Journal of Building Engineering 35 (2021) 102008

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Journal of Building Engineering

journal homepage: http://www.elsevier.com/locate/jobe

Review: Effects of nanoparticles in cementitious construction materials at

ambient and high temperatures
Luís Laím *, Hugo Caetano, Aldina Santiago
ISISE, Department of Civil Engineering, University of Coimbra, Coimbra, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: Nanotechnology is a growing field of application by the use of particles at the nanoscale. The application of
Nanoparticles extremely small particles based on identical grain-size particles can result in materials with enhanced properties.
Cementitious materials Studies have been carried out on cement-based materials and showed their advantages regarding their rheo­
Mechanical properties
logical, mechanical and durability characteristics. This paper presents a collection of the state-of-the-art on the
Optimum content
High temperature
recent progress of using different nanoparticles in cementitious materials both for structural purposes and for fire
Thermal properties protection construction materials succinctly. Therefore, the findings of the current state of knowledge on this
Residual strength topic are summarised and discussed. Limitations and recommendations are also underlined for future research.
Fire protection material Based on recent research works it is clear that the strength level, porosity, mix composition and type, water
content, specimen geometry, nano size scale, nanoparticle type, nanoparticle content, the combination of
nanoparticles and material age take a crucial role in the physical properties of cementitious materials modified
with nanoparticles. It is recommended that different sizes of nanoparticles should be used in such materials as
well as polypropylene fibres when subjected to high temperatures. The content of nanoparticles in such materials
should be also lower for fire applications than for only ambient temperature purposes. Additionally, there is still
an absence of knowledge and comprehension of the response of such materials under high temperatures, which
highlights the urgent need for further research into this topic.

nanoparticles [11], as well as nano-metakaolin [12] and

1. Introduction
Nanotechnology (the nanoscience and nano-engineering of reducing
matter on a nanosize scale [1]) in the construction industry leads to­
wards an optimization of the material. Nanoscience deals with the study
of how nanoscale structure of materials affects their macroscale prop­
erties, whereas nano-engineering focuses on the development of mate­
rials with enhanced mechanical properties using nanoparticles [2].
Nanotechnology has then been bringing forward different nanomaterials
that are designed at the nanoscale, including nanoparticles, nanotubes,
nanorods and nanosurfaces (nano reinforcements) [3,4]. Nanoparticles
can be used (most often as an additive and less than 100 nm in size) to
improve the characteristics of a product, especially on mortar and
concrete products [5,6], coatings and paints [7,8] and other insulation
materials [9]. The mechanical behaviour of cement-based structures
(including their strength, stiffness, hardness, toughness and durability)
depends on processes that occur at micro and nanoscale.
Researchers are manipulating cement-based materials by employing
nanoparticles [10] (such as SiO2, Al2O3, TiO2, Fe2O3, CaCO3 and CuO
nano-magnesium calcite [13]), with the purpose of improving their
durability, mechanical, thermal, and electrical properties [14,15]. It is
expected that those nanoparticles can significantly influence the kinetics
and the hydration of cement (which generally incorporates about 65%
CaO and 20% SiO2 by weight). Due to the composition and pozzolanic
properties of silica fume and fly ash, they are widely used in the cement
and concrete industry as well as nanosilica particles (Nano-SiO2), for
identical reasons, are the most current used nanopowder [16].
It has been found out that nanometakaolin (which generally in­
corporates about 55% SiO2 and 30% Al2O3 by weight), nanosilica and
nano-alumina improve significantly the physical properties of cemen­
titious mortars [17], as a result of the high pozzolanic activity, filling
and nucleating effects of nanoparticles [18], as discussed ahead in the
paper.
On the other hand, fire-protecting mortars (including cement-based
mortars) formulated with lightweight aggregates (including vermicu­
lite and/or perlite) are also usual solutions to protect the wood, rein­
forced concrete and metal structures (including steel structures) [19].
Intumescent paints and cementitious sprays are often selected for

* Corresponding author.
E-mail address: luislaim@uc.pt (L. Laím).

https://doi.org/10.1016/j.jobe.2020.102008
Received 7 September 2020; Received in revised form 7 November 2020; Accepted 11 November 2020
Available online 18 November 2020
2352-7102/© 2020 Elsevier Ltd. All rights reserved.
L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Abbreviations NMK nano metakaolin

NS nano silica
CH calcium hydroxide NT nano titanium dioxide
CM cement mortar OPC ordinary Portland cement
CSH calcium silicate hydrate PP polypropylene
EVM expanded vermiculite SEM scanning electron microscope
FA fly ash SF silica fume
HSC high strength concrete SP superplasticizer
MK metakaolin DTA/TG thermogravimetry (TG) and differential thermal analyzer
MS micro-silica (DTA)
NA nano aluminium oxide UHPC ultra high performance concrete
NC nano calcium carbonate, nano copper(II) oxide or cupric b binder
oxide fc compressive strength
NF nano iron(III) oxide or ferric oxide cm cementitious materials
NMC nano magnesium calcite w water

providing the required fire resistance of steel structural members.

