M.

Mladenov,
J. Jordanov
Journal of the University of Chemical
Technology
and Metallurgy, 47, 1, 2012, 103-108

PREPARATION OF SECONDARY STANDARDS

FOR X-RAY FLUORESCENCE ANALYSIS IN THE PRODUCTION
OF MOLYBDENUM CONCENTRATE
M. Mladenov1,2, J. Jordanov2

University of Chemical Technology and Metallurgy

8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: mladenov@uctm.edu

Received 01 November 2011

Accepted 16 January 2012

Institute of General and Inorganic Chemistry

of the Bulgarian Academy of Sciences,
Department of Analytical Chemistry,
X-ray fluorescence laboratory,
11 Acad. G. Bontchev Str., 1113 Sofia, Bulgaria

ABSTRACT
In practical applications, for X-ray fluorescence analysis (XRF) of molybdenum concentrates, there is not elaborated
and certificated standards. Factories and producers of molybdenum, work with own secondary standards or with the
methods of the wet chemistry. In this aspect for obtaining of correct data from the analysis it is very important the
secondary standards to be prepared correctly and precisely.
In this work data from the preparation of secondary standards for quick quantitative XRF analysis are discussed.
The obtained results from the analysis of Mo, Cu, Fe and Re by methods of Wave dispersive X-ray fluorescence (WDXRF) analysis and total X-ray fluorescence (TXRF) analysis, in the preparation of secondary standards are also presented.
Keywords: secondary standards; molybdenum concentrate; wave dispersive X-ray fluorescence (WD-XRF) analysis;
total X-ray fluorescence (TXRF) analysis; practical use.

INTRODUCTION
In the production, the express method for
determination of the element concentrations in
molybdenum concentrates is indispensable. One such
method is the X-ray fluorescence (XRF) analysis. This
is the most often used technique for analysis of the ore
and the final products in the metallurgical process. The
method is fast and effective and it provides required
accuracy and reproducibility, both for tracking of the
process and for the certification of the final products
[1-3].

Different calibration methods for quantitative

XRF analysis can be employed but the most frequently
used is the method of the calibration curve. In this
method, the calibration curve is drawn from data for
secondary standards with known concentrations of the
analyzed elements. Because of this, it is necessary to
produce secondary standards, adequate in matrix and
phase composition to the ore deposit from which the
ore is mined [4, 5].
The total X-ray fluorescence (TXRF) method is
a practically new method which over the past several
years has become an established analytical technique

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Journal of the University of Chemical Technology and Metallurgy, 47, 1, 2012

for the multi-element determination of trace elements

in various types of samples [6-10]. This method is
basically an energy dispersive XRF technique with a
special geometry. The properties of the method together
with recent instrumental improvements have been
reported by many authors [11-13]. TXRF has been
extensively used not only for the elemental analysis of
various materials but also for depth profiling and surface
analysis.
In the current article, the experimental work for
preparation of the secondary standards is principal
elaboration of the method described in [4]. In the
literature we dont detect similar elaborations for
preparation of secondary standards for XRF analysis of
molybdenum concentrates.
The aim of the current work is the analytical
tracking of the dressing process for molybdenum
concentrates, through preparation and use of secondary
standards for XRF analysis. Here, an important
requirement is the accurately determination of the
elements Mo, Cu, Fe and Re in these secondary
standards.
EXPERIMENTAL
Wave dispersive X-ray fluorescence spectrometer
VRA 20 (Carl Zeiss Jena, Germany), for determination

