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JournalofMiningWorldExpress,Volume32014www.mwejournal.

org
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.

Additionally, plastic deformations also occur. During


prolonged mechanical treatments, the further
dissipation of energy generates the alteration of
superficial and structural properties of materials and
some phenomena can occur such as superficial
amorphization of crystallized solids, polymorphic
phase transformations, surface activation or changes
in surface properties and mechanochemical solid
state reactions. Even moderated mechanical treat
ments can influence the superficial energizing of
minerals that is put in evidence by adsorption
isotherms of molecules having a strong affinity with
thesolid.Thus,variousphysicalandphysicochemical
aspects of a grinding operation have to be known,
which depends on the minerals and mill
characteristics, the energy applied to the system, the
temperature and the pressure of the environment.
Different studies have been developed for several
materialsonthesepoints.
Grinding processes are considered as energetically
expensive and additives are usually used for
fragmentationoperations.Suchadditivesarechemical
compounds which, incorporated with the powder or
into the suspension submitted to grinding, allow
obtaining finer particles. The increase of specific
surface area may vary from several percent up to 20
times the specific surface area of the particles ground
without any additive [Garcia at el., Ding at el,
Toraman, Ahmadian at el.]. Common additives often
used during grinding processes of minerals (calcite,
dolomite, quartz, magnetite, and hematite) are
alcohols, ketones, amines, carboxylic acids, esters,
electrolytes, surfactants, neutral or charged polymers.
Nevertheless, these additives are expected to be used
insmallproportiontoimprovetheprocessandalsoto
makeiteconomicallylessexpensivethanwithoutany.

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

The aim of this work is to produce ground calcium


carbonate by dry grinding using a micronizer called
Planetary Mill under various operating conditions
with and without addition of oleic acid. The effect of
oleicacidconcentrationonthegrindingefficiencyand
resultshasbeenstudied.
Materials and Methods
Materials
A sample of pure calcium carbonate (99.9%) was
kindly delivered from EgyptianJordanian for Mining
Industries Co. Laboratory grade oleic acid, supplied
by Adwic Co., Egypt, was used. Analytical grade
NaOHandHClwereusedforpHregulation.
Methods
The sample was sent as primary crushed lumps of
about 3 in size. It was secondary crushed using a
Denver pilot jaw crusher to less than one inch and
then in a Wedag roller to less than 3.36 mm.The
crushed sample was then thoroughly mixed and
quartered.Thetertiarycrushedmaterialwassampled
into batches and subjected to ultrafine grinding in a
micronizercalledPlanetaryMill.

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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

Results and Discussion


OptimizationofUltrafineDryGrindingwithout
Additives
1)EffectofRationalSpeed
The rational speed was changed from 200 to 360
rpmatconstantgrindingtime,20minute,Fig.3.It
is shown that the surface area after grinding rang
from 7.044 m2/cc to 7.35 m2/cc. Also, on increasing
the rational speed from 200 to 360 rpm, D50, mean
particle size, of the ground sample has been
changedfrom 1.18_ mat200 rpm to 1.20_ mat
360 rpm and D97, top cut size, has been changed
from 3.99_ m to 11.50 _m. Bradley found that
the centrifugal acceleration is proportional to the
square of the speed, and the rate of grinding
should be proportional to 1.5 power of centrifugal
acceleration. It is perhaps of interest to point out
that this result is also encountered by vibration
milling[Zhaoatel].

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 ( )

Where: D(x,t) is the cumulative under size of


particles, x is the particle size, is the size of a
single particle to be broken, xm is the maximum
particle size present. S(x) is the selection function
which represents the probability for a particle of
size x to be selected for grinding, and is specified
byempiricalrelationshipas;

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

XRD was used to identify the mineral components in


the calcium carbonate sample and to determine, in
part, the proportion of the calcite minerals present.
Randomly mounted material was scanned using PW
1170PhillipsdiffractometerwithCoKradiation,Fig.
1. SEM observation was performed using Jeol 5410
unit, and the sample was coated by Au. 200 mg
samples were analyzed with Netzsch STA 409 C/CD
simultaneous thermal analysis apparatus between
roomtemperatureand1100Cataheatingrateof
10C/min. Alumina was used as a reference material,
Fig.2.