Intumescent paints are commonly used in steel structures, but for high
fire resistance rates they may become a very expensive solution [20],
while current portland cement-based coatings are cheaper but they tend
to be brittle, and require higher thickness and polymers for their adhe­
sion to steel surface [21]. Furthermore, the lack of cohesion in light­
weight cementitious coating mortars (with vermiculite and/or perlite)
reduces the mechanical properties of mortars, which results in the
portlandite decomposition, Ca(OH)2 (at approximately 450 ◦ C) and the
presence of cracks due to volume changes, thus decreasing thermal
protection of steel as well [22]. However, the incorporation of nano­
particles in such materials may create a new paradigm in this field due to
their advantages, similarly to what happened in regular concretes by
using polypropylene fibres but for different reasons [21]. Hence,
improving the fire resistance of structural members with new mortar
compositions is a great challenge for the fire safety engineering
community.
Therefore, as a first step into the development of an enhanced fire
resistant mortar product with nanoparticles in the scope of the national
research project PTDC/ECI-EGC/31850/2017 (NANOFIRE - Thermal
and Mechanical behaviour of Nano Cements and their application in
steel construction as fire protection) funded by FCT (Foundation for
Science and Technology), the primary goal of this article is to share a
comprehensive review of the innovations in the area of nano-
engineering research in cement-based materials, along with their in­
volvements and major discoveries/conclusions, as well as in the field of
current passive fire protection mortars/pastes. This article is then
Fig. 1. Flowchart of the structure and keywords of the paper.
divided into three fundamental parts: (i) effects and optimum content of
nanoparticles on cement-based materials at ambient temperature, (ii)
behaviour of cement-based materials under high temperatures, and (iii) under high temperature conditions. Lastly, as conclusions, it is high­
effects and optimum content of nanoparticles on cement-based materials lighted some remarks, gaps and challenges for this research field, as well
under high temperatures. In the first part, a description and discussion of as, potential opportunities for practical applications in this research
the impact of nanoparticles on cementitious materials are presented, topic, especially for high temperature applications (Fig. 1).
focusing on nanosilica particles (most commonly used), the main dif­
ference with other nanoparticles and the role of the combination of 2. Effects and optimum content of nanoparticles on cement-
nanoparticles on such materials. There is already extensive research in based materials at ambient temperature
this area at ambient temperature, but the purpose of this paper just
highlight their main issues as a reference for the topic of such materials 2.1. Nano-SiO2 particles
under high temperatures. Therefore, in the second part of the paper, it is
addressed and discussed the role and behaviour of cementitious mate­ Nanosilica is the most-used nanoparticle in cementitious materials,
rials under high temperatures as non- and structural fire protection allowing for the enhancement of the microstructure of cement
materials, trying to show all fields of possible applications of nano­ (Ca3SiO5–C3S) due to its advanced pozzolanic properties. Calcium hy­
particles in fire protection cementitious materials. Afterwards, the droxide (portlandite - (Ca(OH)2), aluminates (Al(OH)4) and unhydrated
existing pertinent findings, effects and optimum content of nano­ cement (with two main clinker minerals: alite (tricalsium silicate -
particles on cementitious materials after subjected to high temperatures 3CaO⋅SiO2) and belite (dicalsium silicate - 2CaO⋅SiO2)) are the main
are given and discussed, especially in what concerns their residual me­ compounds of the porous cement matrix, which results in a calcium
chanical properties due to the lack of research studies on such materials silicate hydrate (CSH) gel when hydrated.

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L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Fig. 2. Silica fume (a) and nanosilica (b) SEM photographs [26].

Fig. 3. Compressive strength of mortars with SF (a) and NS (b) (adapted from Ref. [26]).

During cement hydration, nanosilica particles reduce the pores of the
cement matrix and react with calcium hydroxide (Ca(OH)2, also known
as portlandite) to form homogeneous clusters of calcium silicate hydrate
(CSH) gel [23,24], i.e., accelerates the consumption of calcium silicate
(Ca2SiO4 or formulated as 2CaO⋅SiO2), including hydrated products of
C3S (3CaO⋅SiO2 + H2O → Ca(OH)2 + xCaO.ySiO2), and C2S.
The main goal of incorporating nanosilica particles into the cement
matrix is to improve the hydration of CSH gel [25], which is the prin­
cipal constituent responsible for the material’s strength. Nanosilica
particles promote the increasing of the pozzolanic activity and act as a
microfiller in such materials [23,24]. However, there is a risk of exces­
sive self desiccation and cracking. Hence, the dosage of nanosilica par­
ticles should be balanced with the water and superplasticizer content in
order to avoid material’s strength loss instead of gain [23,26]. The lower
it is the surface area, the higher the request for water.
It has been observed that the introduction of nanosilica particles
(with a 40 nm particle size, Fig. 2a) in mortars has increased its
compressive strength, comparing to the ordinary mortars. That strength
at 28 days can increase by 28% when the nanosilica dosage rises from
3% to 12% by weight of cement [26]. In addition, the effectiveness of
pozzolanic reactions by using nanoparticles is higher than that pro­
moting by silica fume, SF (with a particle size of 0.1 μm, Fig. 2b). For
instance, whereas the compressive strength of mortars at 28 days can
increase by 8% when silica fume dosage rises from 5% to 15% by cement
weight [26], its maximum gain in strength can be achieved for a lower
amount of nanoparticles when nanosilica is used instead of silica fume
(microsilica). The strength of the mortars at 28 days can increase by 37%
(from 25.6 to 35.1 MPa) adding 5% of microsilica by cement weight and
112% (from 25.6 to 54.3 MPa) adding 3% of nano-SiO2 (Fig. 3) [26].
Such a difference in mortar and concrete products’ strength with
nano-SiO2 is related to the effectiveness of pozzolanic reactions. Nano­
silica particles enhance the microstructure of cementitious materials in
terms of formation of hydration products [27] and reduction of poros­
ity/permeability, and calcium hydroxide crystals (Fig. 4).

