Research Article Effectiveness of the Top-Down

Research ArticleEffectiveness of the Top-Down Nanotechnology inthe Production of Ultrafine Cement (sim220 nm)

Byung-Wan Jo Sumit Chakraborty Ki Heon Kim and Yun Sung Lee

Department of Civil and Environmental Engineering Hanyang University Seoul 133791 Republic of Korea

Correspondence should be addressed to Byung-Wan Jo joyconhanmailnet

Received 14 February 2014 Revised 4 June 2014 Accepted 5 June 2014 Published 25 June 2014

Academic Editor Bin Zhang

Copyright copy 2014 Byung-Wan Jo et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The present investigation is dealing with the communition of the cement particle to the ultrafine level (sim220 nm) utilizing the beadmilling process which is considered as a top-down nanotechnology During the grinding of the cement particle the effect of variousparameters such as grinding time (1ndash6 h) and grinding agent (methanol and ethanol) on the production of the ultrafine cement hasalso been investigated Performance of newly produced ultrafine cement is elucidated by the chemical composition particle sizedistribution and SEM and XRD analyses Based on the particle size distribution of the newly produced ultrafine cement it wasassessed that the size of the cement particle decreases efficiently with increase in grinding time Additionally it is optimized that thebead milling process is able to produce 90 of the cement particle lt350 nm and 50 of the cement particle lt 220 nm respectivelyafter 63 h milling without affecting the chemical phases Production of the ultrafine cement utilizing this method will promote theconstruction industries towards the development of smart and sustainable construction materials

1 Introduction

With the aim to develop high performance smart andsustainable construction material utilization of the ultrafinecement in construction process would be the promising tech-nique Therefore an immediate practical plan is required tobe established for the production of ultrafine cement Regard-ing the production of the ultrafine cement utilization of thenanotechnology would be the encouraging practice becausethe nanotechnology is now being considered with a visionto advance our understanding and control of matter at thenanoscale towards the development of smart economic andsustainable materials It empowers changes at the molecularlevel to improve material behavior and performance of civiland infrastructure systems [1] Keeping in view of the wordwide screening report it is apparent that the Portland cementis one of the largest commodities consumed by mankind butitrsquos potential is yet to be investigated at the micronanoscalelevel [2 3] If the nanoparticles (ultrafine particles) areintegrated with traditional building materials then the newmaterials may process high-value or smart properties How-ever the existing applications of the nanomaterials are limitedto produce antiaging antiseptic and purified air composite

paint [4] Recently the attention of scientist is attractedtowards the development of nanocement andor ecologicalbuilding materials incorporating various nanoscale materialssuch as spherical nanomaterial (namely nano-SiO

2 nano-

TiO2 nano-Al

2O3 nano-Fe

2O3 etc) nanofiber or nanotube

(namely carbon nanotube (CNT) carbon nanofibers (CNF))and nanoclay into cement system [2 5ndash7] Accordinglynanomaterials implanted complex structures of cement basedmaterials are characterized by high strength greater durabil-ity rapid construction and reduced environmental impactwith the whole range of newly introduced ldquosmartrdquo properties[2 6ndash9] Besides the incorporation of the nanomaterials intothe cement concrete system it is also reported elsewherethat the application of the nanoporous thin film on theaggregate surfaces beforemixing of concrete not only brings arange of novel properties such as high ductility self-healingself-crack controlling ability low electrical resistivity andself-sensing capabilities but also improves the interfacialtransition zone (ITZ) in concrete system [10ndash13] Usuallyinclusion of the different nanoparticle in cement systemexposes a higher surface area of the cementing material forthe hydration reaction It is reported that at a particularwater cement ration (WC) the nanoparticle embedded

Hindawi Publishing CorporationJournal of NanomaterialsVolume 2014 Article ID 131627 9 pageshttpdxdoiorg1011552014131627

2 Journal of Nanomaterials

Table 1 Comparative study for the preparation of nanocement or ultrafine cement and their performance reported in the existing literature

Primary material Additivesprocedure Particle size Effectperformance Reference

Portland cementNanosize ingredients such asalumina silica particles and carbonnanotubes were added

lt500 nmNanocement can create newmaterials devices and systems atthe molecular nano- and microlevel

[1]

Portland cementNano-SiO2 nano-TiO2nano-Al2O3 nano-Fe2O3 andnanotubenanofibers were added

sim20 nm and 100 nmCan produce concrete with superiormechanical properties as well asimproved durability

[2]

Portland cement Single wall and multiwall carbonnanotubes were added mdash

Cement materials showed superiormechanical electrical and thermalproperties

[5]

Ordinary Portlandcement

Spherical nanoparticle nano-SiO2nano-Fe2O3 and multiwall carbonnanotube were added

1ndash100 nmSignificant improvement incompressive strength as well asYoungrsquos modulus and hardness ofthe concrete

[6]

Portland cement Spherical nano-Fe2O3 andnano-SiO2 were added

15 nm Mortar showed higher compressivestrength as well as flexural strength [7]

Portland cement Open closed circuit dry grinding ofthe cement by stirring mill 20ndash25 120583m

Grinding of cement increases thesurface area and decreases theparticle size to 20ndash25 120583m

[15]

Ultrafine cementUltrafine cement obtained by drygrinding flyash and admixtureadded

085ndash088 120583mReplacement of ultrafine cementwith flyash decreases the strength ofthe cement material

[16]


Wet grinding of the cement (WMC)using stirred mill 40ndash10 120583m

After 2ndash4min grinding maximum40 120583m and average 10 120583m cementcan be produced

[17]


