Preparation of powder specimen for

quantitative XRD

Reinhard Kleeberg
TU Bergakademie Freiberg
Mineralogical Institute

[email protected]

References

Moore, D.M. & Reynolds, R.C.: X-Ray Diffraction and the Identification and
Analysis of Clay Minerals. Oxford Univ. Press/CMS 1989, 1997.
Bish, D.L. and Reynolds, R.C., Jr. (1989) Sample preparation for X-ray
diffraction. Pp. 73-99 in: Modern Powder Diffraction (D.L. Bish and J.E.
Post, editors). Reviews in Mineralogy 20, Mineralogical Society of America,
Washington, D.C.
Środoń, J., Drits, V.A., McCarty, D.K., Hsieh, J.C.C. and Eberl, D.D. (2001)
Quantitative X-ray diffraction analysis of clay-bearing rocks from random
preparations. Clays and Clay Minerals, 49, 514-528.
Hillier, S. (2003) Quantitative analysis of clay and other minerals in
sandstones by X-ray powder diffraction (XRPD). International Association
of Sedimentologists Special Publication, 34, 213-251.
Kleeberg, R., Monecke, T., Hillier, S. (2008) Preferred orientation of mineral
grains in sample mounts for quantitative XRD measurements: How random
are powder samples? Clays and Clay Minerals, 56 (4), 404-415.

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 Problems Milling Filling Examples
Crystallite statistics 1
Impact of crystallite statistics on the diffraction signal depends on:
• sample volume contributing to diffraction (limited by the primary slit system, sample
holder, absorption)
• section of the diffraction rings seen by the detector (limited by Soller slits, receiving
slit, detector area)
• number of particles per volume unit (limited by particle size)

sections seen by
a point detector

sections seen by
an area detector

coarse material ideal powder

- only the particle size may be optimized by sample preparation

- ideal case: “infinite number of crystallites” = continuous cones of diffraction 3

Problems Milling Filling Examples

Crystallite statistics 2
Practical consideration: How many particles do contribute to our diffraction
signal?
Exemplary calculation at: http://epswww.unm.edu/xrd/xrdclass/07-Errors-Sample-Prep.pdf
Quartz in different particle diameter in a conventional Bragg-Brentano diffractometer
Particle diameter 40 µm 10 µm 1 µm
Diffracting particles 12 760 38 000
To achieve a standard uncertainty of < 1%, > 52900 particles would be needed!

Experimental test see: Klug, H.P. & Alexander, L.E. X-Ray Diffraction Procedures. John Wiley,
New York, 1954
Quartz in different particle diameter in a conventional Bragg-Brentano diffractometer
Particle size fraction /microns 15-50 5-50 5-15 <5
Standard deviation of I quartz 101 /% 18.2 10.1 2.1 1.2
Conclusions:
-If we want to measure single peak intensities of minerals correctly, we should try
to mill any rock samples to < 5 µm.
-This is necessary to get reliable results of Rietveld structure analysis, too. 4

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 Problems Milling Filling Examples
Microabsorption 1

Microabsorption causes loss of intensity inside a particle. If this loss is

different between two phases, the beam is interacting with different phase
volumina! Thus, the QPA results will be falsified.

High absorption Lower absorption

Problems Milling Filling Examples

Microabsorption 2
The theory of BRINDLEY (1945):

- depends on grain diameter d and linear attenuation coefficient µ

- intensity loss / correction factor can not be determined from the powder
data!

- can be ignored if the product µd is equal for all phases

- intensity resp. scale factor can be corrected if µd < ~0.5, and if both
values are known for each phase!

Approximated BRINDLEY correction in the BGMN structure file:

GOAL:forsterite=GEWICHT*exp(my*d*3/4)
GEWICHT Rietveld scale factor, mass weighted
my linear attenuation coefficient in 1/µm, provided by BGMN
d estimated particle diameter in µm, to be set by the user in structure or control file
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 Problems Milling Filling Examples
Microabsorption 3
When does microabsorption occur in practice?

Example: QPA of sulphide bearing rocks

Absorption contrast between quartz and pyrite
coarseness according to BRINDLEY (1945)

phase grain size/µm µd µd

Cu K Co K
quartz 10 0.093 0.146
medium coarse
pyrite 10 1.012 0.516
very coarse coarse

Conclusions:
- No problem for fine clay fractions and silicate minerals having similar (low) µ.
- But, if we want to quantify rock samples containing high absorbing materials, we
should try to mill the samples to < 5 µm.

Problems Milling Filling Examples

What we have
For example, sedimentary rocks:
• large crystals (>mm, e.g. quartz), together with fine grained material (clay)
• hard and soft phases together
• differences in density may occur (pyrite, hematite, rutile, silicates…)
• mechanically or thermally sensitive phases (e.g. clay minerals, zeolites, sulphates)

What we want to get

• mean particle size below 5 µm, optimum 1-3 µm
• narrow particle size distribution, no amorphization, no “rocks-in-the-dust”
• no additional disorder ( e.g. by shifting of layers)
• no contamination (e.g. by grinding elements)
• no loss of material (e.g. by dusting or dissolution)
• no phase transformation (e.g. by dissolution-precipitation, hydration-dehydration…)
• no phase separation (e.g. by hardness, density, primary particle size, electrostatic…)
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4
Problems Milling Filling Examples
Golden rules for milling
General principles:
- If a sample is not homogenous or not representative, any further efforts
(for phase quantification in general) are unnecessary.

- The maximum grinding energy has to be adapted to the most sensitive phase.

- Some overmuch large grains are better than any destroyed phase(s).

- Working in closed containers to avoid loss of material by dusting, checking

for losses by sedimentation, dissolution, electrostatic adhesion...

- Quick working for minimum contact with dissolution agents and air to avoid
any phase alteration.