Fig. 4. SEM photographs of cement matrix with SF (a) and nano-SiO2 (b): 1 – Ca(OH)2 crystal, 2 - CSH, 3 – pore [27].

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L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Fig. 5. Effect of nanosilica on compressive (a) and flexural (b) strength of concrete for different ages [35].

Note that the size and amount reduction of calcium hydroxide

crystals make the interface area between the aggregates and the cement Table 1
Improvement in the percentage of compressive strength of cement mortars with
paste denser as well as itself binding matrix due to a higher filling of the
different sizes and contents of nanosilica particles (adapted from Ref. [27]).
voids of the CSH gel structure (i.e., nanosilica particles have also a
nucleating function), thus allowing for higher durability of concrete Content (wt%) Particle size (nm)

elements as well [28]. 12 20 40 100

Furthermore, consistency and setting time of mortars with nanosilica 3 4.9 25.3 34.5 0.6
or microsilica particles are also different. Cement paste becomes thicker 6 11.0 33.3 42.6 6.0
with nanosilica particles (they shorten the setting time), and its hydra­ 9 23.9 52.9 54.4 12.5
tion process is faster [29]. The effectiveness of nano-SiO2 is higher for 12 19.4 33.2 43.4 8.9

smaller particles of pozzolanic materials [30]. It was also observed that

those nanoparticles enhance the compressive strength of the mortars at
early ages (7 days) in a better way than silica fume, as a consequence of
their hydration process rate. For example, the strength of mortars
increased by 23% (from 18.3 to 22.5 MPa) at 7 days and 37% (from 25.6
to 35.1 MPa) at 28 days when 5% of silica fume by cement weight was
introduced to the mortars, while the strength of mortars increased by
116% (from 18.3 to 39.5 MPa) at 7 days and 112% (from 25.6 to 54.3
MPa) at 28 days when 3% of nanosilica particles were introduced to the
mortars (Fig. 3) [26]. The pozzolanic activity provided by nanosilica
particles is hence significantly higher than that of microsilica for early
ages of mortars [31,32].
Obviously nano-SiO2 has contributed both for the improvement of
the compressive strength and for the flexural strength of mortar and
concrete products at all ages. Nevertheless, its effect is much higher at
early ages, due to not only the high pozzolanic activity of nano-SiO2 at
early ages, but also its hydration hindrance effect on binding paste at
older curing ages [33].
This is also one of the reasons why it can be found an optimal content
of nanoparticles in cement-based materials. Nanosilica particles Fig. 6. The cumulative pore volume of mixtures containing NS and NC [42].
dispersion in the cement matrix becomes difficult for higher amounts
than a critical value, i.e., when nanoparticles agglomeration effect be­ particles (Table 1). Tiny sizes on nanosilica particles may lead to high
comes relevant. In order to ensure that such materials acquire enhanced agglomeration of particles (low dispersion) and involve cement particles
properties, it is then crucial to avoid both the agglomeration of nano­ reducing their hydration process, instead of filling the very small pores
particles and their quantity in the mixture is not higher than the required of material (packing ability) [27,36], whereas large sizes of particles
amount to consume calcium hydroxide [34]. make more porous the material (the less dense, the lower the strength).
The optimum properties of cementitious materials have been ob­ Additionally, the presence of nanosilica particles also makes the
tained in the samples containing 2–3% of nanosilica [33,34], with the cement matrix more resistant to aggressive solutions (ammonium nitrate
higher gain in the flexural strength, as shown in Fig. 5 [35]. However, and hydrochloric acid solutions for instance). They can reduce the
other studies indicate that the maximum replacement dosage of cement cement degradation mechanism due to calcium ions leaching, i.e.,
with nanosilica particles, as well as cement with silica fume, is achieved dissolution of CSH hydrates under harsh environments. Note that low
for 9–12% nanosilica particles by cement weight [26,27]. Such differ­ porosity becomes such materials less vulnerable to chemical attack, i.e.,
ence can be linked to the water-to-binder ratio (w/b) used. While the slows down the Ca-leaching rate. Long silicate chains provided by
optimum replacement content of cement with NS particles was around nanosilica particles also increase calcium stabilization [37].
2–3% for w/b ratio of 0.2–0.4, the optimum NS particles was around
9–12% for w/b ratio of 0.5–0.65. The superplasticizer type can be
another important parameter. 2.2. Other nanoparticles
The dimension of nano-SiO2 particle also takes a key role in the
physical properties of cement-based materials. It has been found out that Nowadays with the aid of supplementary cementitious materials,
nanosilica particles with 40 nm allow for cement-based mortars obtain such as fly ash [38], silica fume [29], metakaolin [39] and blast furnace
higher compressive strength than mortars with 12 and 20 nm SiO2 slag [40], it has been an effort to reduce cement dosage in cement-based
materials in order both to reduce the carbon footprint of concrete and to

