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Sampling for Particle Size Analysis

www.malvern.co.uk
This product support brochure applies to the
following Malvern Instruments’ products:
Mastersizer 2000
Mastersizer S
Mastersizer Micro
Mastersizer Microplus
Author: Dr Alan Rawle
Malvern Instruments, UK
Like most things in life you get out what you put in. This cannot apply more
strongly than in the situation of particle sizing where “garbage in = garbage out”
is an appropriate maxim.
If we consider a pack of cereal such as museli, it is quite obvious that the last
two teaspoons taken from the packet are not the same as the first two. For
systems like this, then it is clear even to the non-scientist that segregation has
occurred (“the contents of the package may have settled during transit”) and that
the properties of the first and last samples from the packet are totally different.
As scientists (hopefully!) we need to quantify these effects and decide when this
phenomenon is important from a statistical point of view and when it is not.
A more serious example of the “garbage in = garbage out” situation was that
resulting from the confusion in UK Government laboratories between cow and
sheep brains (“bovine or ovine?”) resulting in the causes and transmittal mode
of BSE being misinterpreted. This prompted the quotation within the editorial
of the December 2001 issue of Chemistry in Britain that “Sample integrity and
sound data analysis are essential cornerstones of valid analyses for decision making”.
Thus before we even begin the statistical evaluation, we need to ask ourselves the
reason or objective behind the analyses
12
(because one analysis on its own would
be statistically perfect):
What do we want to know?
Why do we need this information?
What happens to the results?
What actions may follow (and the economic and other implications) of the
results being circulated?
We also need to ask ourselves whether we require a bulk powder measurement
designed to investigate say, for example, flowability, filter blockage or dusting
tendency or whether we are concerned with a primary size of the particle system
as the latter may control dissolution rate, gas absorption
and chemical reactivity. We need to be aware that the
energies generated in any particle size “dispersion unit”
or accessory are likely to be many times larger than
those within a production environment. For example,
a hydrocyclone operates only at a few ms
-1
in contrast
to the typical 70W of a low powered sonication bath.
A good illustration of the effect of segregation can be
seen in any large mine spoil heap or, more conveniently,
in small demonstrators available from Jenike and Johanson:
2
Sampling for Particle Size Analysis—
Introduction
A similar photograph of a heap of powder is present in the first figure of the first
chapter of the standard particle size reference text
1
but as no one bothers to read
this chapter we will need to reinforce the science and conclusions therein.
The questions we need to consider are:
How many analyses are needed for statistical validity?
How much sample is required from the bulk (in both number and weight of
particles) in order to ensure that we are taking something that is representative
of the whole?
3
2. How many analyses?
Q
A
Some of the follow up questions in a production sense could concern batch
uniformity—how do we get as many brasil nuts on the last spoon of museli as
the first? Again, with a more serious example, how can we control the amount of
active pharmaceutical a patient receives where our dosage form is made of active
and excipient? It is obvious but if every particle in the system is identical then we
would only need to remove one particle for it to be representative of the whole.
In reality this will never be the case.
The number of analyses needed for statistical validity is the easiest to answer
and we will therefore tackle this first, although it is usually applied more often
to chemical and physical measurements other than particle size determination.
