Journal of Mining Science, Vol. 47, No.

4, 2011

MINERAL DRESSING

NANOSECOND ELECTROMAGNETIC PULSE EFFECT ON PHASE COMPOSITION

V. A. Chanturia, I. Zh. Bunin, M. V. Ryazantseva,

The X-ray photoelectronic spectroscopy data give the grounds for statement that the powerful
nanosecond electromagnetic pulse pretreatment improves sorption activity of pyrite surface and lowers
sorption of a collector at arsenopyrite surface. The research results are verified by test data on the
powerful nanosecond electromagnetic pulse effect on the structure and chemical properties of pyrite
and arsenopyrite surface, as well as their electrochemical and flotation properties.

Pyrite, arsenopyrite, powerful nanosecond electromagnetic pulses, xanthogenate sorption, flotation

The researchers of the IPKON RAS proved experimentally that the powerful nanosecond
electromagnetic pulse (PEMP) effect causes changes in chemical [1] and phase [2] composition of pyrite
and arsenopyrite surfaces, electrophysical [3, 4], electrochemical [4], and physical-chemical [5, 6]
properties of sulfide minerals. The present paper covers the studies of PEMP effect on the structural-
phase state, sorption activity of pyrite and arsenopyrite surface, and their flotation properties, namely, a
doze (pulse-length) of the preliminary electropulse effect.
1. MATERIALS AND RESEARCH TECHNIQUE
ICP-MS and ICP-AES data on chemical composition and impurity content in the test sulfide
specimens are summarized in the Table below.
Table. Chemical composition of pyrite and arsenopyrite specimens.
Fe S As Cu Sb Pb Zn Ca Al Ba Bi Cd Ce Co Ga
Specimen
Mass percent рpm
FeS2 40.61 49.89 0.69 1.29 1.17 0.880.28 0.78 0.09 11.70 10.40 11.30 6.91 1.42 1.68
Not
FeAsS 30.79 19.60 40.30 0.02 0.04 0.01 0.18 0.53 2.40 40.20 0.22 1.04 0.01 3.49
detected
рpm
Ge La Mn Nb Nd Ni P Sn Sr U V W Y Zr
FeS2 0.12 3.96 0.03 0.31 2.90 19.30 0.07 20.8 4.3 1.10 2.20 1.03 3.95 3.58
FeAsS 1.30 0.45 0.02 1.24 0.68 29.93 0.05 6.14 12.7 0.63 11.50 1.09 1.84 14.4

Research Institute of Comprehensive Exploitation of Mineral Resources, Russian Academy of Science (IPKON
RAS), Moscow, Russia. *Institut National Polytechnique de Loraine, Vandœuvre lès Nancy, France. Translated
from Fiziko-Tekhnicheskie Problemy Razrabotki Poleznykh Iskopaemykh, No. 4, pp. 108-116, July-August, 2011.
Original article submitted April 12, 2011.
©
1062-7391/11/4704-0506 2011 Pleiades Publishing, Ltd.
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 The electropulse treatment of the test minerals proceeded at the partial ohm-contact between mineral
particles and PEMP generator electrodes at laboratory facility UOMEP-1 (IPKON RAS, [7]). The pulse
length was about 10 ns, the intensity of the electrical field component was ~107 V/m, the pulse energy
was 0.1 J, the pulse frequency was 100 Hz, the range of variations in the total electromagnetic effect
doze was 0.1-1.5 kJ.
The sorption activity of the test specimens was evaluated by X-ray photoelectronic spectroscopy
for atomic concentration (аtom, %) of sulfur bound with Кх2 or FeKx3 before and after the electropulse
treatment. According to the test procedure, a mineral specimen 1.00 g in weight and – 100 + 50 µm in
size was agitated in the collector solution (S:L= 1:5) with 10 mg/l agent concentration at рН ≈ 7 for
2 min, then the mineral was threefold washed with distilled water and dried in the inert gas atmosphere.
The X-ray photoelectronic spectroscopy spectra were obtained at spectrometer KRATOS Axis Ultra∗.
Electrochemical properties of minerals (current-free electrode potential—EP; φ, mV) was measured
by potentiometrical titration at the medium pH within 5-13. The working electrode was manufactured
from a mineral crystal ~10×10×5 mm with no inclusions and defects visible through a binocular
microscope. The saturated silver chloride electrode was taken as a reference electrode.
The EP/medium pH relation for a crystal in the initial state with no PEMP effect was preliminarily
studied. Then the test specimen was subjected to the electropulse treatment and measurements were
made. The electrode surface was renewed by abrasive tools at each value of pH, then PEMP was
applied to it before EP measurement.
Variations in structural-chemical properties of sulfide surface exposed to the electropulse treatment
were examined by the analytical electronic microscopy (ESM-XRSMA, beam-scanning electron
microscope LEO 1420VP with the energy-dispersing microprobe analyzer Oxford INCA Energy) and
scanning probe microscopy (Scanning-Probe microscopy—AFM, atomic-force microscope INTEGRA
PRIMA, NT-MDT).
Pyrite and arsenopyrite flotation was performed with 1.0 g mineral batches at a laboratory flotation
machine with a 20-ml-cell. Potassium ethyl xanthogenate (PEX) consumption amounted to 10 mg/l,
MIBK (10 mg/l) was used as a frother at рН ≈ 7. The test error did not exceed 5%.
2. ANALYSIS AND DISCUSSION OF TEST RESULTS
X-ray photoelectronic spectrometry (XRPES) is known as a direct qualitative-and-quantitative
method to identify sorption of sulfhydrie collector on sulfide surface [8]. The analysis of publications on
X-ray photoelectronic spectrometry as an instrument capable to identify forms of xanthagenate sorption
makes it possible to outline the following XRPES-spectrum-profile variations, which can be used as the
basis to identify the actual sorption of the collecting agent:
1) growth of peak intensity at bond energy of approximately ~ 165.3 eV, ~ 164.3, and ~ 163.8 eV in
the 2p sulfur content (S2p) spectrum refers to formation of dixantogene on mineral surface [8];
2) increase in peak intensity at bond energy of ~ 285.0 eV, ~286.7, and ~288.0 eV in 1s carbon content
(C1s) spectrum indicates xanthate sorption as dixantogen [8];
3) peak at bond energy of about 533.0 - 533.9 eV can be referred to oxygen atom presence in
sorbed xanthate forms [9].