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L. Laím et al.
Fig. 7. Compressive strength of mortars with NA (a) and NT (b) at different ages (adapted from Ref. [15]).
Fig. 8. Water absorption (a), electrical resistivity (b) and chloride penetration
(c) of mortars containing different nanoparticles (none, Control, nanosilica, NS,
nano iron oxide, NF, and nano cupric oxide, NC) [50].
enhance its durability properties. Nanoparticles also take a crucial role
in such material properties [41], and not only nanosilica particles. Nano
titanium dioxide (NT) and nano calcium carbonate, CaCO3 (NC), can
also help decrease CSH dosage in cement-based materials and reduce
capillary pore space (Fig. 6). Rebar corrosion and Ca-leaching are pre­
venting by making the transport of chloride ions unpractical, for
instance Ref. [42]. Titanium dioxide’s properties are also vital both for
concrete’s self-cleaning and public health. It exhibits excellent photo­
catalytic activity, causing a photocatalytic degradation of pollutants,
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Journal of Building Engineering 35 (2021) 102008
such as nitric oxide and nitrogen dioxide, carbon monoxide, chlor­
ophenols, volatile organic compounds and aldehydes from industrial
and vehicle emissions, thus mitigating the rebar corrosion [43]. As well
as that cementitious materials’ (compressive, flexural) strength im­
proves not only by decreasing their total porosity [44,45] but also by
modifying and reducing the orientation index between calcium hy­
droxide crystals [46]. Abrasion resistance of such materials might still be
improved by titanium dioxide nanoparticles.
Aluminium oxide (alumina, Al2O3) is a compound with high hard­
ness, refractoriness and good thermal properties and excellent dielectric
properties, which make it useful for a wide range of applications.
Nanoparticles of aluminium oxide (NA) have a limited impact on the
compressive strength of cementitious materials, but can significantly
enhance their modulus of elasticity (up to 143% at a content of 5%)
[47]. Previous results have shown an optimum replacement content of
cement with aluminium oxide nanoparticles by 1% and with titanium
dioxide nanoparticles by 5% for the best compressive strength (Fig. 7)
[15].
Water absorption (related to the water permeability), electrical re­
sistivity (concerning the ion transport, porous microstructure, moisture
and permeability in mortar/concrete) and chloride permeability of
cementitious materials (based on charge passed) can be still enhanced
with the increase/addition of iron oxide (Fe2O3, NF) and copper (II)
oxide (cupric oxide, CuO, NC) nanoparticles [48]. Such parameters can
provide information regarding the protection capacity of materials
against aggressive substances (chlorides and sulphates, for instance),
including protection against corrosion of partially or fully encased steel
sections or steel reinforcements. The maximum allowable water ab­
sorption, chloride content and sulfate content depend on the standard
specification, but usually, their values are respectively around 10%,
0.05% and 0.8% [49]. High probability of the corrosion may occur for
electrical resistivity values between 5 and 10 kΩcm and/or charge
passed values higher than 4000 Coulombs, whereas the low probability
of the corrosion may happen for electrical resistivity values higher than
20 kΩcm and/or charge passed values lower than 1000 Coulombs. This
is why, in general, the best durability properties of the respective mix­
tures are reached at the expense of low contents of nano-Fe2O3 (2%),
medium contests of nano-SiO2 (3%) or of high dosages of nano-CuO
(4%), as shown in Fig. 8 [50]. Nevertheless, cementitious materials
with nano-CuO can show better performance.
2.3. Combinations of different nanoparticles
The combination of different particle sizes (nano and micro) also
have significant synergistic effects on microstructure and strength of
mortars. For instance, 10% silica fume (also called micro-silica, MS) or
only 1% nanosilica particles would provide approximately the same
enhancement of 7-day and 28-day strength, but a combination of both
different particle sizes has a higher synergistic effect, especially for low
L. Laím et al.
Fig. 9. 7- and 56-Day compression strength as a function of water-to-cement ratio for combinations of different particle sizes (MS & NS) [51].
Fig. 10. Sulfate expansion of cement mortar with different nano-magnesium
calcite dosages in magnesium sulfate solution [13].
water-to-cement ratios (w/cm) and later ages (Fig. 9). The higher the
nanosilica dosage, the larger the synergistic effect [51].
Others nanoparticles recently used in cement-based materials are the
nano-magnesium calcite and nano-metakaolin, which are combinations
of different nanomaterials. Nano-magnesium calcite (NMC) can be a
waste and achieved by hardness loss from groundwater. This can be
obtained by dissolving urea and plant-derived urease enzyme in
groundwater, thus removing Ca2+ and Mg2+ as nano-Mg-calcite pre­
cipitate (i.e., precipitation of calcium carbonate, CaCO3, and magnesium
carbonate, MgCO3), which is a beneficial recycling method [52]. The
addition of NMC, 1% by weight of the binder, has been led to a sub­
stantial improvement of the compressive strength (increasing by 85% at
3 days and 34% at 28 days), total porosity reduction (decreasing by 18%
at 3 and 28 days), and the resistance to sulfate attack (assessed by
thermogravimetric and differential thermal analyses) [13]. Note that
nano-Mg-calcite can have an average particle size of 8 nm [52]. Mag­
nesium calcite nanoparticles can contribute significantly to the
decreasing of sulfate expansion for all ages, especially in cementitious