of molybdenum concentration in the samples and total

X-ray fluorescence analyzer S2 PICOFOX (Bruker AXS,
Germany), for determination of the concentrations of
rhenium (Re), cuprum (Cu) and iron (Fe) were used.
Laboratory muffle-furnace LM-212.11 type, with
temperature range up to 1500 oC and temperature
control within 2 oC deviation was used for the process of melting. The samples and the synthetic standards were melted in platinum-golden crucibles (95
% Pt, 5 % Au) with a volume of 25 cm3. A hot plate
with possibility for regulation of the temperature with
2 oC, was used in appropriate thermal regime in the
effusion and the cool down of the melts. An ensemble
composed by an iron form and an aluminum stamp
(Fig. 1), was employed in the effusion of the melt and
it mould in disc form.
The following reagents and elements were used
for the experiments: CuO (B.D.H., pure, England), CaO
and Fe powder (Merck, p.a., Darmstadt, Germany), MoS2
(Alfa Aesar, Karlsruhe, Germany), SiO2 (Chimsnab,
pure, Dimitrovgrad, Bulgaria) and Triton X-100 (B.D.H.,
England). Ga(NO3)3.8H2O (Johnson Matthey and Co,
London, England) was used for preparation of the
internal standard for the TXRF analysis.
The used melting reagents were: Spectromelt A10
(Li 2 B 4 O 7 ) (Merck, Darmstadt, Germany), LiCO 3
(Chemapol, Praha, Chechoslovakia), KNaCO3 (KCO3/

 15 mm

 24 mm

h = 52 mm

h = 6 mm
h = 8 mm
 44 mm

 39 mm
 38 mm

h = 8 mm mm

1 mm

3
2 mm
 50 mm

Fig. 1. Ensemble for effusion of the melts.

104

M. Mladenov, J. Jordanov

Table 1. Contents of the elements in the synthetic

standards

Standard , % Cu, % Fe, % Ca, % Si, %

Mi1

35

0.5

59.5

Mi2

40

55

Mi3

45

46

Mi4

50

1.5

44.5

Mi5

55

0.5

41.5

Na2CO3) (Riedel de Haen, Hanover, Germany) and

NaNO3 (Fluka AG, pure, Buchs, Switzerland).
RESULTS AND DISCUSSION
Determination of Mo
Determination of the Mo concentrations in the
secondary standards samples was done by the method
of XRF. In general, the following procedure is used: 1)
five primary standards for calibration of the XRF
apparatus are prepared. These five standards are melted
and after forming of glass discs they are used for
calibration of the XRF apparatus and the calibration
curve preparation; 2) twelve samples of the Mo-ore,
are mixed with the melting reagents and are melted.
These samples represent the secondary standards. After
their cooling and obtaining of the glass discs, the
prepared calibration curve was used to determine concentration of Mo in the secondary standards.

The used methods in details are given below:

Melting method
1. Twelve samples covering the interval of concentrations for element Mo in the ore, are selected.
2. By mixing of appropriate chemical compounds
in right ratios, which cover the full interval of
concentrations (see Table 1), the synthetic primary
standards are prepared.
3. The accurately weighed (0.00001 g) amounts
of the components are mixed for preparation of the
amounts of synthetic primary standards.
4. By 0.2 g from each sample and each synthetic
standard, are mixed with respective quantities from the
melting reagents in ratio 1:32 [4]. The used quantities
of the melting reagents are: Spectromelt A10 4.2 g;
LiCO3 1.6 g; KNaCO3 0.8 g; and NaNO3 0.5 g.
5. The mixtures are melted at temperature 1120
o
C for 90 min, and are effused into the ensemble. By

55

Mo (%)

50

45

Y=A+B*X
Parameter
Value
A
-5,67939
B
0,00139
R = 0,99569

40

35

28000 30000 32000 34000 36000 38000 40000 42000 44000

CPS

Fig. 2. Glass-mode disc of the synthetic standard

Fig. 3. Calibration curve for Mo

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Journal of the University of Chemical Technology and Metallurgy, 47, 1, 2012

