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ssImpact of Nanotechnology on High Performance Cement and

Concrete

Ammar Sadik Dahlan

PII: S0022-2860(20)31221-7
DOI: https://doi.org/10.1016/j.molstruc.2020.128896
Reference: MOLSTR 128896

To appear in: Journal of Molecular Structure

Received date: 8 May 2020

Accepted date: 13 July 2020

Please cite this article as: Ammar Sadik Dahlan , ssImpact of Nanotechnology on
High Performance Cement and Concrete, Journal of Molecular Structure (2020), doi:
https://doi.org/10.1016/j.molstruc.2020.128896

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Highlights
1. Nanotechnology has a very important impact on high performance cement
and concrete.
2. High performance concrete can be prepared using various nanoparticles

additives.

3. The strength of the cement is improved with nanoparticle additives

 Impact of Nanotechnology on High Performance Cement and
Concrete

Ammar Sadik Dahlan

Department of Architecture- Faculty of Architecture and Planning - King AbdulAziz University-

Saudi Arabia

Abstract

The nanoparticles are promising materials for the construction components in

terms of compressive strength, density, porosity and novel applications. High
performance concrete (HPC), functionalized concretes and coating materials can be
prepared using various nanostructured Carbon cement additives, polymeric additives,
ionic cement additives. CNT and graphene functionalization are the most promising
routes to create cement nanocomposites. The strength of the cement for construction
buildings can be improved with nanoparticle additives. The nanoparticles or nanoparticle
mixture exhibit the best performance in terms of compressive strength, capillary
absorption coefficient, and pore radius of cement mortars. It is evaluated that
nanotechnology has a very important impact on high performance cement and concrete.

Corresponding author: adahlan@kau.edu.sa (Ammar Sadik Dahlan)

Keywords: Nanotechnology, nanoparticles, construction

1. Introduction
Nanotechnology is loosely defined as the application of technology whose
materials possess features of about 100nm or below, although some authors stretch this
definition up to 1µm[1]. The application of nano-sized components has already
revolutionized fields such as electronics, energy harvesting, and medicine among others.
Recently nanotechnology is being spread towards more established fields, construction
technology being one of them. The global construction industry is expected to be worth
10.3 Trillion USD by 2020.[2] Given the potential of nanotechnology to revolutionize the
construction industry, research in this field can drive to great economic remuneration.

Nanotechnology can essentially be applied to all components of construction,

reinventing materials thus allowing designs previously only left for imagination. Key
niches in the construction industry include high performance concrete (HPC),
functionalized concretes and coating materials. Among the HPC are the high strength
concretes, self-compacting concretes, quick setting concretes, or concretes with some of
these characteristics. High strength concretes must have a compressive strength of at least
41 MPa at 28 days as defined by the American Concrete Institute Committee (ACI) 363
R[3]. Self-compacting concretes must be able to flow under their own weight onto its
mold without vibration, and quick setting concrete must set faster than ordinary Portland
cement. Before the use of nanotechnology, these characteristics could only be
interchanged. Recent material developments are paving a new route for construction
materials.

2. Literature Review

2.1. Silica, alumina and other nanoparticles as cement additives

Silica, or silicon dioxide, has been researched since 1960’s as a pozzolanic
material for Portland cement. Silica fumes (SF), amorphous polymorphs of silicon
dioxide, are used nowadays as a cement additive. Crystalline silica is not used as an
additive for it does not perform as well as amorphous silica.[4]

Nano-sized Silica particles or nanosilica (NS) with an average particle size lower
than 120nm exhibit a superior pozzolanic effect over SF. It has been reported that NS
serves as nucleation site. Properly dispersed NS particles enhance the density of
interfacial grain zones improving the strength of the cement[3]. X-ray diffraction (XRD)
and differential scanning calorimetry (DSC) studies clearly show that NS increases the
pozzolanic activity of cement mixtures[5]. By comparing qualitatively the powder XRD
patterns of cement mixtures with NS and with silica fume, it can be observed that the
evolution of day 3 XRD pattern of the former mixture is comparable with the day 60 of
the latter mixture. DSC shows a similar trend when measuring the content of the
precursor calcium hydroxide (CH). Day 3 NS mixture contains a commensurate amount
of CH with the SF mixture at day 28.