mortars with 1% NMC (Fig. 10).
High pozzolanic properties in cementitious materials can also be
attained with the aid of metakaolin (MK), which is obtained by firing
kaolinite clay (Al2Si2O5(OH)4) up to 700–800 ◦ C [12]. Calcium hy­
droxide reacts with metakaolin producing CSH, C4AH13 and C2ASH8,
which strengthen such materials [53,54]. Results have been shown that
the optimum replacement of ordinary Portland cement (OPC) mortar by
metakaolin nanoparticles, NMK (with particles having sizes in the range
of 50–200 nm), for obtaining the best compressive strength, was found
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Journal of Building Engineering 35 (2021) 102008
to be 8–10%, using a w/c ratio of 0.3 by weight [12,55].
Nano-metakaolin has also been employed for enhancing the prop­
erties of cement-based materials incorporating high volume re­
placements, including fly ash, perlite, vermiculite, and others inorganic
cellular materials. These aggregates may present very soft and porous
structures, as is the case with expanded vermiculite (EVM). Conven­
tional plain cementitious materials have usually higher strength than
those with high volume replacements (50–70%). Nevertheless,
substituting such replacements with 10 wt% nano-metakaolin particles
has been observed to be very convenient in compensating the
compressive strength loss [56]. On the other hand, other researchers
observed that the best substitution ratio of OPC by NMK was 3% [57]
instead of 10%, which conflicts with previous studies [55,56]. The larger
specific surface area of NMK (119.14 m2/g) attained by exfoliation
treatment (i.e., type of morphology) may be one of the reasons for such
difference. Also, low hydration products and unhydrated calcium hy­
droxide particles, owing to the agglomeration of nano-metakaolin par­
ticles around CSH structures, can happen when nano-metakaolin dosage
exceeds 3% [57].
The addition of NMK in mortar/concrete is also to enhance the
microstructure of UHSC (ultra high strength concrete, fck > 100 MPa),
promoting the effectiveness of pozzolanic reactions and a compact
concrete with fewer voids and pores. In NC (normal concrete) and HSC
(high strength concrete, 60 MPa < fck < 100 MPa) porosity between
aggregates and cement paste can compromise its strength, whereas the
porosity in CSH microstructure itself is the problem for UHSC. The
uniformity of the CSH gel ensures the performance of the concrete. The
optimum strength improvement of UHSC was found to be for the
introduction of only 1% by weight of nano-metakaolin particles (and not
3, 5, 7 and 9%, for instance). Nonetheless, UHSC with nano-metakaolin
particles has lower workability than metakaolin and OPC owing to the
combination of their ultrafine size and clay properties [58].
3. Behaviour of cement-based materials under high
temperatures
3.1. Thermal behaviour as fire protection materials
Fire is one of the terrifying natural phenomena, and if not appro­
priately managed, can lead to devastating consequences [59,60]. The
fire protection of structures can be achieved by the combination of the
use of passive and active fire protection systems and management sys­
tems (including communication and evacuation procedures, compart­
mentation, smoke exhaust system, fire detection systems etc.) [61]. The
active fire protection comprises systems and/or items (such as fire
extinguisher, standpipe, sprinkler systems, fire blankets, etc.) [62],
which demand quick action, response to stop or control a fire, in op­
position to passive fire protection [63]. Active systems usually have high
installation and maintenance costs [64]. On the other hand, when pas­
sive systems are employed, it is quite a certainty that they will remain
L. Laím et al.
Fig. 11. Thermal conductivity of typical fire protective materials as a function
of temperature [67].
operational during a fire event. Passive systems include the fire resis­
tance of the (structural or non-structural) members of a building (col­
umns, beams, walls and ceilings).
There are basically two passive protection methods: i) internal for
fire structural members and ii) external for (non-)structural building
members, which are designed to stand there for the lifetime of the
building, to contain fire spread and guarantee their structural stability.
Their purpose is to ensure adequate evacuation times, minimum safety
conditions for firefighting and rescue operations, as well as to minimize
property, economic and life losses [65]. The external fire protection
systems involve the application of insulating materials, which is the
most common method to protect a member from extreme high tem­
peratures exposure.
Insulation materials protect the structures from direct contact with
the fire and have low thermal conductivity so that the time required for
the heating starts to affect the stability and/or integrity of the elements
is increased.
Therefore, with the purpose of enhancing the fire resistance of
structural elements (especially metallic elements, such as steel and
aluminium elements), different fire protective materials can be used,
including cementitious coating mortars, board systems (plaster or sili­
cate calcium boards, for instance), spray systems and intumescent
coatings [66]. These should be cheaper than the steelwork (for
instance), easy of application, safe (i.e., not be hazardous during the
application and in service, or toxic in the event of a fire), and should
insulate and remain undamaged under fire attack (with limited de­
tachments and fractures during the required fire resistance) [67]. The
thermal conductivity of ordinary plain concrete (2000–2400 kg/m3)
varies from 0.62 to 3.3 W/mK due to the types of coarse aggregate,
moisture content and temperature [68]. To make the cementitious