∗Spectrometric studies were performed at Laboratory of Environment and Mineralogy (Nancy School of Geology, INPL,
Nancy, France) within the French-Russian program “Arcus-Materials and Environment” with financial support from the
Foreign Affairs Ministry of France and Regional Council of Lorraine.
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 It is known from the experimental practice that a mineral surface is generally contaminated with
organic compounds even before its interaction with a collector [10, 11] These inclusions consist of
hydrocarbons and their functional derivatives, molecules of which contain bonds (С = С, С – Н, С = Н,
С – О, С = О) with energies very close to bond energies of hydrocarbon radicals in xanthate molecules.
This fact makes impossible to separate correctly a signal emitted by the study bond in an organic
impurity molecule and a bond signal emitted by a collector. In view of the above, it is explicit that the
analytical data on (С1s) and (O1s) spectra can not be trusted because of uncertainty in interpretation of
(O1s) and (C1s) spectra, therefore, the more reliable information is obtained from the analysis of (S2p)
spectrum.
Figures 1 and 2 demonstrate results of spectrophotometric examination of sorption activity of
pyrite surface in the initial state (with no PEMP effect; doze is 0 kJ) and after different-mode
electropulse treatments with/without interaction with ethyl potassium xanthate solution.
The analysis of (S2p) spectrum for a specimen in the initial state after interaction with the collector
revealed the growth of intensity peak at ~ 164.4 eV bond energy (Fig. 1b) as compared to a specimen
not interacting with the collector (Fig. 1a). Based on the data reported in [9] this fact can be referred
to sorption of xanthate as dixantogen. Thereto, the relative concentration (atom, %) of sulfur atoms in
S-S bond in dixantogen amounted to 5.9%.
The analysis of (S2p) spectrum recorded from pyrite surface treated with PEMI (0.1 kJ, 103 imp.)
with/without interaction with a collector did not identify profile changes which are specific for the
collecting agent sorption.
The increase in an electropulse doze up to 0.5 kJ provoked the growth of the intensity peak at
~ 164.5 эВ bond energy (Fig. 1d) as compared to that of the initial test specimen (Fig. 1c) in (S2p)
spectrum for pyrite specimen after contact with collector solution. In this case the relative concentration
(atom, %) of sulfur atoms in S-S bond in dixantogen was 20.6% or 3 times higher than this parameter
for the initial test specimen, thus indicating the growth of sorption activity of pyrite surface subjected
to PEMI pretreatment (Figs. 1b and 1d).

