Opportunities&ChallengesforUseofNanotechnologyinCementBasedMaterials

Dr Rakesh Kumar, Scientist Dr Renu Mathur, Scientist & HoD and Dr Arun Kumar Mishra, Scientist,
RigidPavementsDivision,CentralRoadResearchInstitute(CRRI),NewDelhi
Exploring and manipulating inner characteristics at nanometer scale of matter in order to obtain
exceptionalpropertiesandperformanceofmaterialsisoneofthemostactiveresearchareasofthepresent
time. The potential for application of nanotechnology in cementbased materials is huge. Currently,
applications of nanotechnology in cementbased materials in several areas including construction of
concreteroadsarebeingexplored.Nanotechnologyhasimmensepotentialtoresultinanewgenerationof
concrete,strongerandmoredurable,withdesiredstressstrainbehaviorandpossiblywiththewholerange
of newly introduced properties. Enhanced flexural behavior of the concrete may lead a reduction in the
concrete slab thickness used in the construction of concrete pavements. This paper presents brief
informationonnanotechnologyresearchopportunitiesandchallengesincementbasedmaterials.
Introduction

Nanotechnology has immense potential and abilities to control the materials world including cementbased
materials. It is the science of extremely tiny particle that deals with the study and use of materials and
devicesthatoperateatunimaginablenanometerscalei.e.onebillionth,or10"9,ofameter.Ananometeris
sosmallthatwecannotseesomethingofthissizewithouttheuseofverypowerfulmicroscopes.Itisused
to measure things that are very tiny i.e. atoms and molecules. Another way of putting it: a nanometer is
the amount an average mans beard grows in the time it takes him to raise the razor to his face [1]. It is
more about taking advantage of novel properties that arise solely due to the nanoscale and producing
useful or functional components. Materials at this scale behave very differently from when they are in
larger form. This technology offers better built, long lasting, cleaner, safer and smarter products for the
home, for medicine, for agriculture, for communication and for industry in general. It is the synthesis and
application of ideas from science and engineering towards the understanding and production of new
materialsanddeviceswithenhancedpropertiesandcapabilities.
Nanoscience&Nanotechnology

Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular and
macromolecular scales, where properties differ significantly from those at a larger scale while
nanotechnology describes design, characterisation, production and application of materials and systems by
controllingthesizeatnanometrescale.Theterm"Nanotechnology"wasinventedbyTaniguchiin1974,and
it was first popularized in the 1980 by scientist and visionary K. Eric Drexler [2] in his book "Engines of
Creation." Nanotechnology is the creation and utilization of materials, devices, and systems through the
control of matter on the nanometre scale. It is more about taking advantage of novel properties that arise
solely due to the nanoscale and producing useful or functional components with new or enhanced
properties.Someoftheimportantfieldswherenanotechnologyapplicationsarebeingactivelyexploredare
showninFig.1.
WhyDoMaterialsatNanoScaleBehaveDifferently?

Figure1:Currentactivefieldswherenanotechnologyapplicationsarebeingexplored

When the dimensions of a material are decreased from macro size to nano size, significant changes in
electronic conductivity, optical absorption, chemical reactivity and mechanical properties occur. Materials
with the size range from 100 nm down to the atomic level can have different or enhanced properties
comparedwiththesamematerialsatalargersize.Thetwomainreasonsforthechangeinbehaviorarean
increased relative surface area and the dominance of quantum effects [13]. An increase in surface area
will result in a corresponding increase in chemical reactivity and making some nanoparticles useful as
catalyststoo.Assizeofthematterisreducedtotensofnanometersorless,quantumeffectscanbeginto
playarole,andthesecansignificantlychangematerialsoptical,magneticorelectricalproperties.
CarbonNanotubes(CNTs)

Carbon nanotubes are among the most extensively researched nanomaterials today. CNTs are tubular
structures of nano meter diameter with large aspect ratio. These tubes have attracted much attention in
recentyearsnotonlyfortheirsmalldimensionsbutalsofortheirpotentialapplicationsinvariousfields.A
single sheet of graphite is called grapheme. A CNT can be produced by curling a graphite sheet. Carbon
sheets can also curl in number of ways. CNT can be considered as the most superior carbon fiber ever
made.Additionofsmallamount(1%bywt)ofCNTcanimprovethemechanicalpropertiesconsistingofthe
main Portland cement phase and water. A CNT can be singled or multi walled. CNTs are the strongest and
most flexible molecular material with Youngs modulus of over 1 TPa. The approximate diameter is 1 nm
with length to micron order. CNTs have excellent flexibility. These are essentially free from defects.
Nanotubes are highly resistant to chemical attack and have a high strength to weight ratio (1.8g/ cm3 for
MWNTs & 0.8G/cm3 for SWNTs). CNT has maximum strain of about 10% which is higher than any other
material. Fig.2 shows the flexible behaviour of CNTs. Electrical conductivity of CNTs are six orders of
magnitude higher than copper, hence, have very high current carrying capacity. Hence, carbon nano tubes
haveexcellencepotentialforuseinthecementcomposites.
OpportunitiesintheFieldsofCementBasedComposites

