MINING AND METALLURGY INSTITUTE BOR ISSN: 2334-8836 (Štampano izdanje)

UDK: 622 ISSN: 2406-1395 (Online)

UDK: 622.765/.356(045)=111 doi:10.5937/MMEB1602031M

Slavica R. Mihajlović*, Živko T. Sekulić*, Dragan S. Radulović*, Vladimir D. Jovanović*

INVESTIGATION THE CALCITE HYDROPHOBISATION OF

DIFFERENT GRAIN SIZES**

Abstract

This paper presents the investigations of possibility of calcite hydrophobisation. Two samples of
calcite of different size classes from the site "Dobar kamen", Arandjelovac, Serbia, were used in the
experimental work. Modifying the surface of calcite was carried out by stearic acid with "dry"
method. Concentrations of stearic acid in the modifying method were as follows: 0.3, 0.5, 0.8, 0.9, 1,
2, 2.5, 3 and 4%. The results showed that a complete hydrophobicity (Io=99.9%) of calcite sample
with the medium diameter (d50) 10.87 μm was achieved at concentration of stearic acid of 0.8%,
while for the sample with the mean grain diameter (d50) of 29.14 μm, it was achieved at concentration
of stearic acid of 3%. These results were confirmed by the microscopic analysis.
Keywords: calcite, stearic acid, degree of coating, grain-size distribution

INTRODUCTION

Limestone is a sedimentary carbonate its hydrophilic surface into hydrophobic

rock that is built of calcite as a dominant [3,4]. As a measure of the achieved surface
mineral, with a slight presence of aragonite, hydrophobicity of calcite, the degree of
as well as the other minerals that represent coating was taken that was presented by the
impurities [1]. Calcite and aragonite are two group of authors in their works [5, 6, 7].
polymorphic forms of CaCO3. By chemical
composition, calcite is CaCO3, hardness per EXPERIMENTAL PART
Mohs 3 and very brittle. Density of pure mi-
neralis 2.72 kgm-3, and if it contains impu- Materials and Methods
rities, density varies from 2.7 to 2.85 kgm-3,
[2]. Limiting factor in the application of Investigations, presented within this pa-
limestone in certain industries (eg. as filler in per, were carried out on a sample of lime-
the polymer industry) is its hydro-philic stone from the deposit "Dobar kamen",
surface. Using the methods of surface calcite Arandjelovac, Serbia. Two fractions were
modifying by organic modifiers, type of used with the following mean grain diameter
surfactants, it is possible to convert (d50): 10.87 μm and 29.14 μm. The results

*
Institute for Technology of Nuclear and Other Mineral Raw Materials, P. O. Box 390,
86 Franshet d’ Esperey St., 11000 Belgrade, Serbia, e-mail address: [email protected]
**
This paper is the result of research on the Project TR 34013 titled "Development of Technological
Processes for Obtaining of Ecological Materials Based on Nonmetallic Minerals", and the Project
TR 34006 titled "Mechanochemical Treatment Under Insufficient Mineral Resources", funded by
the Ministry of Education, Science and Technological Development of the Republic of Serbia for
the period 2011-2014.

No. 2, 2016 31 Mining & Metallurgy Engineering Bor

for a fraction of 25.19 μm, which was an "Perkin Elmer 983 G", the range of 4000-
integral part of these tests, the authors pub- 250 cm-1.
lished before [8]. Modifying the surface of
Grain-size distribution. Grain-size dis-
calcite was carried out by stearic acid
tribution of limestone was determined by
CH3(CH2)16COOH - content of stearic acid:
"Cyclosizer", manufacturer "Warmen". The
0.3; 0.5; 0.8; 0.9; 1; 2; 2.5; 3 and 4%.
mass of sample for determining the grain-
Modifying of calcite. It was done using size distribution is 30 g.
so called "dry" method (without presence of
Determining of coating degree. A
water). Nine samples of 200 g were sampled
method, presented in the works of a group of
where the certain concentration of stearic
authors, was used to determine a coating
acid was added. A vibro mill was used with
degree [5, 6, 7]. The method consists in the
ring operating elements, model "MN 954/3",
following: 10 g of modified calcite is sub-
manufacturer "KHD Humboldt WEDAG"-
merged in 100 ml of distilled water with
Germany. Device operates discontinuously
periodical stirring with a glass rod. After
in the air environment. Modifying time is 7
10 min of standing, the floating fraction and
minutes at temperature of 70oC.
sinking fraction are clearly observed. The
Chemical composition. CaO content floating fraction and sinking fraction were
was determined by the volumetric method, dried at 60oC, and measured. The form 1 can
while the content of SiO2 and loss by calci- be applied for calcuting the coating degree
nation (900oC) was determined by the Io:
gravimetric method (JUS B.B8. 070). Ato-
mic absorption spectrophotometer, type mp
Io 100% (1)
"Perkin Elmer Analyst 703 300", was used mp mt
for determining Al2O3, Fe2O3, MgO, Na2O
and K2O. where:
Mineralogical composition. Qualitative Io - coating degree, %;
mineralogical analysis was carried out under mp - mass of floating fraction, g;
a polarizing microscope for rejected and mt - mass of sinking fraction, g.
transmitted light, brand "JENAPOL", com-
pany Carl Zeiss Jena, using the immersion RESULTS AND DISCUSSION
method (immersion xylene) with qualitative
identification of present minerals. Magni- Characterization the Starting Sample
fition of lens is from 3.2 to 50X. Binocular of Limestone from the Deposit
magnifies is of the Leitz Wetzlar company. "Dobar kamen"
System for microphotography "STUDIO
A detailed chemical and mineralogical
PCTV" (Pinnacle Systems).
composition and X-ray diffraction analysis
X-ray diffraction analysis. The XRD was given by the authors in an earlier pub-
samples were obtained on a Philips PW-1710 lished report [4] (dominated by calcite and
automated diffractometer. JCPDS (Joint the CaO content is 55.43 %).
Committee on Powder Diffraction Stan- Infrared spectroscopy. Infrared spectro-
dards) base was used to identify minerals. scopic analysis was carried out on the star-
Infrared spectroscopy (IC). Infrared ting sample of limestone, and the resulting
spectra were recorded on apparatus infrared spectrum is shown in Figure 1.

