the correct trendency .

As long as you do not really give us some more details, the whole discussion stays highly speculative, what i would like to know is:

What is the material you are working on and what is the reference powder where you claim to have the same peak width/crystallite size.

Maybe the reference itself consists of bulky particles of agglomerated nanocrystallites and so only appears to be coarse but in fact it is not.

A typical example for such behaviour are some qualities of Y-TZP

I completely agree with Ch. Kishan Singh explanation for your question.

Yes Kishan,

Small angle x-ray scattering (SAXS) was exactly what I had in mind. I find a lot of people that are not in the x-ray scattering field who aren't aware of just how powerful SAXS can be, especially for nano-materials and polymers, and how very different the length scale information you get compared to wide angle xrd. Particles, clusters, fractal structures in polymers, any structural order between the length scales of 1nm and 10 microns can be measured. Four orders of magnitude in length scale probed simultaneously. There are not many methods that can claim that.

If ur particle = domain/crystallite, than u can start to distinguish from < 500 nm (std FWHM 0.026 2theta). Rather than that u can't, unless u use SAXS but it typicaly 1 - 100nm.

SAXS can measure length scales between 1nm and 10 microns. How many times have I written that sentence?

@lawrence, what I mean typically it is about the most anode that usually used (Cu, with focusing mirror). To reach 10 micron, what is ur instrument settings?

A Synchrotron.

Broadening of the X-ray diffraction peaks in nano-crystalline materials mainly attributed to the following factors:

• Instrumental Broadening

• Crystallite Size Broadening

• Strain Broadening

If breadth consistent for each peak then assured broadening due to crystallite size. Crystallite size is a measure of the size of coherently diffracting domains. The crystallite size of the particles is not generally the same as the particle size due to the formation of polycrystalline aggregates. Lattice strain is a measure of the distribution of lattice constants arising from crystal imperfections, such as lattice dislocations. Other sources of strain include the grain boundary triple junction, contact or sinter stresses, stacking faults and coherency stresses.

Shiv,

There are many many other factors that can produce peak broadening.

@Lawrence. No wonder.

Just curious, if not make 2theta min so small, than make the lambda so big or both. Am I in the right track?

It's about making 2theta min small, which is done using a double crystal analyzer with a 2D detector behind. Also having a very large sample to detector distance is key. You don't want to have too low an x-ray energy, otherwise you begin to have to worry about a lot of other effects.

Broadening is essetially zero when the particle size exceeds about 1000 A or 1/100000 cm. The width of the diffraction curve increases as the thickness of the crystal decreases . The width B is usually measured in radians , at an intensity equal to half the maximum intinsity . Broadening is Chiefly used to measure the particle size. The chief applications of the line - broadening methode have been in the measurement of the particle size of the materials. When the size of the individual crystals is less than 1/100000 cm (1000 A ), the term particle size is usually used . The crystal in this size cause broadening of the Debye rings , the extent of the Broadening B  being given by

B = 0.9 wavelength  / diameter of crystal particle  x  cos theta

So  briefly the XRD broadening of diffraction peaks of nanoparticles  must be happened due to the above disscusion iIt is Okay or you have another opinions or scientific  views.

I am also agree with SHIVE  KUMAR Banaras Hindu University, and  other popular answers .

@Mustafa. Either somethin wrong with ur optics or ur stadard sample. It easily to guess that ur instrument profile has FWHM >0.2 (2theta), that's why u only can distinguish the domain/crystallite size less than 1000 A (100 nm).

If u still using Scherrer formula than the result might be doubtful because there so many factor need consider before u apply Scherrer formula or Williamso-Hall approach... One of them is the Scherrer constant as discuss in this link: https://www.researchgate.net/post/Can_anybody_tell_me_why_in_the_Scherrer_formula_the_constant_K_is_taken_as_094

1) Your sample may be in bulk size. Please confirm particle size by some other method like DLS or TEM etc. (2) Some errors due to mishandling of XRD machine. (3)Some faults in XRD machine

i done DLS, FESEM and TEM the particles size in all three characterization below 50 nm, but reviewer ask the explaination for not observed in broadness of peak in XRD. 

Please show the XRD diffactogram. So that, suggestions can be given. Also, mention FWHM value of each peaks in your paper which is the confirmation for peak broadening.

Did u take a diffraction pattern from standard sampel?

I guess ur raw material is micro particles contained nano crystallite and has smaller or equal size to ur nano particles. That's why the diffraction profiles look the same, both raw and nano particles.

Attach the standard sample an ur data (raw and nano particle here)

Yes i did XRD of both standard along with Nanoparticles, and confirm by DLS, FESEM TEM.........if these three are confirming particles size below 50 nm then is it impotant XRD also.

U can use the WPPM method from Prof. P. Scardi and Prof. M. Leoni. It called PM2K that implementing the whole powder pattern modeling method.

Or perhaps u can attach ur XRD data (standard and samples).

