Jiangsu Skyray Instrument Co., Ltd.

Technique of sample preparation

The technique of sample preparation is essential for obtaining a better result when
analyzing samples. The technique of sample preparation will affect the accuracy of the result
of the X-ray fluorescence analyzing.
1.the preparation of standard samples

the X-ray fluorescence analyzing method is different from the chemical method, it is a
comparative measuring method ,which gets the accurate result by establishing the
corresponding mathematical model after measuring a certain mount known samples (standard
samples) .in another word, a series of good standard samples is as important as a good
instrument. A good instrument is provided by us, while a good series of standard samples is
provided by the users’ laboratory. A good series of standard samples be of the following
features: Be representative, Be of certain content range, and Be of accurate chemical
analyzing result, the details are as follows:

●Sample amount:5-10.each mass:50-100gram

●Be representative: the samples can represent the actual products of your factory, and is
the instantaneous samples from the actual production line, and try to avoid the artificial
prepared samples, which will bring in subjective factors. and do not use national standard
samples, for each factory use different raw materials and different formula, and will get
different mathematical model.

●The content range of main chemical constituents.

The content range of main chemical constituents in standard samples should cover the
variation range of content of main chemical constituents in normal products, and should keep
distance with each other and be well-distributed. take the cement raw material as an example:
in normal condition, in raw material (white raw material) if the target value of content of
CaO is 42%, then, to keep distance, the minimum of the content of CaO will be about
39%,and the maximum of it will be about 45%,to make the content of CaO well-distributed,
the content of CaO should be 39%(minimum),40%,,41%,42%,43%,44%,45%(the maximum).
You may prepare extra several this kind of standard samples of which the content be in the
normal variation range(41%~43%). (Tab 1)
It’s a series of standard sample of white raw material, and the target value of main
chemical constituents is as following respectively:
Al2O3:3.1%, SiO2:13%, CaO:41.5%, Fe2O3: 3.5%
In tab.1, we can get that: the content of main raw material keep a certain distance from
each other and be well-distributed. the variation range of Al(the maximum subtract the
minimum) is2.5%, the variation range of Si is 4-6%, the variation range of Ca is 4%-6%, the
variation range of Fe is 3%.there is no factitious regularity between Al and Si, Si and Ca, Ca
and Fe.
Generally speaking, the variation range of high content element is larger than the
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variation of low content element, and the lower the content is , the smaller the variation range

Tab.1 white raw material data:

Na2O MgO Al2O3 SiO2 SO3 K2O CaO Fe2O3
1# 0.22 2.84 3.46 16.38 0.66 1.08 38.60 3.46
2# 0.38 2.50 3.73 15.79 0.18 1.31 38.89 3.24
3# 0.22 1.97 3.57 15.61 0.18 1.01 40.03 3.59
4# 0.18 1.79 3.06 13.92 0.16 0.94 40.42 5.29
5# 0.43 1.93 3.48 14.72 0.45 1.17 40.39 3.44
6# 0.17 3.28 2.87 12.16 1.18 0.92 40.66 3.29
7# 0.16 2.25 4.38 12.93 0.30 0.96 40.92 3.50
8# 0.17 1.92 3.19 13.62 0.18 0.98 41.22 4.33
9# 0.18 1.81 3.04 13.04 0.16 1.10 41.72 3.54
10# 0.56 1.82 4.10 11.96 0.75 0.87 41.94 3.21
11# 0.26 2.30 2.80 11.37 0.11 1.11 43.03 2.11
12# 0.12 1.94 2.53 10.50 0.15 0.75 44.30 2.66
13# 0.11 1.70 2.09 8.84 0.14 0.70 45.86 2.26
covers. those element with the content 40%~80% cover the rang:5%~10%. The variation
range of those elements whose content is between 10% and 30% is 4%~8%,for the elements
whose content is under 10% ,its variation range is 3%~5%.

●Preparation of the high content samples and low content samples.

In the series of samples, the samples whose content is near the target value can be
collected from the production line. Those samples whose content is much higher or lower
than the target is hardly available directly from the normal production line. We must prepare
those samples by ourselves. Take the white raw material as example (Tab.1). In normal
conditions, the content of CaO is controlled in 41%~42%，If we want to get the samples
above 45%, we must add limestones in the raw material to increase the content of CaO and
decrease the content of Al2 O3, SiO2, Fe2O3, in the same way, we can prepare high SiO2
samples and high Fe2O3 samples. the samples whose content is near the target value must
be collected directly from the production line.
NOTICE: try to avoid preparing artificial samples. When sample has to be prepared
manually, you should add only a little raw material to a mass of practical manufacture
samples, and the raw material must be same as the manufacture samples. In order to reduce
factitious regularity, users must not use the same manufacture material to prepare different
samples (one manufacture sample can be use to prepare for only one manual sample).

●mixing material:

When users prepare sample manually, it must be well-distributed. We discovered that

many users don't do well in mixing material .If the materials are not well distributed, even for
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the same sample, the parts for total-chemical analysis may be different from the parts for
instrumental analysis, this may lead to large error between the chemical analytical values and
instrumental analytical values, and then influence the accuracy of the instrument. Mixing
material is critical for subsequent process though dreary, however, If this step is not done
well, even if subsequent processes is done so strictly, so meticulously, the result will be
beyond remedy. Mixing material must be done in a entirely sealed environment, for lessening
the loss of light matrix element content. And avoiding the variance between sample and the
things which will be tested. Generally, it needs 15-30 minutes to mix a sample manually.

●Chemical analysis:

Fluorescence spectrometer analysis is based on chemical analysis, if chemical analysis is

not accurate, the mathematical model will have great errors, even can not be used. So, for the
sake of accuracy of chemical analysis, this step must be done by two excellent operator, and
adopt the average as the final result when the error of each result is within the allowable
range of the GB/T176-1996. If the error is oversized, users should check and delete and
wrong value. In this process, the operators must not compare with each other, nor juggle the
results.