coating mortars more competitive comparing to the other fire protective
materials in terms of thermal conductivity (Fig. 11), lightweight
cementitious (C) coating mortars should be chosen. The thermal con­
ductivity of lightweight ordinary concrete, LOC (with perlite and/or
vermiculite, V [69], for instance), ranges from 0.4 (V/C = 6 by volume,
for example [70]) to 1.89 W/mK at ambient temperature [71], whereas
the lightweight concrete with expanded polystyrene particles or light­
weight cellular concrete (also known as heat-insulation foamed con­
crete) even has a thermal conductivity between 0.07 and 0.33 W/mK
[72,73]. The differences in the thermal conductivity values might be
related to the measurement techniques, ambient and boundary tem­
peratures, suitability to material and mixture ratio [74].
Perlite consists of a siliceous volcanic rock with 2–6% of combined
water. Its chemical composition is approximately 75 wt% of SiO2 con­
taining oxides of aluminium (14.8 wt%), potassium (4.8 wt%), sodium
(2.9 wt%), calcium (0.9 wt%), magnesium (0.1 wt%), and others. When
little perlite grains are subjected to high temperatures (870 ◦ C) they
7
Journal of Building Engineering 35 (2021) 102008
strongly increase their volume with countless tiny, sealed air cells, like
popcorn. This makes perlite expand in such a way that attributes to
lightweight perlite excellent insulating properties.
While the colour of perlite ore can vary from transparent through
light grey to glossy black, lightweight expanded perlite (LEP) can vary
from snowy white to greyish white. LEP has low thermal conductivity
(0.04–0.06 W/mK), relatively high melting point (1260–1343 ◦ C) and
low density (loose: 50–400 kg/m3) [75].
Vermiculite consists of a mica-like mineral containing a shiny flake
(belonging to the phyllosilicate group) and is created under ambient
conditions from the weathering/hydrothermal alteration of phlogopite
or biotite. Vermiculite comprises SiO2 (37–42 wt%), MgO (12–14 wt%),
Al2O3 (10–13 wt%), Fe2O3 (5–17 wt%), H2O (8–18 wt%) and a small
quantity of FeO (1 to 3 wt%). Similarly to perlite, when vermiculite
particles are subjected to high temperatures (from 650 to 950 ◦ C) they
expand. Also known by the exfoliation process. The exfoliated vermic­
ulite exhibits low density (loose: from 80 to 120 kg/m3), relatively high
melting point (from 1240 to 1430 ◦ C) and low thermal conductivity
(from 0.04 to 0.12 W/m K) [69].
Perlite (or Vermiculite) plaster is a mixture of a bonding material
(plain portland cement, gypsum, and so on) and expanded perlite (or
expanded vermiculite) aggregate with water, for lining by trowel or gun
to ceiling or wall surfaces or to structural steel members as fire protec­
tion insulation due to their lightweight and insulating characteristics,
with high resistance to heat transfer by conduction (up to four times
higher than sand). Gypsum has some advantages over portland cement,
including its quality as a fire barrier, ease of production, availability and
low cost. Not only gypsum has lower thermal conductivity than cement
[76], but also it contributes to the energy loss from fire due to its
endothermic dehydration process [77]. With the goal of improving the
fire-resistant behaviour of cement pastes, supplements are commonly
added, in the same way for the gypsum matrices.
Studies have shown that perlite–Portland cement and perli­
te–gypsum coatings are the most effective plasters as fire barriers and in
retarding the conduction of high temperatures across their thickness
among different kind of coatings, such as traditional-cement plaster,
vermiculite cement/gypsum based mortar, intumescent coating, cal­
cium silicate board and LECA-cement plaster [78–80]. Perlite may be a
better supplement than vermiculite, not because of their thermal con­
ductivity but due to higher retraction of the vermiculite. However,
attention should be paid to the porosity of their mixtures. Porosities
higher than 40% may contribute to the phenomenon of air percolation
[81]. For fire protection, instead of perlite and vermiculite, others ad­
ditives can also be used such as mica, alumina, ceramic hollow spheres
and magnesium by-products [82].
3.2. Mechanical behaviour as non-structural fire protection materials
The major goal of non-structural fire protection materials is to block
temperature propagation that compromises the fire resistance of the
(non-)structural building members. For example, the temperature at the
interface between the fireproofing material and the structural member
should always be restricted at values lower than 300 ◦ C for the structural
concrete members [83], 350 ◦ C for thin-walled steel members [84] and
450–550 ◦ C [85] for carbon steel members (with class 1–2
cross-section), avoiding in this way both material/member softening
and damage. Carbon steel loses significatively its mechanical properties
at temperatures in-between 500 and 600 ◦ C, which might compromise
the stability of the steel structural members, thus requiring most of the
applications external fireproofing under high temperatures [86]. Steel
and reinforced concrete members might require fireproofing protection.
In addition to the thermal properties of passive fire protection ma­
terials such as mass density, specific heat and thermal conductivity, the
strength loss under elevated temperature, the fracture behaviour, the
thermal incompatibility between the different materials [87] and the
vapour pressure of water (during heating) are also important parameters
L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Fig. 12. Compressive strength of self-compacting mortars at the age of 3, 28 and 90 days (a) and after exposing to temperatures of 300, 600 and 900 ◦ C at 28 days
(b) [90].