Wet grinding of cement using beadmill and alcohol used as grindingagent

350ndash220 nmWet grinding produces sim220 nmcement particle (50) withoutaffecting chemical phases

Present work

cement is hydrated in a faster rate as compared to that ofthe conventionally available cement [1 2 14] The fast rateof hydration reaction leads to developing early strength incement composite which in turn reduces the time for thebuilding construction

The methods discussed above focus on the incorporationof foreign nanoparticle in the cement system Howeververy limited reports are available based on the productionof ultrafine cement by physicomechanical crushing of theconventional cement particle [15ndash17] Table 1 summarizesvarious procedures used for making of the nanocement andtheir application Based on the critical literature survey it isassessed that the fine cement of the particle size 200ndash2120583mcan be produced by the grinding of the cement using ballmill vibration mill Raymond mill mixing mill or air-blowmill stirred mill and so forth [15ndash17] Accordingly it is alsoreported that due to the milling of the cement surface areaof the cement particle increases consequently agglomerationof the particle occurs Therefore a special arrangement isrequired for its storage and packing which in turn increasesthe cost of the cement [17] However to the best of our knowl-edge and belief no research report is yet available which canproduce cement (50ndash90 of the weight) of the particle size200ndash300 nm using physicomechanical crushing Thereforereviewing the literature it is apparent that wet grinding of thecement particle utilizing top-down nanotechnology for theproduction of ultrafine cement (sim200ndash300 nm) has not beenstudied yet

In order to produce ultrafine (submicro) cement usingphysicomechanical crushing (top-down) method beadmilling process has been selectedThe chemical compositionparticle size distribution and SEM and XRD analyses werepreferred selectively to evaluate the effectiveness of thebead milling process in production of ultrafine or submicrocement Based on the analyses it is assessed that beadmillingprocess is demonstrated to be very effective to produce theultrafine cement of the particle size 200ndash300 nm retainingthe chemical phases unaffected

2 Experimental21 Materials Ordinary Portland cement provided bySsangyong Cement Industrial Company Korea was usedas the principal material for the production of ultrafinecement The particle size specific gravity and fineness ofthe used ordinary Portland cement are 10ndash30120583m 315 andsim2800 cm2g respectively

Methanol and ethanol purchased from Merck Germanywere used as crushing aid for the production of ultrafine(submicro) cement using bead milling process The generalfeatures of the methanol and ethanol are represented inTable 2

In this investigation Zirconia ceramic beads purchasedfrom Shanghai Pangea Import and Export Co Ltd Chinawere used as a grinding media due to its extreme lowwear loss high grinding efficiency and high durability as

Journal of Nanomaterials 3

Table 2 General features of the methanol and ethanol used as grinding agent for the production of ultrafine cement

Grinding agent Molecular formula Purity Specific gravity Melting point Boiling pointMethanol CH3OH 99 0791 minus9778∘C 6465∘CEthanol C2H5OH 99 0789 minus1145∘C 7832∘C

Table 3 Components and mixing ratio for the production ultrafine cement

Components Volume (L) Cement (kg) RPM Grinding time (h)

Grinding agents Methanol (CH3OH) 10 4 3600 1 3 6Ethanol (C2H5OH) 10 4 3600 1 3 6

Beads Disc Compartments

Separation gab

Figure 1 Schematic representation of bead mill for the productionof ultrafine cement

compared to that of the glass and alumina based grindingmediaThe Zirconia beads are generally composed of ZrO

2sim

95 and Y2O3sim5 respectively The standard shape of the

used Zirconia beads is spherical in size of the diameter 04ndash06mm The specific density bulk density roundness andcolor of the used Zirconia beads are reported to be 60 gcc38 gcc gt95 and white respectively

22 Production ofUltrafineCement Thebeadmilling processwas used for the production of the ultrafine cement in thisinvestigation A 30 L capacity horizontal bead mill purchasedfrom the Planetary Mixer Unitech Korea was used for thewet grinding of the ordinary Portland cementThe schematicpicture of the horizontal bead mill is represented in Figure 1The mill used in this investigation consists of a cylindricaltube with a stirring part situated at the center of the longitu-dinal axis of the tube The stirring part of the mill containsa number of pins or discs for creating the shear force on thematerials An electricmotor is connected with stirring part torun the stirring part for comminuting the cement particles Inthe bead milling process cement particles were comminutedcontrolling the several parameters such as grinding mediagrinding force and agitation speed Accordingly the emptyvolume of the tube was filled with the same size (04ndash06mm)Zirconia beads as a grindingmedia to comminute the cementparticle As the bead mill is a type of the stirring milltherefore abrasive and shear forces were produced by themill as grinding force to comminute the cement particlesTheagitation speed of the bead mill was 3600 rpm which was

controlled by a pulley arrangement During grinding of thecement due to the high RPM and shearing force the millcould be heated adequately Therefore for cooling purposethe grinding chamber is equipped with a water jacket inwhich cold water is flowing from a thermostatic bath

Thus for the production of the ultrafine cement usingbead milling process initially the empty volume of the millwas filled with the ordinary Portland cement particle of thesize 10ndash30 120583m and allowed to grind in the mill by controllingthe above parameters In this study grinding of the cementwas done in the presence of the two different grindingagents namely methanol (CH

3OH) and ethanol (C

2H5OH)

for three different times such as 1 h 3 h and 6 h Table 3represents the details for the production of the ultrafine orsubmicro cement using bead milling process