No. 2, 2016 32 Mining & Metallurgy Engineering Bor

 Figure 1 Infrared spectrum starting sample of calcite “Dobar kamen“

Characteristic strips for calcite are calcite spectrum, which belong to the basic
observed in the infrared spectrum of starting vibrations 2, 3 and 4, since 1 IC is
limestone sample, thus confirming the inactive, and 3 and 4 are double degene-
results obtained by the X-ray diffraction that rated. In addition to the strips of funda-
calcite is the primary mineral in sample. The mental vibrations, the strips of the sum and
strips of various intensity appear in the area high harmonics, i.e. the strips of upper tones
of wave numbers of 3000 cm-1 to 700 cm-1. (overtones) also appear in the spectrum [9].
The carbonate functional group in calcite is Thus, two strips of low intensity at 2977 and
planar (space group D3h), and as a non-linear 2873 cm-1, strips of upper tone (2 3) of fun-
with the number of atoms N=4 has 3N-6=6 damental valence 3 vibration of carbonate
fundamental vibrations, out of which N-1=3 functional group are observed in the spec-
as valence. Symmetrical valence vibration trum of starting samples, and which occur in
1 is infrared inactive. A broad and strong the range from 2980 to 2830 cm-1 [10].
strip at about 1430 cm-1 is attributed to the According to Osman and Suter [11], the
asymmetrical valence vibration of 3, which strip at 2515 cm-1 belongs to bicarbonate
is a double degenerated ( 3a and 3b). A ion, CO3H-, on calcite surface. However,
sharp strip at 873 cm-1 belongs to the according to Gilbert and associates [9], that
deformation vibration 2 of the planar car- strip is the strip of the sum ( 1 (1083 cm-1) +
bonate group. Also, 4 is a deformation one 3) of fundamental vibrations of carbonate
by type, double degenerated vibration ( 4a group. The strip at 1790 cm-1 is also the strip
and 4b), for which the strip at 709 cm-1 is of the sum, that is ( 1 + 2) of the funda-
characteristic in spectrum in Figure 3. mental vibrations of ion [12]. The
Generally, 3 strips occur instead of 6 in broad strip at about 3440 cm-1 originates

No. 2, 2016 33 Mining & Metallurgy Engineering Bor

from the valence vibrations of water mole- grain diameter (d50): 10.87 μm and 29.14 μm
cules that are present in the sample, connec- as follows: direct curve (1), cumulative cur-
ted to each other by the hydrogen bonds. ve of oversize (2) and cumulative curve of
Grain-size distribution: Figures 2 and 3 undersize (3). Also, the upper limit coarse-
show curves of particle size distribution of ness (ulc) was read for samples using the
the limestone starting samples with mean cumulative curve of oversize.

Figure 2 Curves of particle size distribution of limestone d50=10.87 μm

Figure 3 Curves of particle size distribution of limestone d50=29.14 μm

No. 2, 2016 34 Mining & Metallurgy Engineering Bor

Coating Degree of Modified Calcite

Limestone modifying actually means determined on all modified samples ac-

calcite modifying as the main mineral. In cording to the form 1. Values of coating
order to monitor the results of calcite modi- degree for all three size classes of calcite at
fying using stearic acid with "dry" method, various concentrations of stearic acid are
and achievement the satisfactory surface shown in Table 1; the comparative graphs
hydrophobicity, a coating degree was in Figure 4.