The probable error or standard error (SE) in multiple measurements is given by:
SE = 2/3 [∑(x – x
m
)
2
/n]
0.5
where x is any sample measurement and xm the mean of the samples and n the
number of samples.
Let us take an example of taking 5 samples in which the average particle size is
(perfectly measured) 29.0, 27.5, 24.5, 22.0 and 20.5 microns.We may ask ourselves
what is the number of measurements needed to give a precision of 1 µm on the
mean? Excel handles this easily but in long-hand:
The mean is easily calculated as:
x
m
= ∑x/5 = (29.0 + 27.5 + 24.5 + 22.0 + 20.5)/5= 24.7 µm
∑(x – x
m
)
2
= (29.0 – 24.7)
2
+ (27.5 – 24.7)
2
+ (24.5 – 24.7)
2
+
(22.0 – 24.7)
2
+ (20.5 – 24.7)2 = 4.32 + 2.82 + (- 0.2)
2
+
(- 2.7)
2
+ (- 4.2)
2
= 18.49 + 7.84 + 0.04 + 7.29 + 17.64 = 51.3
The standard error is 2/3 X (51.3/5)
0.5
= 2/3 X (10.26)
0.5
= 2/3 X 3.20 = 2.1 µm
If a precision of ± 1µm is required then we can calculate the total number of
samples to be taken as:
2.1/1.0 = (n/5)
0.5
= 22.1
Thus 23 samples would be required.
This is not the usual situation that we are trying to deal with in particle size
analysis. Indeed in the above situation we are so subject to the vagaries of the
sampling method (are these independent samples?) and the dispersion method,
that this answer is almost meaningless. Besides the British Standard Customer
(BSC) will only take one measurement anyway…
The more important question that is usually requiring a statistical answer is the
minimum amount of sample that would be needed to ensure that it could be
representative of the whole or at least a rough guide to what we would expect
to need. Clearly there will be a number of assumptions needed to answer this
particular issue. It is an issue that has occupied chemical engineers since 1880
or so (e.g. Reed). Taggart’s Handbook of Mineral Dressing (1948) gives a
nonogram for minimum weight (based on type of ore—rich or lean—and
particle size) based on the assumptions of Richard (1903) which has been
the reference in the mining industry from thereon. Gy’s work
2, 3
(1953, 1982)
is extensively quoted where the weight of sample required is proportional
to d
a
where the exponent is a variable between 2 and 3 but theoretically 3
(the number – volume/mass relationship). The constant of proportionality is
dependent on the accuracy desired, the homogeneity and value of the ore.
Even later pragmatic work by Kraft (1978 and summarised in 4) is of little value
as multiple determinations (he recommends 20 and talks of 1 kg shovels full!)
are needed and this is not helpful to engineers seeking ballpark figures before
beginning an analysis.
So we need to seek more practical solutions. Let us start from the basis that we
require a standard error of 1% and that the mid-point of the highest size band
is known (d
99.5
is close enough unless the pedants insist on a more accurate
geometrical midpoint assuming a logarithmic spacing of size classes).We will further
assume that this highest size band contains 1% of the material by mass or volume
(constant density assumed of a single component system).This is probably reasonable
if the customer believes that 100 size classes equate to resolution! So we can
calculate the number of particles required in this highest size band:
1/100 = 1/n
0.5
leading to a need for 10000 particles in the highest size band. The number 10000
is interesting (although it does not provoke a large entry in the Book of Interesting
Numbers
5
. In fact it provokes no entry at all in the aforementioned volume) as it is
the same number of images (not particles) that NBS (National Bureau of Standards)
stated that was needed for statistical validity in image analysis
6
:
“S(tandard error) is proportional to N
-1/2
where N is the total number of particles
measured…This consideration implies that image analysis may require the analysis
of on the order of 10000 images to obtain a satisfactory limit of uncertainty”
(p718, paragraph 1).
4
Weight of sample versus maximum size
0
20
40
60
80
100
120
140
160
180
0 100 200 300 400 500 600
Mid point of last size band
W
e
i
g
h
t