I'm still curious to see the width of your peaks. What is the material? A metal, a ceramic? What was done to the raw materials to produce nanoparticles from it? There are a lot of possible explanations, but to narrow them down this type of information is key, otherwise we are just really guessing here.

if your particles is smaller than your raw material your peaks become sharpen and thinner for example nano particles have thinner peak than micro particles

hai dear Mehrdad Rashidzadeh, i know that and in case no thinner peaks were aobserved but SEM, TEM, DLS giving particles size below 100 nm. then i am asking the explaination for that, why not observed thinner peaks in my sample, that is a Q ?

Raj, above 50 nm ur FWHM linewidth is smaller than 0.5 (2theta), it's difficult to distinguish by looking to the graph only... Would u tell me what is FWHM for ur sandard? pick a single peak in between 20 - 40 (2theta). Btw, what is the SRM u used?

In general, broadening can be due to an amorphous or nano sized material. If it is amorphous, so the pattern shows a complete broadening in all 2 theta values. However, if it is nano material, the peaks are broadened. But you should know that Debye scherrer equation is a theory and calculate crystal size not particle size and sometimes it is in opposition to the SEM images.

in our research results amorphos nano particles has been shown broad bond in XRD

I think this link can help

http://www.instanano.com/characterization/theoretical/xrd-size-calculation/

When using Scherrer equation note that it doesn't account for the deformation of the cell parameter. This has an effect on the broadening as well. Often you may neglect the deformation. However, the two broadening effects can be summed.

The broadening B due to the deformation e is given by: B = e*tan(theta) where theta is diffraction angle (not 2theta).

More informations can be found in : B. D. Cullity, Elements of X-Ray diffraction, Addison Wesley (1956)

and R.A. Young, The Rietveld Method, Oxford University Press, 1993

I have a question. What is the B unit in williamson hall equation. As well as the theta unit in the equation?radian or degree??

always radian

Thank you andrea. You mean when we want to calculate cos (theta), theta must be in radian unit?

there are two source of broadening, sample and instrumental parameters.

I suggest you to take a look at the following site

http://pd.chem.ucl.ac.uk/pdnn/peaks/broad.htm

Extent of broadening of peaks can be attributed to distribution profile of particle size or polydispersity index and thereby the average particle size obtained by employing Debye Scherrer formula.

In nanocrystals most often than not, band broadening occurs due to strain in crystal lattices. While applying Debye Scherrers equation one has to be careful

Dear Raj

The broadening of XRD peaks of nanoparticles compared to those of the corresponding raw materials can be explained as follow:

It is well known that the mean size of a microcrystal, i.e., ≤1μm, can be determined by a mathematical relationship originally derived by Scherrer[1], based on the X-ray diffraction pattern. The relationship is described as follows:

D = [Kλ / β Cos θ] (1)

Where:

θ is the diffraction angle.

λ is the wavelength of the radiation.

β is the line broadening, β = B-b where B is the breadth of the diffraction line at its

half intensity maximum, b is the instrumental broadening.

K is the shape factor which usually takes a value of about 0.9.

Details of the derivation of Eq. (1) are given elsewhere [1,2].

It is clear from Eq. (1) that the mean size of a microcrystal (D) is inversely proportional to the line broadening. In other words, as the line broadening (β) increases, the size of the microcrystal decreases.

This sort of behavior was observed in two different metallic glasses [3] , in which the boundary line between microcrystal in amorphous, short range ordered, structures and crystalline, longrange ordered, structures is defined. Therefore, your observation can be due to a transition of your sample from nano-crystal, short orderred, structures to macrocrystal,longrange ordered,structures. This structure transition could occurred because of a localized heating of the nano-particles.

References

[1] P. Scherrer: Göttinger Nachrichten Vol. 2 (1918), p. 98.

[2] H.P. Klug, L.E. Alexander, X-ray Powder Diffraction Procedures, Wiley, New York, pp. 24, (1954).

[3].Article Boundary Line of Microcrystallites in Amorphous and Crystall...

Dear Raj,

Sources of Peak Broadening are (i) sample contributions and (ii) instrumental contributions . Following to the above useful comments, I would like to suggest you to take a look at the Size-Strain Round Robin - http://pd.chem.ucl.ac.uk/pdnn/peaks/broad.htm

Please noted that, the results of the round robin and comparative analysis using three different line-broadening methods were published as

D. Balzar, N. Audebrand, M. Daymond, A. Fitch, A. Hewat, J.I. Langford, A. Le Bail, D. Louër, O. Masson, C.N. McCowan, N.C. Popa, P.W. Stephens, B. Toby, Size-Strain Line-Broadening Analysis of the Ceria Round-Robin Sample, Journal of Applied Crystallography 37 (2004) 911-924

Please enjoy reading it.

Best wishes,

Husin SITEPU

The below article might be useful information on how to calculate the crystalline size a d micro strain using Materials Analysis Using Diffraction (MAUD) software:-

Structural and magnetic studies of nanocrystal me Mg-doped Li(0.5)Fe(2.5)O(4) particles prepared by mechanical milling,

July 2008; Journal of Physics D Applied Physics 41(16):165006; DOI: 10.1088/0022-3727/41/16/165006

Additionally, the MAUD software can be found at the link - http://maud.radiographema.eu/

Hopefully, the above information is helpful!!!

The question is some tested samples by XRD technique offer two broad band, what the origin of presence two broad bands at different diffraction angel?