It is to be noted that NS agglomeration leads to detrimental effects on cements

lowering their strength. Moreover low NS loadings fill the concrete pores while higher
loadings enhance pore formation.[3] By compensating with a higher superplasticizer
percentage, NS helps decrease the porosity and capillary water absorption.[3] Lower
porosity decreases the chloride ion penetration, which adversely affects the cements
lifetime. For example, Jo et al. showed that loadings of 6% of NS to Ordinary Portland
Cement (OPC) can achieve a compressive strength of 88 and 102.28 MPa at an age of 7
and 28 days, respectively. OPC exhibited a compressive strength of 18.3 and 25.6 MPa at
age 7 and 28. Water to cement ratio was readjusted to 0.23 for NS addition to achieve the
higher 7 and 28 day compressive strengths.[6] Moreover sufficient polycarboxylate
superplasticizer (Econex) was added to avoid bleeding, nanoparticle agglomeration, self-
desiccation and cracking.[6] [7]

Uncompensated cement/water/superplasticizer mixture is only benefited by

maximum content loading of around 1.25% of NS, nano-iron oxide (NF), and/or nano-
alumina (NA).[8] Further loadings showed a detrimental effect on compressive strength
and porosity as described by Oltulu et al.[8] In the same work they use NS, NF, NA, or
mixtures thereof to test which nanoparticle or nanoparticle mix show the best
performance in terms of compressive strength, capillary absorption coefficient, and pore
radius of cement mortars. The results indicate that the compressive strength increases in
the following order NS<NF<NA and that the capillary absorption coefficient decreases in
the same order. The less porous cement was obtained when a total of 1.25% content (by
weight) of a mixture of NS, NF, and NA was employed. The highest compressive
strength obtained by Oltulu et al. was of 77MPa with a 1.25% content of NA. While
studies conducted by Li et al.[5], show that a dosage of 5% NA increases the elasticity
modulus by 143%.

CaCO3 nanoparticles have been used to accelerate the hydration rate in OPC.[9]
This effect is significant for nano-sized particles in the range of 50nm to 120nm but not
with micron sized particles from 5 to 20 µm. A common practice is to mix OPC with
fillers such as fly ash. CaCO3 is added to compensate for the fillers main drawback, early
hydration stages cement mix hardness reduction. For example an OPC-fly ash with a 1:1
weight ratio, the hardness at day 1 reduces from 56MPa to 15MPa. Nevertheless, with a
20% load of CaCO3 nanoparticles added to the OPC-fly ash mixture the hardness was
improved to 35 MPa.

Alike other nanoparticles, titanium dioxide nanoparticles (NT) also increase the
mechanical properties of cement. Li et al contrasted the benefit of NT and NS addition
over plain Portland cement.[10] As with other non-optimized concrete/nanoparticle
mixtures, the best performance was achieved at 1% NT loading. The theoretic fatigue
number, also known as fatigue life, of concrete is increased by 475% and 267% at a stress
level S of 0.85 and 0.75. (S= flexural fatigue strength/flexural strength). Furthermore 1%
NT increase the abrasion resistance of concrete by 180%.[11]

An additional property of NT enhanced concrete is the surface contact angle

reduction of water. Concretes exhibiting hydrophobic surfaces are likely to have
enhanced self-cleaning properties. Since water does not prefer to stay on the hydrophobic
surface, the dust particles adsorbed on the surface are more likely to be transported
elsewhere. According to Ruot et al [12], the photocatalyitic activity of NT loaded cement
pastes is significant above a 1% content threshold. Air pollution can be reduced for
indoor and outdoor application by utilizing NT. Indoor volatile organic compounds levels
can be reduced by a third upon the addition of 10% TiO2.[13] Vehicular emissions such
as NOx are reduced by 40% to 80%. [14-17]

Commercial superplasticizers, such as Gaia, are already utilizing nanoparticles as

additives to double the compressive strength of concrete at ages of 7 and 28 days.

Nanoparticle synthesis:
Experimental results show that the sol-gel method can be used effectively for the
synthesis of nanoparticles of SiO2 by either acidic (nitric acid) or basic (ammonia)
reaction media.[18] Generally, temperature treatments above 600°C adversely affect the
surface area of NS and lower the NS performance. Heat treatment at 400°C posses the
highest surface area but achieved a lower compressive strength than the NS treated at
600°C. The amorphicity of the NS treated at 400°C could have a detrimental impact in
the hardening of the cement.

2.2.Nanostructured Carbon cement additives:

Carbon nanostructure research is booming for widespread of applications,
construction materials being one of them. Cement pastes have been doped with several
carbon allotropes, obtaining a widespread of effects on the cement. For example, by using
less that 3% of single walled or multiple walled carbon nanotubes (CNT), the
compressive strength of OPC has been reported to be increased by 50% and the Vickers
hardness by 600%.[9] The observed effect manifested on the early stages of hydration,
and no significant improvement was observed after two weeks. Measurements on bulk
samples have been inconsistent. This is attributed a lack of proper CNT dispersion. A
method to effectively disperse CNTs has not yet been established. A proposed route is to
attach carboxylic groups to functionalize the CNT and enhance its dispersion in water
solvents. Sonication of the CNT-cement mixture has also been endeavored. The
drawback of sonication is that the grain surfaces of the cement are damaged on the
process.