o
f

s
a
m
p
l
e

(
g
)
Weight of sample and maximum size
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 20 40 60 80 100 120
Mid point of last size band
M
i
n
i
m
u
n

w
e
i
g
h
t

o
f

s
a
m
p
l
e

r
e
q
u
i
r
e
d

(
g
)
This minimum number of particles for 1% or better SE is then more useful as
with knowledge or assumptions about the particle density, a spreadsheet is easily
constructed and we are able to get a feel for the sort of sample size required:
3. How much weight/mass of sample is required?
Q
A
More rigorous theoretical solutions are provided by Masuda and Gotoh
7
and
enhanced by Wedd
8
, but the figures crudely calculated above in the spreadsheet
are in the same ballpark. We note that the old maxim that 75 or 100 µm provided
the point at which sampling became the predominant error in particle size
analysis is easily understood if a sample size of around 1g is assumed for many
analytical techniques. See below:
5
D Diameter Radius Density Weight in top Total weight (g)
(µm) (cm) (cm) (g/cm
3
) size fraction (g) (= Last column X100)
1 0.0001 0.00005 2.5 1.31358E-08 1.31358E-06
10 0.001 0.0005 2.5 1.31358E-05 0.001313579
100 0.01 0.005 2.5 0.013135792 1.313579167
1000 0.1 0.05 2.5 13.13579167 1313.579167
10000 1 0.5 2.5 13135.79167 1313579.167
200* 0.02 0.01 3.15 0.13240878 13.24
80 0.008 0.004 3.15 0.008474162 0.85
This is the weight This is where 1%
of 10000 particles of the particles are
in the top size band
Assuming spheres
*This represents a typical cement
4. Reliability of sampling methods
We can then decide on appropriate sampling regimes for the mass of material
that we take as a (minimum) base sample calculated from the above spreadsheet.
Note that it would be meaningless if we have material up to say 500 µm in the
sample to try to measure 50 mg or so (1 particle?). At 1mm we need over 1 kg of
material to have 10000 particles in the highest size band. To examine Allen’s
(frequently quoted) summary of sampling methods at this stage is extremely
educational (and will lead on to answering the question “How do we take the
sample as opposed to how should we take the sample?”):
Reliability of selected sampling methods using a 60:40 sand mixture
Sampling technique Standard deviation
Cone and quartering 6.81
Scoop sampling 5.14
Table sampling 2.09
Chute slitting 1.01
Spinning riffling 0.146
Random variation 0.075
Taken from Table 1.5 page 38,T.Allen Particle Size Measurement, 5th Edition Volume 1
Chapman and Hall 1997 ISBN 0 412 72950 4
The most common way that sample are taken within industry (scoop or spatula)
is subject to an expected standard deviation of just over 5%. Thus if we are using
this technique we could not expect to specify our material to better than 20% or
so (3σ covering 99.7% of a Gaussian distribution is around 16% with this method).
The choice is either to employ a spinning riffler for sample division or widen
the permitted specification. Thus the recommendations in ISO13320
9
Section
6.4 which deal with repeatability allow for 3 consecutive aliquots a deviation
of 3% for the D
50
and 5% for the D
10
and D
90
in the tails of the distribution.
This could only be achieved for samples that have either been correctly divided
or were small enough that sufficient particles were in the highest size band. Thus
this is a reasonable check on the homogeneity or otherwise of our sample rather
than on the performance of the instrument. By the way, the doubling of the
“permitted” deviations under 10 µm is more related to control of the dispersion
of the material than to sampling.
6
7
5. Practical sampling methods
Back to our important question on the best way to take a sample. Spinning rifflers
have been around for at least 100 years. Here is an early version made of wood
and buckets
10
:
The modern version is with stainless steel trays or glass bottles:
From companies such as Retsch or Microscal units can be obtained that will
deal with 10 g – 100 kg of sample. These are conveniently and usually used in the
laboratory in order to split a primary sample into a size suitable for measurement
for, say, XRF or laser diffraction. One must realise at this stage that this method is
the only one capable of producing less than 1% sample to sample variation. If one
does not employ a rotary dividing technique and one wants less than 1% coefficient
of variation sample-to-sample then this will certainly end in tears. The other
alternative is to use scoop sampling and work with a larger acceptable specification.
Vibrating Sample Hopper
Sample Trays
Cone and quartering, although reasonably common, should never be employed
11
:
Chute riffling is barely acceptable
(just over 1% RSD):
Riffle sample divider
(Reproduced by permission
from BS 5309, Part 4, 1976)