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]:

It was found that; the moving distance, frequency


and the contact force of the Suring appear to be
important quantitiesaffecting the rate of grinding.
It is predicted that these quantities will be
determinedbythefractionalballfillingofthemill
[Houssa]. A schematic picture is given in Fig.5,
showing the motion state of ball in the mill based
onphotographicanalysis.

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www.mwejournal.orgJournalofMiningWorldExpress,Volume32014

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

At the same time, the cascading of balls does not


occurinthemill.Itisalsoknownfromtheanalysis
result that the entire charge of the mill, as a
coherent mass, surges on the mill wall. Thus, for
one part of the cyclical motion, the charge moves
aroundtheaxisofthemillinthesamedirectionas
themillsshell;whileduringthesecondpartofthe
motion,itmovesintheoppositedirection.Itcould
be expected that most of the comminution; under
thiscondition,occursbetweenthemillwallandthe
ball. The compressive, friction, abrasive and shear
stresses of the ball mass applied on the particle
layer that adhered to the mill wall and it partly
occurswithintheballmassbytheshearstress,due
to the speed gradient of moving balls. The results
in Fig.6 showed that the product in all ratios is
more or less the same properties, where; surface
area increased from 7.7 m2/cc to about 8 m2/cc.
However,meanparticlesize,D50,hasbeenchanged
from1.0_mto0.93_mastheratiochangedfrom
50% to 25% and the top cut size, D97, has been
changed from 4_m to 3_m, respectively.
Therefore,theoptimumratiois50%asthechanges
intheproductpropertiesarenotdistinguishedall
overthedifferentratios.
100
25 %
30 %
40 %
50 %

Cumulative wt % passed

80

60

40

20

0
0.1

10

Size, m

FIG.6EFFECTOFFRACTIONALBALLFILLING

DryGrindingWithAdditionofOleicAcid
1)EffectofDosageofOleicAcid

The dose of oleic acid was changed from 0.5% to

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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

JournalofMiningWorldExpress,Volume32014www.mwejournal.org

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.

The FTIR spectra in Fig.9 shows the characteristic


absorption bands of calcite (CaCO3) located at 1421,
875 and 711 cm1, corresponding to the asymmetric
stretching (3); outofplane bending (2), and the in
planebending (4) modes of the carbonate CO32 ion
group are found to be active [Kajima and Tonaka,
Zhao at el]. The FTIR spectra of calcite treated with
oleic acid, in Fig.10, shows a band at 1423_cm1. This
suggests the formation of a metal complex involving
the COO group (monocoordinated surface calcium
oleate COOCa+). The absorption band at 1133 cm1 is
related to CO bonds and the band at 1296 cm1 is
assigned to the bending vibration of (CH2). Two
bandsat2956and2853cm1arecharacteristicof(CH)
asymmetricandthesymmetricstretchingrespectively.
The band at 3612 cm1 is characteristic of OH
stretching.Fromtheseresults,itcanbeconcludedthat
oleate anions are chemisorbed on the calcite surface;
which agrees with data on the dependence of the
COOfrequency on the metal nature [Kumar at el.,
Labidi,N.S.andDjebaili],asshowninFig.9andFig.
10.
Conclusions

FIG.8ZETAPOTENTIALOFCALCITEINABSENCEAND
PRESENCEOFOLEICACID

Investigations about the influence of additives on


ultrafinegrindingofcalciteparticleswerecarriedout.
Ground without additive; calcite has a strong
tendency to aggregate under the attractive Van der
Waals forces. After some minutes of grinding, the
number of fine particles became significant and
aggregates appeared. The grinding efficiency of the
process was altered due to a great increase of the
surface area of the particles. By preventing the
aggregation of the particles, an additive allowed
increasing the surface area of the particles. The
requiredamountofadditivetobeaddeddependedon
thefinenessofthegroundproducttobeobtained.The
mechanism of the adsorption of oleic acid on the
surfaceofcalcitehasbeensuggestedinFig.11.

FIG.9FTIROFORIGINALCALCIUMCARBONATE

FIG.11SCHEMATICREPRESENTATIONOFOLEICACID
CALCITEADSORPTIONATTHECALCITE/WATERINTERFACE
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