23 Characterization Chemical composition of the ordi-nary Portland cement as well as ultrafine Portland cementobtained after wet grinding in bead mill was measuredusing Rigaku NEX QC energy dispersive X-ray fluores-cence (EDXRF) analyzer Applied Rigaku Technologies IncAustin USAThe cement samples were analyzed packing thesamples on a 40mm rectangular hollow area of the sampleholder The analysis was done in helium environment Inthis instrument a 50Kv X-ray generator tube is used togenerate the X-ray for the analysis of the sample and a highperformance SDD semiconductor based recorder is used todetect the signal Before the analysis cement samples weredried in oven at 105∘C and cooled to room temperature bystoring the samples in a vacuum desiccator

Particle sizes of the normal OPC and ultrafine OPC sam-ples were analyzed using LA-950 laser particle size analyzerinstrument purchased from Horiba Ltd Kyoto Japan Forthe analysis of the cement samples initially the samples weredried in oven at 105∘C to remove the moisture During theparticle size analysis exactly 1 g of the dry samples was fedinto the PowderJet Dry Feeder of the LA-950 laser particlesize analyzer Furthermore samples were analyzed basedon the Mie scattering theory In this instrument two lightsources are used to analyze the particle size namely 5mW650 nm red laser diode and 3mW 405 nm blue LED In themeasurement array the high quality photo diodes are used todetect the scattered light over a wide range of angles

Micrographs of the cement particle before and aftermilling were recorded using JEOL JSM-6700F JEOL USAInc USA In this electron microscope electrons are emitted


Table 4 Particle size of the Portland cement before and after milling in bead milling process

Featurescomponents Particle size (120583m)Milling time (h) 0 1 3 6Sample code aD10 D50 D90 D10 D50 D90 D10 D50 D90 D10 D50 D90

Grinding agent Methanol 243 1257 3877 025 080 163 021 068 087 020 051 078Ethanol 243 1257 3877 013 032 054 013 024 037 011 020 033

aD cumulative passing percent

from a bent tungsten filament (withstanding high temper-ature without melting) that acts as cathode The emittedelectrons are accelerated by the application of high voltage(maximum 30 kV) and strike on the surface of the samplewhich in turn assists to liberate the electron from the outershell of the sample These liberated electrons are termed assecondary electron focused by electromagnetic lenses witha maximum magnification capacity 1000000x The scanningof the electron beam over the sample surface is controlled bydeflecting the electron beam using a scanning coil Duringthis investigation a very thin gold was sputter coated on thesurface of the moisture free dried samples to avoid chargingThereafter samples were placed on the SEM stub and allowedto analyze The digital scanning electron micrographs wererecorded at 10ndash20 kV accelerated voltage and 15 kx magnifi-cation

The structural characteristics of ordinary Portlandcement as well as ultrafine Portland cement producedutilizing bead mill were investigated using an X-raydiffractometer (Ultima III Rigaku Inc Japan) The CuK120572radiation (40 kV 40mA) and Ni filter were used to producethe X-ray The X-ray diffractograms of the samples wererecorded in the 2120579 rage 5∘ndash60∘ maintaining a scan speed of1∘minminus1 with a step difference of 00210158401015840 In this investigationX-ray diffraction of the oven dried samples was recordedby packing the samples in a rectangular hollow area of theglass made sample holder In this instrument a tungsten(W) filament is used as cathode and a desired targetmetal for example Cu is used as an anode to produce themonochromatic X-ray beam of the wave length 15 A

3 Results and Discussion31 Particle Size Distribution In this investigation the parti-cle size distribution of the ordinary Portland cement aswell asultrafine cement produced by the bead milling process playsan important role in predicting the desired characteristics andthe performances of the final product Figure 2 representsthe particle size distribution pattern of the OPC particlebefore and after milling From Figure 2(a) it is observed that10 50 and 90 of the cement show the particle sizessim243 120583m sim1257 120583m and sim3877 120583m respectively beforemillingTherefore it is considered that the ordinary Portlandcement contains microparticles of the average particle sizesim1257 120583m Table 4 represents the summary of the particlesize distribution of the ordinary Portland cement as well asultrafine (submicro) cement produced by the bead millingprocess As envisaged from Table 4 the particle size of thecement is significantly reduced by the milling of the cement

utilizing bead milling process It is also observed fromthe table that the size of the particle decreases graduallywith increase in milling time irrespective of the grindingagents such as methanol (CH

3OH) and ethanol (C

2H5OH)

Additionally it is visualized from the table that the particlesize of the 50 cement is significantly reduced from 1257120583mto 320 nm after 1 h milling in the presence of ethanol asa grinding agent Figure 2(b) represents the particle sizedistribution pattern of the cement particle produced after 6 hmilling From the figure it is envisaged that 10of the cementcontains 110 nm particles and 90 of the cement containssim330 nmparticleTherefore it is considered that wet grindingby top-down process (bead milling) is efficient to producenanosized cement particle Figure 2(c) represents the com-parative particle size distribution pattern of the cementparticle milling for 1 h 3 h and 6 h in the presence of ethanolas grinding agent Moreover as summarized in Table 4 theparticle size of the 50 cement is reduced to 240 nm and200 nm after 3 h and 6 h milling respectively in the presenceof the ethanol (C

