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doi:10.14355/mwe.2014.0301.02
OnFragmentationandAgglomeration
PhenomenainanUltrafineDryGrinding
ProcessoftheEgyptianCalciumCarbonate:
theRoleofOleicAcidAddition
K.A.SelimandF.H.AbdElRahiem
CentralMetallurgicalResearchandDevelopmentInstitute(CMRDI)
P.O.Box:87Helwan,Cairo,Egypt
*
rababrashad2003@yahoo.com
Abstract
This study deals with ultrafine dry grinding of Egyptian
calcium carbonate particles using a micronizer called
Planetary Mill. As the size decreases during the process,
theparticlesarestronglysubjectedtoattractiveinterparticle
forcesleadingtoanaggregationphenomenonthatgenerates
a decrease in the surface area. In order to improve the
processefficiency,theuseofgrindingaids,suchasoleicacid,
has been tested. The adsorption of the oleic acid on the
particlesurfaceisfoundtopreventtheaggregationthrough
an electrostatic effect that allows the surface area to be
increased.
Keywords
Ultrafine Dry Grinding; Oleic Acid; Agglomeration; Egyptian
CalciumCarbonate
Introduction
Grindingisoneofthemostusedprocessesthatallow
the production of very fine particles. Many industrial
applications are concerned by ultrafine wet grinding
processes. Examples of applications are fillers for
paper or plastic, coatings, pigments, ceramics for
abrasivesandstructuralapplications,pharmaceuticals,
agrochemicals, etc. However, the prediction and the
control of the ground product properties are still
difficult, especially related to ultrafine grinding
processes[Garciaatel.].Comminutionincludesallthe
processes allowing a size reduction or an increase of
thespecificsurfaceareaofparticles,butotherphysico
chemicalpropertiesaremodified[Somasundaran,Lin
atel.,Dandurand,Yvon].Indeed,duringafragmenta
tion step, the stress energy is converted into elastic
energy applied to the lattice lacks (vacancies,
dislocations, grain joints, etc.), which gives rise to
cracking.
www.mwejournal.orgJournalofMiningWorldExpress,Volume32014
Duringagrindingprocess,themainpartoftheenergy
inputisdissipatedinheatlossinsteadofbeingusedto
create new surfaces. Minimizing losses with an
exterior agent may increase the grinding efficiency
[Garciaatel.,Dingatel,Toraman,Ahmadianatel.].
The efficiency of the additives can be explained by
different approaches, strongly dependent on the
natureofthematerial,thesizeofthegroundproduct
and the grinding technology used. This can be
described by the prevention of the aggregation
phenomenon that may result from interparticle
attractive forces, considering the DLVO theory [Rose
at el.]. In the case of wet processes, when sufficient
additive amounts are used, allowing reducing
significantly the suspension viscosity. The rheological
behavior of the ground pulp is thus an important
parameter that must be controlled during the process
in order to obtain finer particles. Moreover, for wet
ball milling, when the viscosity of concentrated
suspensions becomes too important, the pulp may
causethegrindingmediatobestuckonthesurfaceof
thegrindingchambersoalteringthefragmentationof
the particles [Garcia at el., Ding at el, Toraman,
Ahmadianatel.].Thisphenomenoncanalsobeeduced
and the hydrodynamics in the grinding chamber is
improved.
TABLE1COMPLETECHEMICALANALYSISOFCALCIUMCARBONATE
SAMPLE
Constitute
CaO
SiO2
Al2O3
Fe2O3
Na2O
MgO
K2O
P2O5
MnO
TiO2
L.O.I.
%
58.50
0.72
0.16
0.02
0024
0.47
0.01
0.05
0.005
0.028
40.00
FIG.1XRAYDIFFRACTIONPATTERNSOFCALCITE
10
FIG.2SEMIMAGEOFCALCIUMCARBONATE
Thematerialwasprimarilygroundbythehighenergy
impactofgrindingballandinpartbyfrictionbetween
the balls and the wall of the grinding bowl. The
grinding bowls with material and balls rotate around
their own axis in a counter rotating planetary disc.
The centrifugal forces are caused by rotation of the
grinding bowls and supporting discs work in the
contents of the grinding bowls, from which it is clear
that the force resulting from rotation of the grinding
bowlwhenthemillisstartedcausestherotatingballs
to rub against the inside wall of the bowl thus
grinding the material. The chemical analysis of this
sample is shown in Table 1. Size distribution of the
ground products was measured using Fritsch
Particle Size Analyzer manufactured by GAMBH,
Germany. Complete chemical analysis of the bulk
sample was carried out using ARL XRF/Uniquant.