Table 1 Coating degree of modified calcite

Concentration of stea- d50=10.87μm d50=29.14μm
ric acid, % Io, % Io, %
0.3 92.6 25.72
0.5 96.6 42.78
0.8 99.9 69.08
0.9 99.9 68.89
1.0 99.9 71.2
2.0 99.9 73.4
2.5 99.9 80.2
3.0 99.9 99.9
4.0 99.9 99.9

Figure 4 Comparative graphs of coating degree of modified calcite samples

No. 2, 2016 35 Mining & Metallurgy Engineering Bor

 Coating degree of 99.9 %, in calcite the obtained products [13], the results indi-
d50r = 10.87 μm, was achieved at concentra- cate that total hydrophobicity of calcite sur-
tion of stearic acid of 0.8%, while in calcite face with "dry" method was achieved at
d50 = 29.14 μm it was achieved at concentra- stearic acid concentration of 0.8 % for sam-
tion of 3%. By further increasing the con- ple d50 = 10.87 μm, and at concentration of
centration of stearic acid in the modifying 3% for sample d50 = 29.14 μm.
procedure, the coating degree remains un-
changed. This indicates that the orientation X-Ray Diffraction Analysis of
of hydrocarbon chains was not changed in Modified Calcite
the adsorbed layer with an increase of stearic
acid concentration available for adsorption. In order to monitor the structural chan-
Adsorption was always such that the mole- ges of calcite occurring during modifying,
cule of surfactant, in this case stearic acid, the X-ray diffraction analysis was carried
was kept an orientation of its hydrophobic out on fully modified, or completely hydro-
portion (hydrocarbon chain) in the opposite phobic samples. Comparative X-ray diffra-
from calcite surface. As coating degree can ctograms of calcite powder are shown in
be taken as a measure of hydrophobicity of Figure 5.

Figure 5 X-ray diffractograms of powders of coated calcites

d50=10.87 μm and d50=29.14 μm

Calcite upon modifying with stearic acid lysis of the fundamental diffraction peaks of
and achieving a complete hydrophobicity calcite that there are no changes in their dif-
retains the basic structure irrespective of size fraction angles ( ) and intensities, and that
class, which is modified. These results indi- there was no systematic displacement of
cate that the adsorption process occurs on reflections and amorphization after adsorp-
the phase boundaries. It can be seen by ana- tion of stearic acid.

No. 2, 2016 36 Mining & Metallurgy Engineering Bor

Infrared Spectroscopy of the Starting
Sample and Modified Sample

The infrared spectra of the starting 2). In modified sample dsr = 29,14 μm
sample and modified calcite sample of the (spectrum 2), in the range from 3000 to
largest size classes d50 = 29.14 μm are 2800 cm-1, the strips are observed at 2950,
shown in Figure 6. Compared to the typical 2918, 2873 and 2852 cm-1, originating from
strips of starting calcite (spectrum 1), it is valence vibrations of C-H bonds in -CH3
observed that there was no change in the and -CH2 groups of hydrocarbon chains
position and intensity of most strps in of the adsorbed organic component [11-
modified calcite dsr = 29.14 μm (spectrum 13].

Figure 6 Comparative infrared spectra:

1) starting sample of calcite; 2) sample d50=29.14 μm

When the wave numbers of IC strips of This displacements towards smaller wave
C-H vibrations in the spectrum of 2 are numbers as well as poorly expressed strips
compared to the strips that Osman and Suter of valence C-H vibrations in -CH3 group,
[11] observed in the spectrum of crystalline indicate a greater representation of the
stearic acid (2954, 2916, 2872 and Gauch conformation and sloping orientation
2849 cm-1), it is seen that the strips in of the hydrocarbon chain regarding to the
calcite, treated with stearic acid, are slightly calcite surface, i.e. lower density of "pac-
displaced towards higher values, except the king" the hydrocarbon chains in the
strip corresponding to the asymmetrical C- adsor-bed layer of modified calcite
H vibration of –CH3 group (2950 cm-1). dsr=29.14 μm.

No. 2, 2016 37 Mining & Metallurgy Engineering Bor

Microscopic Analysis of Modified
Calcite

Microphotographs are shown in Figure 7.

a) b)

c) d)
Figure 7 Microphotographs of the starting calcite sample a) d50=10.87 μm;
b) d50=29.14 μm and modified calcite sample c) d50=10.87 μm;
d) d50=29.14 μm (magnification 20X)

CONCLUSION

In microphotographs 7a i 7b, free grains Coating degree increases with increa-

of calcite are clearly observed, which have sing the concentration of stearic acid used to
the characteristic interference colors of high- modify. However, it can be noted that for
order, what is the feature of uncoated calcite the same concentration of stearic acid, di-
mineral. However, in Figures 7c i 7d sho- fferent coating degree was achieved in dif-
wing the microphotographs of sample with ferent class sizes. Maximum value of coa-
the coating degree Io = 99.9%, only the ting degree of 99.9%, in calcite of size class
aggregates are observed indicating a comp- d50 = 10.87 μm, was achieved at stearic acid
lete coating of calcite. concentration of 0.8%, while in calcite of

No. 2, 2016 38 Mining & Metallurgy Engineering Bor

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