So what if we have a large mine dump or a glacial moraine (“so what?” you may say):
8
1
2
3
4
5
6
60˚
Alternative sections collected
on each side
7
8
9
10
11
11
9
7
5
3
1
12
What are the rules for sampling here? Allen provides two words of advice—don’t
and never. However, this is more flippant than practical (thus appeals to me!) and
we need to outline the golden rules of sampling as expounded by Allen and
others on many occasions:
Take the sample when the product is moving. This could be when a large
drum or container is packed. Once in the drum we’re then subject to any
settling that takes place during transport. If this is not practical then we’re back
to the choice of either spinning riffler or a wider specification or experimental
evidence/statistics on the basis or real-world experiments
Take the entire stream for a short period rather than part of the stream for a
long period. This is to avoid taking samples say at the edge where air currents
could influence what is sampled or in the middle of a pipe where particle size
distribution is not the same as close to the edges. This indicates that cross-
stream and Vezin type samplers must be statistically better than putting a fixed
probe into a stream.
The above photographs show the boulder-like particles (larger than a man together
with the sub-micron rock flour in suspension at the Franz Josef Glacier in New
Zealand). In all cases repeated samples (to reiterate, Kraft’s recommendation is 20)
should be taken to assess the homogeneity or otherwise and to get a feeling for the
expected variations. Even this may have problems with friable or fragile material
(e.g. needle-like pharmaceutical) where the simple act of sampling a barrel or
container of powder with a spear is likely to cause damage to the particles:
Open-sided sampling spear and divided spear for dry, free-running powders (Reproduced
by permission from ‘The Sampling of Bulk Materials’, by R. Smith and G.V. James,
The Royal Society of Chemistry, London, 1981)
9
TYPICAL CROSS SECTIONS
For mines and piles of materials then trenches can be dug and the literature
(e.g. 1 and 11) contains details of these methodologies. However, actual measurements
will indicate the huge spread of particle sizes in such situations and would be more
practical than the flippant “Don’t/never!” advice.
Slurry sampling is potentially much worse than sampling of dry powders in
that segregation or settling is almost certain to be occurring. Extreme care and
evaluation needs to be taken when sampling from a pipe or in a wet grinding
situation as it is a virtual impossibility that the system is homogenous from
a particle size point-of-view A Burt sampler is normally recommended
for slurry or suspension sampling:
The Microscal suspension sampler, 100 mL to 10 mL
10
6. Experimental results
It is reasonable now to examine some practical results of sampling that we have
carefully undertaken at Malvern Instruments on purified teraphthalic acid (PTA)
both as a dry powder and as a prepared slurry in water.The material is quite large
and exhibits the potential for significant sampling errors.The recommendations of
ISO13320 were followed in that, for riffled samples, the complete sampled sub-lot
was used for the measurement. Repeatability was assessed for wet measurements
(the marks on the plots indicating the full set of results) by taking 10 consecutive
repeat measurements.
Consecutive dry sampling of large material (PTA)
20
70
120
170
220
270
1 2 4 6 8 10 3 5 7 9 11
Record number
Trend graph
d (0.1)
d (0.5)
d (0.9)
Mean
SD
% Variation
37.88
3.03
7.99
121.21
4.05
3.34
257.17
13.68
5.32
D10 D50 D90
P
a
r
a
m
e
n
t
e
r
For successive scoop sampled aliquots we see standard deviations in line with those
noted by Allen:
11
We note too that the effect is only just seen at the D
90
end of the distribution—
there is virtually no effect on the smaller D
10
and median, D
50
, points.There is
a gradual fall in D
90
as we remove the larger material (the nuts and raisins in the
museli), which sits on top of the pile, but one can see why this type of (subtle)
trend is rarely noted. In the case of a slurry sample we get an interesting step-effect:
The initial samples were taken by pipette withdrawal from a well and continuously
stirred (magnetic stirrer) slurry of the material contained in a beaker.This material
in suspension shows little change.The step is at the point when no liquid remained
and one started to sample, by spatula, the paste sitting at the bottom of the beaker.
This shows segregation effects by the gradual rise in key parameters shown above.
D10
D50
D90
Consecutive wet sampling of large material (PTA)
Sedimentation in Sample
0
100
200
300
400
0 20 40 10 30 50
Sample number
S
i
z
e