Table 2. Contents of Mo, Fe, Cu and Re in the secondary

standards.
Standard

, %

Fe, %

Re, ppm

P1

18.550.15 4.050.02 4.010.03 152024

P2

38.310.12 1.520.13 1.300.03 136023

P3

22.650.40 4.570.15 4.520.04 171033

P4

38.080.56 2.730.10 2.030.03 153081

P5

0.640.10 0.330.04 119033

P6

44.590.10 0.680.06 0.400.01 113012

P7

49.510.55 0.480.02 0.250.01 113059

0.490.04 0.250.01

12402

P9

37.070.49 2.770.30 2.540.25 157065

P10

49.150.38 0.770.01 0.450.01 149059

P11

37.560.36 1.700.01 1.290.01 152023

P12

43.980.28 1.110.09 0.570.07 137083

P13

1.260.22 0.820.10 142594

P14

42.280.33 2.250.25 1.600.01 203028

P15

44.390.45 1.470.01 1.180.01 144021

this process the phase structure and the granulometric

composition of the samples are equalized, and also the
matrix influences are eliminated.
6. The cooling of the melt has been done by
reaching 120 oC and keeping for 20 min, and then
cooling down to room temperature, on a turned-off
plate.
Table 1 presents the compositions of the synthetic
standards.
XRF method
1. The obtained glass-mode synthetic primary
standards (Fig. 2) are used for calibration of the XRF
apparatus.
2. By the analysis of the glass-mode synthetic
primary standards the standard curve for Mo is prepared
(Fig. 3).
3. The concentrations of Mo in the selected
samples, which now are called secondary standards,
are determined from the obtained calibration curve.
4. The analysis is done under the following working conditions: line o- (2 = 22.89o), X-ray tube

106

Cu, %

with Rh anode, voltage 35 kV, current 45 mA, crystal LiF220, detector SZ, collimator 0.14 o, discriminator 2-8 V and measuring time 20 s.
Determination of Cu, Fe and Re
For determination of the concentrations of the
elements Cu, Fe and Re the method of TXRF was used.
1. The fifteen samples are ground in an agate
mortar and from there samples of 0.04000 g are weighed
(on analytical balance with accuracy 0.00001 g) into
Eppendorf test-tubes with volume 2.0 ml. To that
quantity 1.5 ml of detergent solution and 10 l from
solution of the internal standard (1 mg/L Ga) are added
[14].
2. The prepared suspensions in portions of 10 l
are poured drop-wise upon quartz discs. After that the
discs are dried under vacuum.
3. The quartz discs with the fixed on their surface
samples are putted into the apparatus for measuring.
Three parallel measurements are done for each sample.
4. The used measuring condition for the TXRF
apparatus were: X-ray tube with Mo target, Ni/C monochromator with 80 % reflection and a liquid nitrogen

M. Mladenov, J. Jordanov

free Silicon Drift Detector (SDD) with an energy resolution of < 159 eV, voltage 50 kV, current 1 A and
measuring time 300 s.
RESULTS
The determined concentrations of the elements
in the secondary standards are shown in Table 2.
The obtained results for the element Mo in the
secondary standards cover the concentration interval
from 18 to 50 % and allow for analysis of the
molybdenum concentrate from the beginning of the
process to its end (after enriching of the ore).
The determined concentrations of the elements
Cu, Fe and Re in the secondary standards, allow their
content to be followed in the ore during the technological
process. These results can be used also for taking
decisions on the final products, for example: reuse,
certification, sale, etc.
The prepared secondary standards were applied
in factory for production of Mo concentrate in the
Republic of Bulgaria. Before their application, the results
from analysis for Mo were obtained after 1-2 days, by
chemical method and after that within 15 min. The
prepared secondary standards now are successfully used
in the practical process for the molybdenum concentrates
production, for fast, effective and adequately accurate
control of the concentrations of the above elements.
CONCLUSIONS
Fifteen secondary standards for the production
process of Mo-concentrates were prepared. In twelve of
them the Mo concentration and in all of them the
concentrations of Cu, Fe and Re were determined.
After application of the secondary standards the
time for analysis of Mo in the ore was very significantly
shortened.
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