- Samples should not be exposed any enhanced temperature.

- Note (or keep in mind) what treatments and changes your sample was
exposed between sampling and XRD measurement.
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Problems Milling Filling Examples

Grinding methods useful for clay-bearing rocks 1
Hand grinding in agate mortar
- easy, but strenuous
- allows a stepwise sieving of < 20 µm, very mild
- resulting powder is mostly to coarse for high absorbing materials
- danger of loss by dusting

Foto: Detlev Müller Foto: Detlev Müller 10

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 Problems Milling Filling Examples
Grinding methods useful for clay-bearing rocks 2
McCrone micronising mill
- wet grinding (in water or alcohol) produces optimum grain distribution
- crushing the starting material < 0.4 mm is necessary
- danger of contamination by grinding elements (corundum, quartz, ZrO2)
- dissolution and/or alteration by the grinding liquid (water, ethanol, hexane…)
- filtering or drying of the slurry and additional homogenisation is necessary

Milling time /min 48 24 12 6

6 Mean diameter /µm 1.8 2.6 5.8 11.4

4
Volume %
3

0
0.04 0.1 0.4 1 2 4 10 20 40 100 400
Particle diameter/µm
Particle size distribution of McCrone milled quartz, 11
from Hillier (2003) Foto: Detlev Müller

Problems Milling Filling Examples

Homogenisation
- is necessary for admixing of any standards as well as to overcome the
(unavoidable) separation processes during grinding, sieving, and sedimentation
- should be applied with minimum energy

- can also used for destroying of aggregates

- should be done immediately before filling the sample

Useful methods:
- admixing of standards by grinding together (to get
similar grain size and intimate mixing)
- larger amounts of easily flowing powders by
overhead-shaking
- small amounts by manual stirring
- homogenisation and destroying of aggregates by
swirling the powder with small steel balls („Ardenne
vibrating mill“ or Fritsch mini-mill “pulverisette 23”)

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 Problems Milling Filling Examples
Making the powder mount for Bragg-Brentano XRD 1
are an old matter of debate, and sometimes treated like religion…

Possible pre-treatment of powder before filling:

- No pre-treatment (filling the milled and homogenised powder “as is”)
- Forming irregular shaped aggregates
- by freeze-drying
- by spray-freeze-drying
- by admixing glass powder, plastics or organics, e.g. cork powder
- Forming spherical aggregates
- by spray-drying with binder (cellulose-acetate, polystyrene, polyvinyl-alcohol)
- by spray-drying without binder, application of heat
- by mechanical aggregation in a shaking/sieving procedure (“sieving in”)

Aspects for decision: time consumption, material consumption, stability and density
of the samples, loss of intensity by dilution, sample transparency, alteration
of minerals, reproducibility, labour protection…

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Problems Milling Filling Examples

Making the powder mount for Bragg-Brentano XRD 2
Simple tricks may make the difference…
Front-loading (standard holders, very popular)
- powder pressed using a glass slide: very easy, but extreme PO
- powder roughened by emery paper: not so much PO, but badly reproducible
and depending of the properties of the powder
- surface roughened by a razor blade: as above, plus high roughness
- sprinkling/sieving some powder on the surface: good randomness, but errors
in sample height, high roughness, sometimes phase separation
- possible to do with any kind of aggregates, perfect randomness possible

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 Problems Milling Filling Examples
Making the powder mount for Bragg-Brentano XRD 3

Back-loading (special Philips/Panalytical equipment)

- easy to do, but extreme PO
- no chance to use for unstable aggregates like freeze-dried clays

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Problems Milling Filling Examples

Making the powder mount for Bragg-Brentano XRD 4
Side-loading (with special side-opened holders, but also for standard holders)
- with normal powder: relatively easy, reproducible, acceptable PO
- with irregular aggregates: perfect randomness possible
- general problems are density, homogeneity, and stability, e.g. for rotated
samples

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Problems Milling Filling Examples
Errors in sample preparation 1
Influence of overmuch large grains on the powder pattern

Comparison of 2 Scans
300

< 63 µm
< 20 µm
plag 002/040
200
topaz 230
kfsp 002/040
Intensity / cps

preferred „rocks in the dust“

orientation!
100

0
25 30 35 40
2 Theta / ° ( Sc an Axis : 2:1 s ym. cons t. area )

topaz bearing granite, samples ball-milled < 63 µm and hand-ground < 20 µm

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Problems Milling Filling Examples

Errors in sample preparation 2
Phase separation and loss of material during powder preparation

mica + quartz lost by

dusting during dry
sieving

halite dissolved
in ethanol

Mineral mixtures, ground by hand/dry sieving < 20 µm and

McCrone milling/ethanol, filtered slurry
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Problems Milling Filling Examples
Errors in sample preparation 3
Sample contamination by abrasion from grinding elements

corundum line positions

Kaolin Spergau reference sample, McCrone ground using

corundum grinding elements and using agate grinding elements
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Problems Milling Filling Examples

Errors in sample preparation 4
Preferred orientation of grains/aggregates dependent on filling technique
Comparison of 2 Scans

400 bentonite, fraction < 0.2 µm

02,11

300

side-loading
Intensity / cps

200
front-loading
005

100
06,33

0
20 30 40 50 60
2 Theta / ° ( Scan Axis: 2:1 sym. ) 20

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Problems Milling Filling Examples
Errors in sample preparation 5
Preferred orientation of grains/aggregates dependent on filling technique

Ms+Dc
110,
Ms
020
Dc 060
002 Dc
060
Ms Ms
002 004 Spray-dried
front-loaded

Powder
side-loaded

Powder
front-loaded

Mixture quartz/dickite/muscovite 40:30:30, McCrone milled, different

filling techniques (from Kleeberg et al., 2008)
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