(
M
i
c
r
o
n
s
)
Mean
Standard deviation
% RSD
Number of samplings
52.11
8.83
16.34
40
141.12
22.22
15.75
316.02
49.80
15.76
D10 D50 D90
In terms of samples extracted by spinning riffler and measured in their entirety we
see no discernible trends in D
90
over the 25 trays of the riffler:
12
We note that in practical terms I cannot approach the wonderful (ideal?!) s.d.
figures quoted by Allen but I can considerably improve on the values generated by
simple scoop or slurry sampling and remove any systematic variation.
7. Implications for product homogeneity and mixing
Last, but by no means least in practical terms let us examine some rules of thumb for
product homogeneity.The author has witnessed a large pharmaceutical manufacturer
being unable to control the dose of active ingredient with an inactive base material
and this type of observation has been reported in the literature on numerous
occasions
13, 14
.This was simply due to the large differences in sizes—micronized
drug together with inactive up to 1000 µm or so.The general rule here is that we
will reduce the propensity to “unmix” by mixing particle size distributions that do
not differ by more than 0.3 – 1.4 (or 40% or so).The solution for the pharmaceutical
customer above was obvious—micronize both the active and inactive. As an example
if the drug is of mean size 50µm then to introduce a filler of 100 µm is inadvisable.
Rather the filler should be within the range 15 – 70 µm. Small particles or a broad
distribution aid packing and compaction strength and can help flowability issues.
When small particles adhere to coarse ones then more homogenous mixtures can
result but this could be in conflict of making smaller drugs for more rapid dissolution.
As is usually the case a balance must be sought between particle size distribution,
flowability and homogeneity.
A corollary to this relates to the recommendations within ISO13320 relating to
verification of laser diffraction equipment. Here spherical materials of no more
than 1 decade in diameter distribution are stated to be preferred. Although a 1 – 10 µm
(or 10 – 100 µm) range in diameter does not appear significant it is equivalent to a
1000-fold difference in weight or volume so segregation is a real possibility unless
the particles are particularly small where attractive forces bind them together.
USE OF SPINNING RIFFLER
0
100
200
300
400
0 20 10 30
Riffled sampling variation
Record number
S
i
z
e