2H5OH) as grinding agent Therefore it

can be assessed that the wet grinding of the cement utilizingbead milling process is able to produce the nanoscale cementparticle As reported by Balaguru and Chong [1] the cementparticle less than 500 nm can be termed as nanocement Priorto this investigation a very few researchers have attemptedto produce ultrafine cement [15ndash17] For example Pilevneliet al [15] reported that dry grinding of the cement canproduce cement of the particle size 20ndash25120583m NeverthelessHuang et al [17] reported that the wet grinding of theordinary Portland cement can produce 50 of the cementparticle less than 10 120583m Table 1 compares the particle sizeof the cement produced by different techniques Hence inthe present investigation the wet grinding of the cementusing bead mill is able to produce the cement particle ofthe average size sim200ndash300 nm Therefore it is assessed thatthe process used in this investigation is the initial approachthrough which nanosized cement particle can be producedDuring this investigation the physicomechanical crushing ofthe cement leads to produce the nanosized cement particleIn this process stirred mill was used which mainly producesabrasive and shear forces for comminuting the microscalecement particle to nanoscale particle Production of the ultra-fine nanosized cement particle by the grinding of ordinaryPortland cement in the bead mill can further be clarified bySEM analysis

Additionally irrespective of the grinding time differentgrinding agents play a significant role in controlling theparticle size of the cement As it is reported in Table 4the particle size of the cement (50) is reduced to 800 nm


20

18

16

14

12

10

8

6

4

2

0

Chan

nel (

)

Pass

ing

()

006

009

015

023

038

058

091

144

228 36

569 9

1422

2249

3556

5623

8891

14058

22228

35146

55571

87867

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

Passing ()Channel ()

(a)

20

18

16

14

12

10

8

6

4

2

0


Chan

nel (

)

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

0001

00016

00027

00045

00076

00128

00215

00361

00608

01022

01719

0289

0486

0818

1375

2312

389

654

(b)

00001 0001 001 01 1 10 100 1000

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

MicrocementMilling 1h

Milling 3hMilling 6h

(c)

Figure 2 Particle size distribution pattern of (a) ordinary Portland cement (before milling) (b) ultrafine cement produced by 6 h beadmilling and (c) comparative distribution pattern of the ordinary Portland cement and ultrafine cementmilling for 1 h 3 h and 6 h in presenceof ethanol as grinding agent

Table 5 Chemical composition of Portland cement before and after milling

Type of cement Milling time (h) Chemical compositionCaO SiO2 Al2O3 MgO Fe2O3 SO3 Loss of Ig

Ordinary Portland cement 0 613 211 52 40 28 24 20Ultrafine Portland cement 6 613 211 52 40 28 24 20

680 nm and 510 nmafter 1 h 3 h and 6 hmilling respectivelyin the presence of the methanol as grinding agent Whereasthe particle size of the cement (50) is reduced to 320 nm240 nm and 200 nm after 1 h 3 h and 6 h milling respec-tively in the presence of the ethanol as grinding agent Itindicates that the ethanol as a grinding agent is performingmore efficiently as compared to that of the methanol incontrolling the particle size of the cement during the wetgrinding of the cement in the bead milling process Thisis might be due to the evaporation of low boiling (sim64∘C)methanol from the grinding chamber which in turn assistsin grinding the cement particle in dry medium The drygrinding of the cement leads to agglomerate the ultrafinecement particle as a result large size particles are observed

32 SEM Analysis The efficacy of the bead milling processin the production of the nanocement is further clarified bySEM analysis Figures 3(a) 3(b) 3(c) and 3(d) represent theSEM micrographs of the cement particles before and aftermilling As envisaged from Figure 3(a) the particle size of thecement before milling was in the microscale level Howeverthe particle size of the cement significantly decreases by themilling of the cement as evidenced from Figures 3(b) 3(c)and 3(d) From Figure 3(b) it is observed that the beadmilling process is able to produce 50 of the cement particleless than 1 120583m after 1 h milling As discussed in the precedingsection the particle size of the cement component decreaseswith increase in milling time which is entirely proved bySEM analysis (represented in Figure 3(c) and Figure 3(d))


(a) (b)

(c) (d)

Figure 3 SEMmicrograph of cement particle before and after bead milling (a) before milling (b) after 1 h milling (c) after 3 h milling and(d) after 6 h milling

From Figure 3(d) it is visualized that the particle size of thecement (sim50) is less than 300 nm after 6 h milling Fromthe figure it is also envisaged that the decrease in particlesize of the cement due to the bead milling increases thesurface area and reduces the pores at disperse conditionsThus increased surface area of cement particle may lead toincrease the extent of cement hydration reaction which willassist in developing the early strength in concrete systemAs it is observed from the SEM micrographs that pores arereduced in the disperse condition of the ultrafine cementsubsequently it may lead to increase the compaction ofthe hydrated cement components Therefore it is expectedthat the phenomenon may lead to enhance the strength ofnanocement based concrete composites

33 Chemical Composition Analysis Chemical compositionsof the cement samples were analyzed using energy dispersiveX-ray fluorescence (EDXRF) analyzer The detailed descrip-tion of the instrument and the analysis procedure is pre-sented in Section 23 Chemical compositions of the ordinaryPortland cement before and after milling are presented inTable 5 Usually OPC contains various oxide componentssuch as CaO SiO

2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar

and Wheeler [16] reported the same chemical compositionspresent in the ultrafine cement type III Based on the chemicalcomposition analysis of the ordinary Portland cement aswell as ultrafine (sim200ndash300 nm) cement produced by beadmilling it is observed that the weight percentage of thechemical components is the same irrespective of the grindingtime and grinding aids Therefore it is considered that thereis no change in chemical composition which occurred evenafter 6 h milling This phenomenon can further be clarifiedby X-ray diffraction analysis Thus from this result it is

ensured that the bead milling process is able to reduce theparticle size to the nanoscale level retaining the chemicalphases of the cement unaffected Accordingly it is expectedthat the ultrafine cement particle will definitely influencethe properties of the final product which will encouragethe cement research towards the development of the highperformance and sustainable construction materials