The CNT surface acts as a nucleation site for the CaO-SiO2-H2O (C-S-H) bonds.
As a result CNT are not in direct contact with one another and the electrical conductivity
does not improve significantly. Nevertheless by adding 0.1% of CNT by weight, the
cement mixture exhibits piezoresistive properties.[19] In other words, a cement/CNT
mixture can be used to sense stress or weight by measuring a change electrical
conductivity. The piezoresistivity of cement could be exploited to measure the weight
and speed in real time.
 CNT will not represent a viable additive for concrete mixtures until further
research reduces the CNT production costs and specialized delivery techniques are
developed.

2.3.Polymeric additives
The use of grafting polymers have been proposed to increase the elastic modulus.
The polymers are expected to bind to defective sites and bind the silicate chains. The
grafting polymer could be seen as the stem of a plant bridging leafs and branches into
place. Proposed grafting polymers include hexadecylmethylammonium, polyethylene
glycol, PVA, PDMA, polyacrylic acid and methylene blue. Although no direct evidence
of it has been tested an apparent increase of the elastic modulus 40-100% could be
achieved at low polymer to cement loadings.[9]

2.4.Ionic Cement additives

An alternative to pore reduction is the mixing ionic exchangers to the cement. By
utilizing an inorganic cationic exchanger and an inorganic anionic exchanger, namely a
calcium zeolite and hydrocalumite respectively, the durability of the concrete can be
enhanced. Tests indicate a reduced corrosion or rebar and a decrease of the alkali-
aggregate reaction.[9]

2.4 Coatings, treatments, and applications

Deletum, an anti-graffiti paint, which are simultaneously hydro and oleophobic,
are easy to clean.[20] Moreover these paints are able to withstand repeated graffiti
attacks. Other brands such as Ultra-Ever Dry (Ultratech International) had international
attention as urine repellent coating for concrete in San Francisco. This brand claims to
make the coated material anti-wetting, anti-corrosion, anti-icing, anti-contamination and
self-cleaning hence extending the lifetime.

Mechano-chemically activated cements, are an attempt to reduce the particle size

by ball milling.[21] Additives such as sulfonated naphthalene formaldehyde condensate
(SNF) or sulfonated melamine formaldehyde condensate (SMF) were admixed with the
cement. Although a particle reduction of 40% was achieved after ball milling for 3 hours
with SNF or SMF, the surface area only increased by 80%.
Tarmac has developed a super permeable concrete. Topmix permeable concrete
contains a 20-35% void spaces. The gaps allow a drainage capacity of up to 1000 litres
per minute square meter. The application of permeable concretes can prevent floodings
for they can permeate the excess water onto the natural aquifers. The trade-off for the
high permeability is an average compressive strength of 10 to 20 MPa.[22]

3. Future work / Investigation routes

 In previous works, nanoparticle addition provides the highest gain for cements in
terms of compressive strength, density, porosity and novel applications. Nanoparticles
(NP) exhibiting enhanced catalytic activity could further increase the cement nucleation
and hydration process. Select transition metal oxides nanoparticles have proven their
potential for cement applications. Given their ease of availability, catalytic activity, and
modest cost, period 4 transition metal oxides such as V2O5, MnOx, CoOx, NiO, and CuO
could be pursued. Nanoparticles of MgO, Ce2O3, MoOx, and WOx, could also pose as
viable additives. Ce2O3 and V2O5 NP could function as a starting point for their
coordination chemistry capabilities. Compounds of the previously mentioned
nanoparticles, NS, NF, NA, and/or ZnO could be investigated. Doping of the previous
nanoparticles could be endeavoured for a higher catalytic activity. Albeit NPs have great
potential, their toxicity must be considered, especially when considered for commercial
applications. A revision of standard cement (and concrete) mixing ratios should be
conducted for NP additives. The proportions relative to cement of water content,
superplasticizer and fillers must be optimized to exploit the full potential of NP inclusion.

Carbon nanotubes (CNT) and other novel carbon allotropes are potential
candidates to reinforce concrete, and give self-sensing capabilities. CNT and graphene
functionalization are the most promising routes to create cement nanocomposites. If
CNTs can be tailored to contact one another during the cement nucleation and hydration,
the electrical properties could be increased by 13 orders of magnitude, as it has been done
with alumina.[23]. As of now the limiting factor for carbon allotrope inclusions are their
production costs, although research is being conducted worldwide to solve that issue.

Investigating processes for making concrete permeable for asphalt applications.

Ideas could revolve on sacrificial materials, self-compacting cements, coated aggregates
and/or irregular aggregate size distribution.

[1-43]
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