that should be taken into account for the selection of the respective
passive fire protection material to be used, in order not to compromise
the fire resistance of the members to be protected.
Gypsum can have good thermal properties, but it has low strength
and poor toughness (low fracture strength and low resistance to crack
propagation), for instance Ref. [88]. On the other hand, although the
addition of perlite or vermiculite in plaster matrices still lead to an in­
crease of their thermal properties, such additions can decrease even
more their mechanical properties. This decrease can be linked to their
high porosity which increases with the addition of perlite or vermiculite
to the mixture [89].
This is why gypsum matrices can be usually replaced by cement
matrices. Non-structural lightweight aggregates (such as expanded
polystyrene, vermiculite and perlite, which have very low density) have
replaced the sand in cementitious materials. Even using cement instead
of gypsum, the compressive strength of concretes can decrease by 30%
(from 62.28 MPa to 43.48 MPa) for 10% replacement level of sand by
expanded vermiculite and 52% (from 62.28 MPa to 29.95 MPa) for 40%
replacement level at 28 days (Fig. 12a) [90].
In terms of residual compressive strength, the mechanical properties
degradation of self-compacting mortars with expanded vermiculite Fig. 13. Mechanical properties of different cementitious coating materials
(EVM) has been less than that without EVM. It was found out, for [91,93].
example, that the compressive strength decreased by 21% (after
exposing to the temperature of 300 ◦ C) and 35% (after exposing to the alumina and iron oxide (which is around 50% of their composition) and
temperature of 600 ◦ C) for ordinary mortars, by 2% and 22% for mortars it may also have 10% calcium oxide [92]. Bottom ash can then be used in
with 10% replacement level of sand by expanded vermiculite and 14% lightweight cementitious materials, also increasing industrial waste
and 21% for mortars with 40% replacement level, after exposing to recycling, making the world more sustainable and greatly benefiting the
temperatures of 300 ◦ C and 600 ◦ C, respectively (Fig. 12b) [90]. environment. The use of such lightweight fireproofing materials should,
As it can be seen in Fig. 13, the compressive and bonding strengths of however, be adequate and moderate, since reinforcements with suitable
cementitious coating materials with lightweight aggregates are usually wire mesh may be required for thickness higher than 30 mm, in order to
low. With the purpose of increasing compressive strength of mortars be able to stay in place when it is subjected to high temperatures [78].
with lightweight aggregates (such as vermiculite, V, or perlite), silica
fume has been used as a mineral admixture. The compressive strength of
3.3. Fire protection material as structural materials
such cementitious (C) mortars increases when silica fume amount rises.
It is already known, as discussed before in this paper, silica reacts with
Cement-based structural members can also be enhanced to withstand
calcium hydroxide to form CSH, which contributes significatively for the
load-bearing capacity at elevated temperatures, i.e., they can work/be
lightweight mortars’ strength. Their compressive strength (V/C = 6 by
used as passive fire structural materials as well. It is generally accepted
volume) can increase at least up to 45% when silica fume is added by
that normal cementitious materials start to lose their load-bearing ca­
15% of cement (by weight) under different temperatures (20, 300 and
pacity when subjected to temperatures beyond 300 ◦ C. The compressive
600 ◦ C) [70]. On the other hand, owing to vibrations and surface pres­
strength loss of mortars containing microsilica is higher than ordinary
sures on lightweight concrete linings in high-speed railway tunnels (as
mortars at temperatures above 600 ◦ C [94]. During pozzolanic reactions
fire protection coating materials), fatigue failures can occur. This is why,
(cement hydration) calcium hydroxide can stabilize effectively with
bottom ash (rich in silica) is employed in such materials, replacing some
silica (plentiful in silica fume, fly ash, blast-furnace slag and metakaolin,
lightweight aggregate. Hence, bottom ash improves not only the mate­
for instance), which contributes significatively to high-temperature
rial strength but also its thermal properties [91]. Bottom ashes have
resistance, especially up to 300–350 ◦ C. At this temperature calcium
lower porosity than lightweight aggregates, but higher porosity than the
hydroxide turns into water vapour and lime, contributing to
river sand, for instance, as well as their principal compounds, are silica,
micro-cracks. However, its decomposition is worse during the cooling