34 X-Ray Diffraction Analysis X-ray diffraction analysis ofthe ordinary Portland cement as well as ultrafine cement par-ticle was performed to identify the chemical phases presentin the cement samples before and after milling The detaileddescription of the X-ray diffraction analyzer and analysisprocedure is described in Section 23 X-ray diffractogramsof the cement particle before and after milling are presentedin Figures 4(a) and 4(b) Comparing the X-ray diffractionpatterns of the cement samples obtained in this investigationwith the existing literature that is Yousuf et al [18] Trezza[19] Vaickelionis and Vaickelioniene [20] and Panigrahy etal [21] the peak appeared to be due to the different chemicalphases which are identified correctly Table 6 represents thesummary of the X-ray diffractograms of the cement samples(before and after milling) From the table it is envisaged thatthe peaks correspond to the Ca(OH)

2appeared at 2120579 values

181∘ 286∘ 343∘ 469∘ and 551∘ for both of the cementsamples before and after 6 hmilling in the presence of ethanolas grinding agent Additionally the peaks correspond to C

3S

appeared at 293∘ 322∘ and 509∘ and the peak correspondsto C2S appeared at 322 for both of the cement samples before

and after 6 h milling However the peaks correspond to theCa(OH)

2 C3S and ferrite phases which appeared at 538∘

411∘ and 422∘ respectively in the X-ray diffractogram ofthe ordinary Portland cement (before milling) are abolished


Table 6 Summary of the peaks correspond to different chemical phases which appeared at different 2120579 value in the X-ray diffractograms ofthe cement samples (before and after 6 h milling)

Cement type Peaks correspond to the chemical phases which appeared at different 2120579 value in XRD analysis1818∘ 286∘ 293∘ 322∘ 343∘ 411∘ 428∘ 469∘ 509∘ 538∘ 551∘

Before milling CHa CH C3Sb C3S C2S

c CH C3S Ferrite CH C3S CH CHAfter milling CH CH (highd) C3S (low

e) C3S C2S (low) CH (high) mdash mdash CH (high) C3S (high) mdash CH (high)aCalcium hydroxide btricalcium silicate cdicalcium silicate dintensity high in the X-ray diffractogram and eintensity low in the X-ray diffractogram

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)

Figure 4 X-ray diffraction pattern of (a) ordinary Portland cement (before milling) and (b) ultrafine cement produced by 6 h bead milling

from the X-ray diffractogram of the OPC after 6 h millingThis is might be due to the significant reduction in intensityof the particular crystal plane diffraction In the presentinvestigation it is observed from the figures that the peakcorresponds to a particular phase which appeared at thesame 2120579 value for both of the cement samples (ordinaryPortland cement and ultrafine cement sample prepared after6 h milling) It indicates that the chemical phases are notaltered even after 6 h milling of the cement Therefore it isensured that the bead milling process is able to comminutethe cement particle by keeping the chemical phases of thecement unaffected Nevertheless after the critical analysis ofthe X-ray diffraction patterns of the cement samples it isenvisaged that the peaks appeared to be due to the Ca(OH)

2

which become sharper and more intense for the ultrafinecement (produced by bead milling for 6 h) as comparedto that of the ordinary Portland cement (before milling)Similarly peaks correspond to the C

3S and C

2S phases of the

ultrafine cement produced after 6 h milling which becomesharper as compared to that of the OPC (before milling)but appear less intense (except peak at 2120579 = 509∘ highintense) as compared to that of the OPC (before milling)This is might be due to the increase in phase purity after themilling of the cement Due to the bead milling the particlesize of the cement retains at the nanoscale level (sim200ndash300 nm) which in turn resists to overlap with the chemicalphases consequently sharp peaks are observed in the X-raydiffractogram of the ultrafine cement Accordingly the extentof Ca(OH)

2content is increased in the ultrafine cement (after

6 h milling) as compared to that of the ordinary Portlandcement (before milling)

Viewing in light of the above results and analyses it isconsidered that the beadmilling process is an efficient scheme

to produce ultrafine cement of the particle size 200ndash300 nmfrom the ordinary Portland cement (microcement) utilizingtop down nanotechnology concept retaining the chemicalphases unaffected Based on the particle size analysis we aretrying to optimize the time required to produce the smallestsize of the cement particle using bead milling process Asenvisaged from Table 4 the particle size of the cementreduces gradually with increase in milling time Initiallyit was tried to find out the trend for the comminutionof the particle size with the milling time for 50 (D50)and 90 (D90) passed cement particle The trends for thecomminution of D50 and D90 are well fitted (9999 and100 resp) with the equation 119910 = 220+12350 exp(minus4816119909)and 119910 = 350 + 38420 exp(minus530119909) respectively (Figures 5(a)and 5(b)) It indicates that the comminution of the cementparticle withmilling time follows an exponential trend Basedon the trends the variation of the rate of comminutionof particle size (dPsdt) with milling time (t) has beeninvestigated (shown in Figures 5(a) and 5(b)) As shownin Figures 5(c) and 5(d) the plot of dPsdt Vs time (t) isextrapolated up to 10 h milling time using the respectiveequation for D50 and D90 From Figures 5(c) and 5(d) it isfound that the value of dPsdt becomes zero at the millingtime (119905) = 63 h for both D50 and D90 Therefore fromthis curve it is assessed that beyond 63 h milling size ofthe cement particle will not be reduced further because therate of comminution of the particle size becomes zero at 63 hmilling Thus the 63 h is the optimummilling time at whichthe smallest particle of the cement will be obtained Hencefrom the extrapolated figures (Figures 5(c) and 5(d)) theparticle sizes of the 90 (D90) and 50 (D50) passed cementare estimated to besim350 andsim220 nm respectively after 63 hmilling Therefore from the analysis it is concluded that the