Fig. 1. S2p spectra for pyrite specimen in the initial state (a, b) and after PEMI treatment (0.5 kJ) (c, d):
(a, c)—with no interaction with ethyl potassium xanthogenate; (b, d)—after interaction with a collector.
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 Fig. 2. S2p spectra for a pyrite specimen treated with PEMI (1.0 kJ): a—no interaction with collector
solution; b—after interaction with a collector.

With increase in the time of electropulse treatment of pyrite (up to 1.0 kJ) S2p spectrum for the test
specimen treated with xanthgenate solution shows the reduction in the spectrum component portion
responsible for iron sulfate (Fig. 2b) as compared to the specimen not contacting with a collector (Fig. 2a).
However, the diagnosed formation of the shoulder in the spectrum at Есв ~ 163.6 eV (Fig. 2b) can be
referred to sorption of a collector as Fe(Kx)3 iron xanthate according to Buckley data [9]. The
quantitative characteristics of sorption at the given mode of the electropulse treatment are difficult to
identify because peaks for S-Fe bond in FeKx3 composition (Есв ~ 162 and ~163.5 eV) are in the
domain of energies of the same bond in FeS2 composition [12, 13]. Therefore, it is complicated to
separate correctly the signals in question, but the shoulder formation in S2p spectrum is an ambiguous
indicator of the collector sorption.
Thus, the effect of increase in sorption activity of pyrite surface as a result of PEMI application is
experimentally established at the following electropulse modes: 0.5 kJ (total 5·103 imp.) and 1.0 kJ
(104 imp.). No noticeable changes in spectrum lines were detected to prove xanthate sorption in the
electropulse pretreatment of minimum duration (0.1 kJ, total 103 imp.).
It is found from SEM-XRSMA data that as the time of electropulse pretreatment (103-104 imp)
grew, the concurrent disintegration and oxidation processes caused structural-chemical transformations
of pyrite surface (Figs. 3a-3d): formation of multiple breakdown-path “outputs” and Lichtenberg
figures in the form of thread- and asteroid-like traces of surface discharges (Figs. 3a and 3c),
destructuring finest low-dimensional films (Fig. 3b) consisting of hypothetically non-aqueous iron
(II/III) sulfates, iron-deficient sulfides, iron oxides and hydroxides [16], which are detected at the
mineral surface by AFM methods. The breakdown values tend to grow (Fig. 3c) and fine oxide films
tend to arise and peel off (Fig. 3d) with the rise of electromagnetic radiation doze up to 0.5-1.0 kJ.
Characteristic types of new formations at arsenopyrite surface are established at regularly
increasing dozes of the electropulse effect. They are crack-porous “coverings” with local swellings of
thorn and irregular spherical shape (Figs. 3e and 3f), autonomous spheroidal metallic forms of iron and
non-autonomous elongated reniform formations (non-stoichiometrical iron oxides) of 3µm and less in
size (Figs. 3f and 3h). The increased time of the pulse treatment promoted the overgrowth of modified
surface areas (Fig. 3h), their energy-dispersion spectra contain a sharply discernible oxygen peak,
which intensity indicates that these areas are poor in sulfur.
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 Fig. 3. New formations at pyrite (a)-(d) and arsenopyrite (e)-(g) surface, generated by powerful
nanosecond electromagnetic pulse treatment. Scale lines—10 µm (d), (f); 20 µm (a), (e), (g); 90 µm (c)
SEM; scanning field 3×3 µm, height Z ≈ 100 nm (b) AFM.

The analysis and interpretation of research data on PEMI effect on the sorption activity of
arsenopyrite surface were based on the following assumption: the oxidation of sulfur as a component of
arsenopyrite surface composition resulted in formation of exclusively open-chained sulfur forms, such
as polysulfides of Sn2 – (n < 8) type. This assumption was made on the basis of numerous studies under
different oxidation conditions where arsenopyrite oxidation did not give sulfur formations in the form
of closed S0 cycles [14, 15].
In this connection it is pertinent to suggest that the peak of ~ 164.4 eV bond energy (Fig. 4)
appeared in (S2p) spectra for arsenopyrite specimens after interaction with xanthate solution is solely
due to the signal emitted by S-S bond being a component of sorbed collector. Therefore, the relative
spectrum component percentage (atom, %), characterized by 164.4 eV bond energy, can be considered
as a quantitative sorption characteristic.