Nanotechnology is being used for the creation of new materials, devices

and systems at molecular, nano and microlevel [49]. Interest in
nanotechnology concept for portland cement composites is steadily
growing. The most reported research work regarding application of
nanotechnology in cementbased materials is either related to coating or
Figure2:FlexiblebehaviorofCNTs
enhancementofmechanicalandelectricalproperties.Someofthewidely
reportednanoparticlesincementconcreteindustriesareTitaniumdioxide
( TiO2), Nanosilica (SiO2), Alumina (Al2O3), Carbon nanotube (CNT) etc. Currently, the most active

research areas dealing with cement and concrete are: understanding of the hydration of cement particles
and the use of nanosize ingredients such as alumina and silica particles [47]. A typical scale of various
constituentofanormalconcreteisgiveninFig.3.

Figure3:Scalesofvariousconstituentsofconcrete[7]
Average size of Portland cement particle is about 50 microns. In applications that require thinner final
products and faster setting time, micro cement with a maximum particle size of about 5 microns is being
used [4]. Knowledge at the nanoscale of the structure and characteristics of materials will promote the
development of new applications and new products to repair or improve the properties of construction
materials. For example, the structure of the fundamental calciumsilicatehydrate (CSH) gel which is
responsible for the mechanical and physical properties of cement pastes, including shrinkage, creep,
porosity, permeability and elasticity. CSH gel can be modified to obtain better durability. Cementbased
materials containing carbon nanotubes can be used for both strengthening and enhancing electrical and
electronic properties of the concrete besides their mechanical properties. Development of smart concrete
using carbon nano tubes would be easier. If nanocement particles can be processed with nanotubes and
nanosize silica particles conductive, strong, tough, more flexible, cementbased composites can be
developedwithenhancedproperties,forelectronicapplicationsandcoatings.
NanoConcreteandNanoIngredients

Nanoconcreteisdefinedasaconcretemadewithportlandcementparticleswithsizesrangingfromafew
nanometertoamaximumofabout100micrometers[4].Nanoingredientsareingredientswithatleastone
dimensionofnanometersize.Thereforetheparticlesizehastobereducedinordertoobtainnanoportland
cement. If these nanocement particles can be processed with nanotubes and reactive nanosize silica
particles conductive, strong, tough, more flexible, cementbased composites can be developed with
enhancedproperties,forelectronicapplicationsandcoatings.Thereisalsolimitedinformationdealingwith
themanufactureofnanocement.Ifcementwithnanosizeparticlescanbemanufacturedandprocessed,it
will open up a large number of opportunities in the fields of cementbased composites. Current research
activityinconcreteusingnanocementandnanosilicaincludes:
Characterizationofcementhydration
Influenceoftheadditionofnanosizesilicatoconcrete
Synthesisofcementusingnanoparticlesandcoatings(appliedtoprotectconcrete).
The characteristics of nano concrete can be effectively used to create unique products, which can be also
moldedtocomplexshapes.Nanoconcretecontainingcarbonnanotubescanbeusedforbothstrengthening
and creating electric circuits. Recently, Wang et al. [10] has demonstrated the use of nanoclays in the
makingofselfcompactingconcreteforimproveitforslipformpavingfortheconstructionofconcreteroad.
TheNISTresearchershaveclaimedthattheservicelifeofconcretecouldbedoubledbyusingananosized
additive
that
slows
down
aggressive
ion
transport
in
concrete
(http://www.nanowerk.com/news/newsid=9054.php). Rather than change the size and density of the pores
in concrete, they reasoned, it would be better to change the viscosity of the solution in the concrete to
reducethespeedatwhichchloridesandsulfatesentertheconcrete.Thebasicis"Swimmingthroughapool

ofhoneytakeslongerthanmakingitthroughapoolofwater.TheNISTresearchershavedemonstratedthat
the nanotechnology additives can be blended directly into the concrete with current chemical admixtures,
butthatevenbetterperformanceisachievedwhentheadditivesaremixedintotheconcretebysaturating
absorbent,lightweightsand[8]
It has been claimed that all the samples showed a unique nanosignature for the CSH material regardless
ofthesampleorigin.Thisisknownasthematerialsgenomiccodeandmeansthatthestrengthofcement
paste is not a function of specific minerals but relates to the way the nanoparticles are arranged. "If
everythingdependsontheorganizationalstructureofthenanoparticlesthatmakeupconcrete,ratherthan
onthematerialitself,wecanconceivablyreplaceitwithamaterialthathasconcretesothercharacteristics
strength, durability, mass availability and low costbut does not release so much CO2 into the
atmosphere during manufacture." said Professor FranzJosef Ulm from civil and environ mental
engineeringatMIT[11].
NanoSilicaFumeforImprovingConcretePerformance