0 6100

1000

10000

Resultant particle size after millingExponential fit of resultant particle size

Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

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100000

D90

0 6

Resultant particle size after millingExponential fit of resultant particle sizedPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230

Fitted curve of particle sizeExtrapolate fitted curve

dPsdtExtrapolate (dPsdt)

D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

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minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10



Milling time (h)6 7 9

(d)

Figure 5 Variation of the particle size as well as the variation of the rate of comminution of the particle size (dPsdt) as the function of themilling time for (a) D50 and (b) D90 Extrapolate curve for the variation of the particle size as well as the variation of the rate of comminutionof the particle size (dPsdt) as the function of the milling time up 10 h for (c) D50 and (d) D90 to predict the optimummilling time at whichthe smallest size of the particle can be produced

bead milling process is able to produce 90 of the cementless than 350 nm and 50 of the cement less than 220 nmrespectively after 63 h milling As described in Table 1 thepresent investigation for the first time attempted to produceultrafine cement and is able to produce cement of the particlesize sim350ndash220 nm

4 Conclusion

This investigation offers a new idea to produce ultrafinecement utilizing bead milling process Based on the resultsit is considered that the bead milling process is the uniquescheme to produce ultrafine nanoscale cement particle

(sim200ndash300 nm) from microscale particle (sim1257 120583m) Fromthe particle size distribution of the cement particle beforeand after milling it is assessed that irrespective of the useof grinding agents such as methanol (CH

3OH) and ethanol

(CH3CH2OH) the particle size of the cement is significantly

reduced by the milling and it decreases gradually withincrease in milling time Additionally from the particle sizeanalysis it is elucidated that the performance of ethanol asa grinding agent in the production of ultrafine cement ismore efficient as compared to that of the methanol SEMmicrographs of the cement particle before and after millingclearly prove the comminution of the cement particle by thewet grinding of the cement Based on the critical analysis of


the comminution of particle size it is appraised that the beadmilling process is able to produce 50 of cement particle lessthan 220 nm and 90 of cement particle less than 350 nmafter 63 h milling Based on the chemical composition andXRD analyses it is concluded that the bead milling process isable to produce ultrafine cement of the particle size sim200ndash300 nm retaining the chemical phases unaffected Accord-ingly it is expected that the ultrafine cement particle will defi-nitely influence the properties of the final product which willencourage the cement research towards the development ofthe high performance and sustainable constructionmaterials

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

The authors would like to acknowledge BK21 the Govern-ment of Korea for their funding to pursue this researchprogram

References

[1] P Balaguru and K Chong ldquoNanotechnology and concreteresearch opportunitiesrdquo in Proceedings of the ACI Session onNanotechnology of Concrete Recent Developments and FuturePerspectives National Science Foundation Denver Colo USANovember 2006

[2] A K Mukhopadhyay ldquoNext-generation nano-based concreteconstruction products a reviewrdquo in Nanotechnology in CivilInfrastructure a Paradigm Shift K Gopalakrishnan et al Edpp 207ndash223 Springer Berlin Germany 2011

[3] P Mondal Nanomechanical properties of cementitious mate-rials [Doctoral thesis] Northwestern University EvanstonIll USA 2008 httpwwwnumisnorthwesterneduthesisThesis-Paramitapdf

[4] M Schmidt ldquoInnovative cementsrdquo Zement-Kalk-Gips vol 51pp 444ndash450 1998

[5] B Han X Yu and J Ou ldquoMultifunctional and smart carbonnanotube reinforced cement-based materialsrdquo in Nanotechnol-ogy in Civil Infrastructure a Paradigm Shift K GopalakrishnanP Taylor andNOAttoh-Okine Eds pp 1ndash47 Springer BerlinGermany 2011

[6] L Raki J Beaudoin R Alizadeh J Makar and T Sato ldquoCementand concrete nanoscience and nanotechnologyrdquoMaterials vol3 pp 918ndash942 2010

[7] H Li H Xiao J Yuan and J Ou ldquoMicrostructure of cementmortar with nano-particlesrdquo Composites B Engineering vol 35no 2 pp 185ndash189 2004

[8] R P Selvam K D Hall V J Subramani and S J MurrayldquoApplication of nanosciencemodeling to understand the atomicstructure of C-S-Hrdquo inNanotechnology in Civil Infrastructure AParadigm Shift K Gopalakrishnan B Birgisson P Taylor andN O Attoh-Okine Eds pp 87ndash102 Springer Berlin Germany2011

[9] J Makar ldquoThe effect of SWCNT and other nanomaterials oncement hydration and reinforcementrdquo in Nanotechnology in

Civil Infrastructure a Paradigm Shift K Gopalakrishnan Edpp 103ndash130 Springer Berlin Germany 2011

[10] M Kutschera L Nicoleau and M L Brau ldquoNano-optimizedconstruction materials by nano-seeding and crystallizationcontrolrdquo in Nanotechnology in Civil Infrastructure a ParadigmShift K Gopalakrishnan et al Ed pp 175ndash205 SpringerBerlin Germany 2011

[11] B Bhuvaneshwari S Sasmal and N R Iyer ldquoNanoscienceto nanotechnology for civil engineeringmdashproof of conceptsrdquoin Proceedings of the 4th WSEAS International Conference onRecent Researches in Geography Geology Energy Environmentand Biomedicine (GEMESED rsquo11) pp 230ndash235 2011 httpwwwwseasuse-libraryconferences2011CorfuGEMESEDGEMESED-40pdf