Fig. 4. (S2p) spectrum for sulfur content in arsenopyrite after PEMI treatment (0.1 kJ): a—before
interaction with a collector; b—after interaction with a collector.
510
 Fig. 5. Electropulse treatment effect on sorption activity of pyrite and arsenopyrite surfaces.

Relationship between quantity (atom, %) of a collecting agent (S2p), sorbed at pyrite and
arsenopyrite surfaces, and a doze of electropulse pretreatment is presented in Fig. 5. In Fig. 4
arsenopyrite specimens exhibit the tendency to lower sorption activity of arsenopyrite surface treated
with PEMI by 12 atom % in average as compared to a specimen in the initial state. The maximum
reduction in collector sorption, evaluated for specimens after 0.5 kJ PEMI treatment, amounts to
10.2 atom %, it is by ~ 15.4% lower than that for the initial specimen.
As it is stated in [4, 16], the electropulse treatment provokes the growth of the positive electrode
potential for pyrite and the reduction in that for arsenopyrite. The researchers established the influence of
nanosecond electromagnetic pulse treatment on the electrode potentials for pyrite and arsenopyrite (Fig. 6).
It is explicit from the reported evidence that PEMI treatment highers the positive value of the electrode
potential for pyrite and shifts the electrode potential to the negative domain for arsenopyrite. The nature
of this phenomenon can be explained by the lowered number of free electrons (ne) against the number of
holes (np) for pyrite and increased number of free electric-charge (ne) carriers for arsenopyrite [4].

Fig. 6. Variations in electrode potential for pyrite (a, b) and arsenopyrite (c, d) in the range of рН 5-12.5 after
PEMI pretreatment: 0.5 kJ (a, c); 1.0 kJ (b, d): ●—with no PEMI treatment; ■—with PEMI treatment.
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 Fig. 7. PEMI effect on flotation properties of pyrite and arsenopyrite.

Thus, the present research data on variations in sorption properties of pyrite and arsenopyrite
surfaces comply perfectly with the data on changes in electrophysical and electrochemical properties of
sulfides and are verified by flotation results (Fig. 7).
In presence of potassium ethyl xanthate (PEX) the flotation activity of pyrite specimens treated
with PEMI increases by 18.9% in average as compared to that of the reference specimen. On the
contrary, for arsenopyrite the yield into the froth product lowers from 53.4% (with no PEMI treatment)
down to 23.7% in 0.1 kJ PEMI treatment with 36.1 and 29.1% arsenopyrite recovery in 0.5 and 1.5 kJ
PEMI treatment, respectively.
As it was mentioned above, low electropulse treatment dozes (0.1 kJ) did not cause any appreciable
changes in XRPES spectra for pyrite specimens, thus indicating a rate of collector sorption. However,
the yield of the mineral into the flotation froth product increased noteworthily (Fig. 7). This
discrepancy is explained by the structural-chemical transformations in pyrite exposed to PEMI, namely,
by abnormal growth of surface concentration (atom %) of elementary sulfur S0 at early stages of the
electromagnetic pulse effect [4, 16]. In authors’ view, this is probable due to higher flotation activity of
pyrite provided that there is no collector sorption [16, 17].
Thereby, the electropulse pretreatment of pyrite and arsenopyrite causes the structural and chemical
transformations of the mineral surface, modification of electrophysical and electrochemical properties
of sulfides and provides favorable conditions for adsorption of anion collector. Hydrophobization of
pyrite surface hampers xanthate fixation, and lowers arsenopyrite floatability.
CONCLUSIONS
1. The electropulse pretreatment of pyrite at 0.5 and 1.0 kJ contributes to higher sorption activity of
mineral surface as compared to reference mineral specimens, thus, inducing hydrophobization of
mineral surface and higher flotation activity as a consequence. XRPES examination did not detect the
influence of PEMI on collector sorption at pyrite surface at early stages of PEMI treatment (0.1 kJ).
Thus, the higher mineral yield into the flotation froth product is explained by the intensive formation of
elementary sulfur S0 at mineral particle surface.
2. XRPES examination makes it possible to establish the reduction in sorption activity of
arsenopyrite in the entire study range of the electropulse treatment modes. This fact relates to the
growth of number of free electrons and reduction in EP (φ-potential) of mineral surface, and lower
flotation activity of the mineral as a consequence.
ACKNOWLEDGMENTS
The work was supported by the Grant of the Russian Federation President “Academician V. A.
Chanturia Scientific School,” project no. NSh-3184.2010.5, and by the Russian Foundation for Basic
Research, project no. 11-05-00434-a.
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