Nanosilicaismostcommonnanoadditivetoconcrete.Itisreportedthatnanosilicawasfoundtobemuch
effective than micron sized silica for improving the performance such as permeability, and subsequently,
durability. In addition, reduced amount of about 15 to 20 kg of nano silica was found to provide same
strengthas60kgofregularormicrosilica.Fig.4presentsatypicalSEMofnanosilicaparticles.
Nanosilicaiseffectiveadditivestopolymersandconcrete,adevelopmentrealizedinhighperformanceand
selfcompacting concrete with improved workability and strength. Nanosilica addition to cement based
materials control the degradation of the fundamental CSH (Calciumsilicatehydrate) reaction in water as
wellasblockwaterpenetrationandleadstoimprovementindurability.TheadditionofnanoSiO2particles
enhances the density and strength of concrete. The results indicate that nanosilica behaves not only as a
fillertoimprovemicrostructure,butalsoasanactivatortopromotepozzolanicreactionforflyashconcrete
asaresultstrengthoftheflyashconcreteimprovesparticularlyintheearlystages.
CoatingsforConcrete

Another major large volume application of nano powder in cement

based materials is the area of coatings. The attractive colouring on
ancient Czech glasses is found to contain nanoparticles. This shows
that nanotechnology was used for coating surfaces i.e. spraying and
making a product look attractive from ancient time. Nanopowders
have a remarkable surface area. The surface area imparts a serious
change of surface energy and surface morphology. The change in
properties causes improved catalytic ability, tunable wavelength
sensing ability and better designed pigments and paints with self
cleaningandselfhealingfeature.Onepromisingareaofapplicationof
Figure4:SEMofatypical
nanoparticle for cement based materials is development of self
nanosilicaparticles
cleaningcoating.Titaniumoxideiscommonlyusedforthispurpose.It
is incorporated, as nano particles to block UV light. It is added to paints, cements and windows for its
sterilizing properties as TiO2 breaks down organic pollutants, volatile organic compounds, and bacterial
membrane through powerful catalyst reactions and can reduce airborne pollutants applying to outer
surfaces. Additionally it is hydrophilic and therefore gives selfcleaning properties to surface to which it is
applied.
ChallengesfortheApplicationofNanotechnologyinCementBasedMaterials

The primary challenge is to manufacture nanosize cement particles. The second challenge is the heat of
hydration.Duetomanyfoldsincreaseinspecificsurfaceareasthenanocementparticleareveryreactive
andresultsinenormousamountofheatofhydration.Specialorganicandinorganicadditivesareneededto
be developed to control the setting and heat of hydration. For the nanocoatings, the properties of the
coatingsthemselvesneedextensiveinvestigation.Durabilityofcoatingsundervariousexposureconditions,
abrasion resistance, friction resistance, high temperature resistance, failure modes, and electrical
characteristics need to be proven by using exhaustive experiments. Furthermore, huge amount of
expenditure is needed for the equipments to study the behaviour of nano cement and nano additive in

cementbasedmaterials.
Conclusion

There is wide scope for the use of nanotechnology including nano ingredients for harnessing improved
mechanical and electrical properties such as higher strength, toughness, flexibility, stability, conductivity,
besides selfcleaning property of cementbased composites. The challenges are also huge that includes
health hazards working with dry nanoparticle, huge expenditure for procuring equipment for study at nano
level.Currently,limitedavailability/Nonavailabilityofnanocement,sandetc.makesitdifficulttoapplyto
use this technology in cementbased material. Current studies are mostly confined to laboratory stage.
Therefore, a lot more extensive studies are required before the application of nanotechnology becomes
viableandeconomicalwayforenhancingtheimportantpropertiesofcementbasedmaterials.
Acknowledgments

The authors are grateful to the Director, Central Road Research Institute for his permission to publish the
paper.ThehelpprovidedbyMsS.Juneja(RI),MrRanjitKumar(Atraineestudent)andMrM.K.Singh(TA)
arethankfullyacknowledged.
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NBMCWAugust2011

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hand side pics.