JournalofMiningWorldExpress,Volume32014www.mwejournal.org
Cumulative, Wt % Passed
100
200rpm
300rpm
360 rpm
80
2 D ( x, t )
tx
S (x)
D ( x, t )
xm
D ( , t )
( , x ) (1)
S ( )
S( x ) kx n (2)
Fig. 4 represents the effect of the grinding time at
constant rational speed 360 rpm. It is obvious that
the increment in grinding time increases the
surface area of the ultrafine product from 7.35
m2/cc at 20 min. to 8.34 m2/cc at 40 min. and then
decreases sharply at 60 min. to 2.75 m2/cc. This is
due to the fact that fine particles start to be
agglomerated at the highest speed. Also, it can be
noticed that the product at 40 min. grinding time
has the highest surface area. Its distribution curve
shows a bend to coarser sizes at about 90%. At 60
min.grindingtime,theshifttocoarsersizesstarted
from the beginning, where the medium size is
about2.75_m, higher than that at20min.and40
min.,1.10_m.Itisnoticedthattherateofgrinding
in the mill is so fast [Zhao at el]. Therefore, the
best condition; amongst the tested; of ultrafine
grinding by Planetary Mill is 20 min. and 360
rpmrationalspeed.
100
80
Cumulative wt % passed
60
40
20 min.
40 min.
60 min.
20
60
0
0.01
40
0.1
10
100
1000
10000
Size, m
20
FIG.4EFFECTOFTHEGRINDINGTIME
0
0.1
3)TheEffectofFractionalBallFilling
10
Size, m
FIG.3EFFECTOFROTATIONALSPEED
2)TheEffectoftheGrindingTime
Thekineticsofcomminutionismodeledbyusinga
classicalbatchgrindingequationbasedonselection
andbreakagefunctions.Thechangeinparticlesize
distribution of ground material is described as a
functionofgrindingtime,t,asfollows[Zhaoatel]:
11
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2%atconstantgrindingtime,60min.and360rpm
rational speed, as shown as Fig. 7. It can be seen
that by increasing oleic acid dosage, the mean
particle size, D50 has been changed ranging from
5.78_ m at 0.5% to 8.5 _m at 2 %. At the same
time, the top cut size, D97, increased from 11.9 m
toabout17.52_mrespectively.
FIG.5SCHEMATICREPRESENTATIONOFTHEMOTIONOF
BALLSINTHEMILL
Cumulative wt % passed
80
60
40
20
0
0.1
10
Size, m
FIG.6EFFECTOFFRACTIONALBALLFILLING
DryGrindingWithAdditionofOleicAcid
1)EffectofDosageofOleicAcid
12
FIG.7EFFECTOFDOSEOFOLEICACID
Grindingprocesswithoutadditiveindicatedthata
strong aggregation of the particles was revealed
particularly for long grinding times. The influence
of oleic acid concentration has been studied with
regardstothesizedistributionofthefinalproduct.
The evolution of the size versus mass fraction is
presented in Fig. 7. Concerning the run without
any additive, the median diameter of the ground
particles strongly decreased during the first
minutes of grinding. Then, a minimum value has
been reached and increased later, when
aggregationoffineparticleshasoccurred.After60
min,aconstantmediansizehasbeenreachedagain.
Indeed, during an ultrafine grinding process, the
particle size and the interparticle distance
decreased whereas the number of particles
increased. As the size became submicron, the
particles may be submitted to strong attractive
forces (Van der Waals forces). During the first 3
minutes,theadditionoftheoleicacid,whateverits
concentration, slightly enhanced the particle size
reduction.Forlongergrindingperiodsandforthe
two lowest concentrations, the median diameter
decreased first before increment then due to
particles aggregation. This aggregation occurred
earlier and to a larger extent with the lowest
concentration (0.5%). Although the effect of the
oleicacidwasnotclearlyputinevidencelookingat
the evolution of the median diameter versus time,
itwasfoundthatthenumberoffineparticleswas
significantly increased in the presence of the
additive.Inthatcase,thequantityofadditivewas
not sufficient enough after a certain period to
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dispersefragmentsanditcanbeassumedthatthe
numerous fines produced during the first minutes
promoteaggregation.
TheAdsorptionMechanism
The measurement of zeta potential indicated charge
properties of calcite particles and in turn can suggest
what can be adsorbed, penetrate, and adhere. Fig. 8
displays the zeta potential of calcite in absence and
presence of oleic acid as a function of pH. It is clear
that in distilled water the calcite has an isoelectric
point at about pH 9. Above it, the surface charge is
positive. After conditioning with oleic acid, calcite
becamenegativelychargedwithaminimumatpH=8
10,indicatingthatthemaximumoleicacidoccurredin
thispHrange.
FIG.8ZETAPOTENTIALOFCALCITEINABSENCEAND
PRESENCEOFOLEICACID
FIG.9FTIROFORIGINALCALCIUMCARBONATE
FIG.11SCHEMATICREPRESENTATIONOFOLEICACID
CALCITEADSORPTIONATTHECALCITE/WATERINTERFACE
REFERENCES
FIG.10FTIROFCCTREATEDWITHOLEICACID
13
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