(
M
i
c
r
o
n
s
)
Mean
Standard deviation
% RSD
Number of samplings
52.78
1.97
3.74
25
138.18
4.36
3.15
325.16
6.13
1.88
D10 D50 D90
D10
D50
D90
13
8. Implications for particle size measurement by laser diffraction
Measurement by laser diffraction is characterised by a number of requirements
that need to be met.
To avoid multiple scattering (a number/concentration/size constraint) then
measurements are normally run at fairly low concentrations—typically 0.01 – 0.001
volume %. A pharmaceutical manufacturer may ask “What is the smallest amount
of material that can be measured?” and may be wanting to minimise the amount
of sample (expensive R & D material?) or exotic or dangerous or expensive solvent
(at least for disposal). Hence the unwary customer and salesperson may be riding
along the possibly dangerous track of specifying a small volume dispersion unit
without remembering the requirements for adequate sample mass and also the need
to keep material adequately in suspension. Failure to control either leads to lack of
repeatability (consecutive measurements—the small number of large particles is not
integrated a sufficient number of times or the larger particles are only occasionally
“kicked” through the laser beam) and poor reproducibility (sub-sample to
sub-sample variation based on the homogeneity or otherwise of the sample).
With a small volume unit we may only be using a small volume of dispersant and
thus we could never load the amounts of material required for adequate sampling
(at reasonable levels to ensure multiple scattering does not occur
15
) into the unit
especially if the sample has any polydispersity. And if we sub-sample from our
starting material there is an enormous danger that what we take (e.g. 50 mg) will
certainly not be representative of the whole or if the sample has larger material
present that the 10000 particles in the highest size band cannot be met.
Clearly it is the precision in the D
90
or higher point of the frequency curve that
becomes affected. Customers that try to specify a D
99.5
or similar based on sieve
type measurements are either deluding themselves or will have to select much
wider tolerances on acceptable precision. The specification of a D
100
(so if we
don’t find the single largest particle in the glacial moraine then the second biggest
is the D
100
?) is so obviously ludicrous from a scientific point-of-view that such
people need to be subjected to the Inquisition and burnt at the stake. The fact
that some instrument manufacturers put such numbers on their analysis sheets
shows that marketing and ignorance (normally mutually inclusive) rather than
science and logic has played the main role in the decision making.
Thus from a sampling only point of view a small volume dispersion unit may only
reasonably be selected if the particle size is small and/or narrow distribution. Of
course a monodisperse sample would only require a single particle for statistical validity.
Thus a larger sample dispersion unit even if it requires larger amounts of solvent may
be the best statistical route to high precision with a fragile or friable material that is
not capable of dry dispersion.There are constraints to on dry dispersion—the sample
cannot be re-measured again or indeed repeat measurements taken on the same group
of particles as is the case with wet—it’s lost to the vacuum cleaner—which may be
a problem if the sample is expensive and needs recovery. If we have plenty of sample
and the material is capable of being suspended in air plus it will not exhibit attrition
effects then dry would be a reasonable choice.The real answer to the pharmaceutical
customer’s question relates to how much the customer is prepared to lose and the
desired degree of precision based on the material’s particle size distribution. Indeed
in certain cases if the entire universe of material (the whole lot!) is not taken for the
analysis for a larger and/or polydisperse sample then the whole analysis may have
dubious merit and it may be a case of garbage in – garbage out.
9. References
1. T Allen Particle Size Measurement 5th Edition Volume 1 Chapter 1 page 3
(Figure 1.1) Chapman and Hall 1997 ISBN 0 412 72950 4
2. P Gy R. Ind. Min. 36, 311- 345, (1953) (in French)
3. P Gy Sampling of Particulate Material, Theory and Practice 2nd Edition
Elsevier, Amsterdam (1982)
4. G Kraft (Editor) Sampling in the non-ferrous metals industry: concentrated
and recycled commodities Series on Bulk Materials Handling Volume 6 Trans
Tech Publications 9 – 11 (1993) ISBN 0 87849 085 X
5. David Wells The Penguin Dictionary of Curious and Interesting Numbers
Penguin Books: London, 1986
6. A L Dragoo, C R Robbins, S M Hsu et al “A critical assessment of requirements
for ceramic powder characterisation”Advances in Ceramics Vol 21 Ceramic
Powder Science (1987). The American Ceramic Society Inc. (p711 - 720)
7. H Masuda, K Gotoh Study on the sample size required for the estimation of
mean particle diameter Advanced Powder Technol. Vol 10(2) 159 – 173 (1999)
8. M W Wedd Procedure for predicting a minimum volume or mass of sample
to provide a given size parameter precision Part. Part. Syst. Charact. 18 (2001)
109 – 113.
9. ISO13320 Particle Size Analysis—Laser Diffraction Methods. Part 1: General
Principles ISO Standards Authority, Geneva (1999). Note: Can be downloaded
as a .pdf (Acrobat) file from http://www.iso.ch with credit card.
10. Walter Lee Brown Manual of Assaying Gold, Silver, Lead, Copper. 12th
Edition E H Sargent and Son Chicago 1907
11. Perry’s Chemical Engineering Handbook. Images were taken from the
1950 edition.
12. N T Crosby, I Patel General Principles of Good Sampling Practice Royal
Society of Chemistry 1995 ISBN 0 85404 412 4
13. J A Hersey Int. Conf. on Powder Technology and Pharmacy 6 – 8 June 1978,
Basel, Switzerland. Powder Advisory Centre, London (1978)
14. D Train Pharm J. 185, 129 (1960)
15. M Wedd “The minimum mass of particles required to achieve a given repeatability
of a size parameter”To be presented at 4th World Congress of Particle Technology
(WCPT4) Sydney Tuesday 23 July 2002 Stream 1 11:00 hours
14
Malvern Instruments is part of Spectris plc, the precision instrumentation
and controls company.
www.spectris.com
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