[12] K L Scrivener ldquoNanotechnology and cementitious materialsrdquoin Proceedings of the NICOM3 ldquoNanotechnology in Construction3rdquo Z Bittnar et al Ed pp 37ndash42 Springer Berlin Germany2009

[13] E J Garboczi ldquoConcrete nanoscience and nanotechnologydefinitions and applicationsrdquo inProceedings of the 3rdNanotech-nology in Construction Conference (NICOM rsquo09) Z Bittnar Edpp 81ndash88 Springer Berlin Germany 2009

[14] K Sobolev I Flores R Hermosillo and L M Torres-MartınezldquoNanomaterials and nanotechnology for high-performancecement compositesrdquo in Proceedings of the ACI Session onNanotechnology of Concrete Recent Developments and FuturePerspectives Denver Colo USA November 2006

[15] C C Pilevneli S Kızgut I Toroglu D Cuhadaroglu and EYigit ldquoOpen and closed circuit dry grinding of cement millrejects in a pilot scale vertical stirred millrdquo Powder Technologyvol 139 no 2 pp 165ndash174 2004

[16] S L Sarkar and JWheeler ldquoImportant properties of an ultrafinecement-part Irdquo Cement and Concrete Research vol 31 no 1 pp119ndash123 2001

[17] Z Huang M Chen and X Chen ldquoA developed technology forwet-ground fine cement slurry with its applicationsrdquo Cementand Concrete Research vol 33 no 5 pp 729ndash732 2003

[18] M Yousuf A Mollah F Lu R Schennach and D LCocke ldquoAn x-ray diffraction fourier-transform electronmicroscopyenergy-dispersive infrared spectroscopy andscanning spectroscopic investigation of the effect of sodiumlignosulfonate superplasticizer on the hydration of portlandcement type vrdquo Polymer vol 38 no 5 pp 849ndash868 1999

[19] M A Trezza ldquoHydration study of ordinary Portland cement inthe presence of zinc ionsrdquoMaterials Research vol 10 no 4 pp331ndash334 2007

[20] GVaickelionis andRVaickelioniene ldquoCement hydration in thepresence of wood extractives and pozzolan mineral additivesrdquoCeramicsmdashSilikaty vol 50 no 2 pp 115ndash122 2006

[21] P K Panigrahy G Goswami J D Panda and R K PandaldquoDifferential comminution of gypsum in cements ground indifferent millsrdquoCement and Concrete Research vol 33 no 7 pp945ndash947 2003

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


Table 1 Comparative study for the preparation of nanocement or ultrafine cement and their performance reported in the existing literature

Primary material Additivesprocedure Particle size Effectperformance Reference

Portland cementNanosize ingredients such asalumina silica particles and carbonnanotubes were added

lt500 nmNanocement can create newmaterials devices and systems atthe molecular nano- and microlevel

[1]

Portland cementNano-SiO2 nano-TiO2nano-Al2O3 nano-Fe2O3 andnanotubenanofibers were added

sim20 nm and 100 nmCan produce concrete with superiormechanical properties as well asimproved durability

[2]

Portland cement Single wall and multiwall carbonnanotubes were added mdash

Cement materials showed superiormechanical electrical and thermalproperties

[5]


Spherical nanoparticle nano-SiO2nano-Fe2O3 and multiwall carbonnanotube were added

1ndash100 nmSignificant improvement incompressive strength as well asYoungrsquos modulus and hardness ofthe concrete

[6]

Portland cement Spherical nano-Fe2O3 andnano-SiO2 were added

15 nm Mortar showed higher compressivestrength as well as flexural strength [7]

Portland cement Open closed circuit dry grinding ofthe cement by stirring mill 20ndash25 120583m

Grinding of cement increases thesurface area and decreases theparticle size to 20ndash25 120583m

[15]

Ultrafine cementUltrafine cement obtained by drygrinding flyash and admixtureadded

085ndash088 120583mReplacement of ultrafine cementwith flyash decreases the strength ofthe cement material

[16]


Wet grinding of the cement (WMC)using stirred mill 40ndash10 120583m

After 2ndash4min grinding maximum40 120583m and average 10 120583m cementcan be produced

[17]


Wet grinding of cement using beadmill and alcohol used as grindingagent

350ndash220 nmWet grinding produces sim220 nmcement particle (50) withoutaffecting chemical phases

Present work

cement is hydrated in a faster rate as compared to that ofthe conventionally available cement [1 2 14] The fast rateof hydration reaction leads to developing early strength incement composite which in turn reduces the time for thebuilding construction

The methods discussed above focus on the incorporationof foreign nanoparticle in the cement system Howeververy limited reports are available based on the productionof ultrafine cement by physicomechanical crushing of theconventional cement particle [15ndash17] Table 1 summarizesvarious procedures used for making of the nanocement andtheir application Based on the critical literature survey it isassessed that the fine cement of the particle size 200ndash2120583mcan be produced by the grinding of the cement using ballmill vibration mill Raymond mill mixing mill or air-blowmill stirred mill and so forth [15ndash17] Accordingly it is alsoreported that due to the milling of the cement surface areaof the cement particle increases consequently agglomerationof the particle occurs Therefore a special arrangement isrequired for its storage and packing which in turn increasesthe cost of the cement [17] However to the best of our knowl-edge and belief no research report is yet available which canproduce cement (50ndash90 of the weight) of the particle size200ndash300 nm using physicomechanical crushing Thereforereviewing the literature it is apparent that wet grinding of thecement particle utilizing top-down nanotechnology for theproduction of ultrafine cement (sim200ndash300 nm) has not beenstudied yet