● Storage:

When sample series is prepared well, seal them in ground glass bottles, and label them
for long-term use.

2：molding of standard samples and unknown samples

Mineral samples for XRF require proper sample preparation, all the samples need both
coarse grinding and subsequent fine grinding, and molded under 30Mpa pressure to correct
the granular effect, grain effect and matrix effect.

● Fine grinding

Raw material: Weight 30g samples (accurate to 0.05g), 0.2g stearic acid (accurate to
0.0001g) (grinding aids, preventing caking and improving grinding efficiency), fill in
vibration mill, grind for 2 minutes.
Clinkers: weight 30g clinkers (accurate to 0.05g), 1g stearic acid (accurate to 0.0001g), fill in vibration
mill, and grind 3 minutes.
Gypsum, iron powder: weight 30g sample(accurate to 0.05g),1g stearic acid(accurate to
0.0001g),fill in vibration mill, grind 3 minutes.
Sand stone , shale, fly-ash: weight 20g sample(accurate to 0.05g),1g stearic acid(accurate to
0.0001g),fill in vibration mill, grind 1 minutes.
All the above grinding time is for reference only. Users should fix the best grinding time
according to actual grinding efficiency. user can increase the grinding time of a reference
sample, and at the same time, measure the intensity of the characteristic X-ray, until the right
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time that the intensity do not rise with the increase or decrease of grinding time.
NOTES: users must have the container of the vibration mill cleaned before grinding
every sample. And the-grinded sample must be stored in ground bottle flasks, and labeled
with sample number, and date.
Grinding aid plays the role as dispersant, preventing caking, improving grinding
efficiency and reduce energy consumption. There are many sorts of grinding aid, such as
stearic acid, glycerol and alcohol, propanol, isopropanol, triethanolamine, and urea etc.
Standard samples and unknown samples must use the same grinding aid. Changing the
grinding aid must change the standard sample powder, and squash again and establish new
work area.

● Squashing

1. The upper surface of the base of mill, the inner and outer surface of mill sleeve, must be
cleaned and make sure that no residues and boric acid left. Assemble the mill according to
Fig 1.
2. Weight 7g (accurate to 0.05g) grinded sample, and fill in the sleeve gasket and level the
sample by leveling rod.
3. Weight 7g (accurate to 0.05g) boric acid, fill half of it into the middle of the mill sleeve
and sleeve gasket. drop out the sleeve gasket carefully, and fill in the left boric acid and level
it.
4. Assemble the mill rod.(Fig 2)
5. Carry the mill to the center of the working platform of the presser, set the pressure to
30MPa, keep for 30s and disassemble the mill.
6. take the mill base out and invert the mill（Fig.3）. Put on removal, and buttress the middle
of the removal, then beat on the top of the removal with rubber hammer. you can take out the
sample.
7. The sample should not be contaminated, scraped, or splitted, otherwise, you need to do it
again. It is suggested to write the number, date on the back of the sample with the pastel.
8. Clean the mill. if the mill was left unused for a long time, grease should be smeared on the
surface to prevent rusting. The mill should be carried carefully to avoid base scrape.

Fig.1 Fig.2 Fig.3

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Appendix
Analysis on the error source of XRF spectrometer
The stability and reproducibility of XRF spectrometer has little influence on the precision,
and the performance of XRF spectrometer is characteristic of the theoretic statistic error of
intensity of XRF spectrometer. The sample preparation technique plays a important role and
will be reflected in the results. The error source of XRF spectrometer is as follows:
1, sampling error:
Heterogeneous Material
Representative of sample
2. Sample preparation
Stability of the preparation technique
Technique of preparing homogeneous samples
3. Irrelevant standard samples.
Whether the content of unknown samples is in the cover range of the standard samples or
not
Accuracy of chemical analysis result of the standard sample
Stability of the samples and standard samples
4. Instrument error
Statistic error of count
Location of samples
Sensitivity and drift
5. Irrelevant quantitative mathematical models
Irrelevant algorithm
Element interference effect is not calibrated
● granular effect
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the fluorescence intensity of pure material increase with the decrease of the granularity.
In multi-element system, fluorescence intensity of some element has been proved to be
related with matrix effect, which can increase some element intensity and decrease some
element intensity.The relationship between intensity and grinding time is as showed in Fig1:
①the decrease of element granularity decrease the intensity of Fe, S, K, and increase the
intensity of Ca and Si. ②The intensity tend to be stable when granularity decrease to a
certain degree. ③The intensity of low Z element changes a lot with decrease of granularity.
●Material effect
There are some cement raw prepared by different material(Fig 2), the samples marked I
are composed of limestone, shale, iron ore. the samples marked F contains the same
limestone and iron ore, but contains different silicon, in which, shale is replaced by sandstone.
Two kinds of raw material are treated with the same equipment ,and grinded by the same
grinding machine. And 85% of them passed 200 mesh. It’s obvious that change of
intensity-content relationship show the different resource of silicon. In fact, it is just a matter
of granularity, when the sample pass 325 mesh by increasing the grinding time, all points are
located in the same curve.
●Matrix effect
All materials measured by XRF are required that the intensity of element is proportional
to its content. in the complicated matrix such as rock s and ores(the composite of at least two
kind of materials), for the influence of other elements, the intensity may not be proportional
to its content. generally, this nonlinear relationship is caused by elemental matrix effect.
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Matrix effect is absorption effect or enhancement effect, or the combination of them.

Longer grinding can improve the CaO analysis result(Fig 4). After the calibration of
interference of K, the points of two series of samples locate in the same curve.