In order to produce ultrafine (submicro) cement usingphysicomechanical crushing (top-down) method beadmilling process has been selectedThe chemical compositionparticle size distribution and SEM and XRD analyses werepreferred selectively to evaluate the effectiveness of thebead milling process in production of ultrafine or submicrocement Based on the analyses it is assessed that beadmillingprocess is demonstrated to be very effective to produce theultrafine cement of the particle size 200ndash300 nm retainingthe chemical phases unaffected

2 Experimental21 Materials Ordinary Portland cement provided bySsangyong Cement Industrial Company Korea was usedas the principal material for the production of ultrafinecement The particle size specific gravity and fineness ofthe used ordinary Portland cement are 10ndash30120583m 315 andsim2800 cm2g respectively

Methanol and ethanol purchased from Merck Germanywere used as crushing aid for the production of ultrafine(submicro) cement using bead milling process The generalfeatures of the methanol and ethanol are represented inTable 2

In this investigation Zirconia ceramic beads purchasedfrom Shanghai Pangea Import and Export Co Ltd Chinawere used as a grinding media due to its extreme lowwear loss high grinding efficiency and high durability as








Separation gab



2sim






3OH) and ethanol (C

2H5OH)














3OH) and ethanol (C

2H5OH)






20

18

16

14

12

10

8

6

4

2

0

Chan

nel (

)

Pass

ing

()

006

009

015

023

038

058

091

144

228 36

569 9

1422

2249

3556

5623

8891

14058

22228

35146

55571

87867

100

90

80

70

60

50

40

30

20

10

0

Size (microns)


(a)

20

18

16

14

12

10

8

6

4

2

0


Chan

nel (

)

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

0001

00016

00027

00045

00076

00128

00215

00361

00608

01022

01719

0289

0486

0818

1375

2312

389

654

(b)

00001 0001 001 01 1 10 100 1000

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)



(c)








(a) (b)

(c) (d)




2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar






3S











100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










Separation gab



2sim






3OH) and ethanol (C

2H5OH)














3OH) and ethanol (C

2H5OH)






20

18

16

14

12

10

8

6

4

2

0

Chan

nel (

)

Pass

ing

()

006

009

015

023

038

058

091

144

228 36

569 9

1422

2249

3556

5623

8891

14058

22228

35146

55571

87867

100

90

80

70

60

50

40

30

20

10

0

Size (microns)


(a)

20

18

16

14

12

10

8

6

4

2

0


Chan

nel (

)

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

0001

00016

00027

00045

00076

00128

00215

00361

00608

01022

01719

0289

0486

0818

1375

2312

389

654

(b)

00001 0001 001 01 1 10 100 1000

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)



(c)








(a) (b)

(c) (d)




2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar






3S











100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials












3OH) and ethanol (C

2H5OH)






20

18

16

14

12

10

8

6

4

2

0

Chan

nel (

)

Pass

ing

()

006

009

015

023

038

058

091

144

228 36

569 9

1422

2249

3556

5623

8891

14058

22228

35146

55571

87867

100

90

80

70

60

50

40

30

20

10

0

Size (microns)


(a)

20

18

16

14

12

10

8

6

4

2

0


Chan

nel (

)

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

0001

00016

00027

00045

00076

00128

00215

00361

00608

01022

01719

0289

0486

0818

1375

2312

389

654

(b)

00001 0001 001 01 1 10 100 1000

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)



(c)








(a) (b)

(c) (d)




2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar






3S











100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




20

18

16

14

12

10

8

6

4

2

0

Chan

nel (

)

Pass

ing

()

006

009

015

023

038

058

091

144

228 36

569 9

1422

2249

3556

5623

8891

14058

22228

35146

55571

87867

100

90

80

70

60

50

40

30

20

10

0

Size (microns)


(a)

20

18

16

14

12

10

8

6

4

2

0


Chan

nel (

)

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)

0001

00016

00027

00045

00076

00128

00215

00361

00608

01022

01719

0289

0486

0818

1375

2312

389

654

(b)

00001 0001 001 01 1 10 100 1000

Pass

ing

()

100

90

80

70

60

50

40

30

20

10

0

Size (microns)



(c)








(a) (b)

(c) (d)




2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar






3S











100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)




2 MgO Al

2O3 Fe2O3 and SO

3 Sarkar






3S











100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials









100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(a)

100

80

60

40

20

0

Inte

nsity

0 10 20 30 40 50 60

2120579 (deg)

(b)



2


3S and C

2S phases of the







0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0 6100

1000

10000


Part

icle

size

(nm

)

D50

dPsdt

1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

2

1

0

minus1

minus2

minus3

minus4

minus5

times104

y = 21999 + 12350 exp(minus4816x)

(a)Pa

rtic

le si

ze (n

m)

1000

10000

100000

D90

0 6


1 2 3 4 5

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

times104

y = 34999 + 38420 exp(minus531x)

60

00

minus60

minus120

minus180

(b)

Part

icle

size

(nm

)

5 8 10210

215

220

225

230



D50

Milling time (h)

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)10

00

minus10

minus20

minus30

minus40

minus50

times10minus6

6 7 9

(c)

Part

icle

size

(nm

)

340

345

350

355

360

365

00

D90

Cum

min

utio

n ra

te o

f par

ticle

size

(dPsdt)

minus60

minus90

minus30

times10minus7

5 8 10




(d)



4 Conclusion



3OH) and ethanol







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







Acknowledgment


References






























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Documents

Research Article Effectiveness of the Top-Down