8
L. Laím et al.
Fig. 14. DTA/TG curves of cement pastes showing dehydration and crystalli­
zation of amorphous calcium carbonate, Ca(OH)2 dehydroxylation and CaCO3
calcination [99].
period, owing to lime expansion. High temperatures can then damage
cement-based materials, not only due to water evaporation causing
shrinkage and steam pressure, but also chemical changes in the aggre­
gates and cement matrix structure. Between 100 and 150 ◦ C, the
decomposition of the hydrated products of cement pastes (CSH, CFH and
CAH) starts. Then, calcium hydroxide turns into calcium oxide at about
500 ◦ C (Ca(OH)2 + heat → CaO + H2O). At 570 ◦ C quartz (present in
many siliceous aggregates) changes its polymorphism. In limestone ag­
gregates, calcium carbonate also turns into calcium oxide at around
800 ◦ C (CaCO3 + heat → CaO + CO2), as it is typically highlighted in
DTA/TG curves (Fig. 14). During all these processes, volume changes
and damage happen in such materials [94]. The most unfavourable
applications of structural cement-based materials without external
passive fire protection is underground structures, namely tunnels. They
are in confined ventilated conditions and accidental events on large
tanker vehicles transporting oil or petrol must be considered during the
design phase, in other words, the highest aggressive fire scenario must
be chosen for the thermal action (i.e., the temperature–time Rijkswa­
terstaat, RWS, standard curve proposed by the Netherlands Ministry of
Transport, instead of the well known ISO834 standard fire curve,
commonly used for the interior of buildings [91,95]). Besides, the
relative humidity in the air in tunnels (75% or above) is much higher
than that inside the buildings (around 50%), which leads to higher
moisture contents in cementitious linning pores in tunnels than those in
buildings. In such environments, cementitious materials under elevated
and rapidly rising temperatures may exhibit delamination and spalling,
resulting in the detachment of solid pieces from the material surface and
reduction of its thermal protection layer. Spalling might occur at tem­
peratures between 300 and 450 ◦ C [96], depending on concrete
strength, porosity, mix composition and type, water content, heating
scenario [97], the geometry of the specimen, mechanical boundary
conditions (compressive load level), among other parameters [98]. In
structural reinforced concrete members its covering might be reduced or
damaged under these fire scenarios, leading to higher rapidly temper­
ature rises of such materials, especially of reinforcement bars, faster
mechanical properties losses of the materials and in the worst case to the
reduction of the fire resistance of the respective members.
Nonetheless, the assessment of the parameters that most affect
spalling in cementitious structural members under high temperatures is
difficult as well as their comparison between different authors owing to
differences in the testing methods (namely, full-scale, medium-scale and
small-scale tests) and procedures used to obtain the results [100].
The actual construction and design guidance [101,102] for spalling
prevention is solely established by prescribing a dosage of poly­
propylene (PP) fibres, excluding extra/additional coverings, i.e., the use
9
Journal of Building Engineering 35 (2021) 102008
of PP fibres is only a mitigating measure to reduce the risk of spalling,
instead of eliminating its occurrence. Nevertheless, the effectiveness of
such PP fibres on spalling prevention strongly depends on fibre
cross-section (diameter) and its dosage [103]. Usually, their diameter
ranges from 10 to 40 mm and their length from 6 to 12 mm. Regarding
their dosage, European specifications [101] suggest to include 2 kg/m3
in high strength concretes (higher than 55 MPa for cube specimens),
and/or concretes with high silica fume content (higher than 6 wt%) or
moisture content (higher than 3 wt%).
To sum up, to enhance the mechanical behaviour of cement-based
structural members subjected to high temperatures, the addition of fi­
bres (including polypropylene as well as steel fibres) is generally pro­
posed. Note that steel fibres additions to concrete may better control its
cracking (i.e., the cementitious material may present higher ductility)
[104,105].
4. Effects and optimum content of nanoparticles on cement-
based materials under high temperatures
Cementitious materials are notorious for their ability to withstand
high temperatures and fires, mainly due to their high specific heat and
low thermal conductivity. Nevertheless, this does not imply that con­
crete members are out of any damages when exposed to high tempera­
tures, as discussed above. As well as that it has already been seen in this
paper that when nanoparticles are employed as supplementary materials
in concrete, great progress can also be achieved at room temperature,
thus contributing to improved permeability and strength, among other
features. Regarding residual mechanical and physical properties, sup­
plementary cementitious materials (including slag, fly ash or silica fume,
for instance) in cement paste have been shown to be an efficient measure
[106], in the same way as the replacement of cement with pozzolanic
nanoparticles (including nanosilica [107], nano-metakaolin [108],
nanoclay [109], nano-alumina [110], nanotitania/titanium oxide [111],
nano iron oxide and zinc oxide [112]), making them more reactive and
effective [113]. Amorphous nanoparticles, namely nanosilica, can
contribute both to changes in the hydration process and to pozzolanic
reactions, interacting with the available calcium hydroxide produced by
the reaction between water and tricalcium silicate (Ca3SiO5 or C3S) and
generating the secondary calcium silicate hydrate (CSH) which makes
the cementitious paste denser, i.e., dicalcium silicate and tricalcium
silicate are the main composts in normal Portland cement, contributing
to its binding characteristics and mechanisms and strength [114].
Although the compressive strength of cementitious materials de­
creases after exposing to high temperatures (above 300 ◦ C), higher re­
sidual compressive strengths (10–20% higher) can be maintained when
is added 1% of nanoparticles to those materials up to 700 ◦ C [106,108,
109,114,115], as shown in Fig. 15. When higher percentages of nano­
particles are used, lower permeability can be attained, which is a benefit
for HSC, but as discussed before it can be a detrimental effect when such
materials are exposed to high temperatures. Nevertheless, when the
water to cement ratio increases the best replacement level on nano­
particles can increase up to 3%, in spite of the lower strength of the
cement-based compositions [116]. Superplasticizer (SP) can also have a
beneficial effect on the residual properties, usually higher than at
ambient temperatures [117]. Besides, the addition of 1% nano-alumina
can also improve the elastic modulus of such mixtures up to 400 ◦ C
(Fig. 16). Alumina causes the concrete to become progressively stiffer
but more brittle [110]. On the contrary, to attain the highest residual
strength of cementitious mortars with the introduction of nano-titania
particles, 2% of those nanoparticles was required [111]. Furthermore,
it has been observed that the combined addition of microsilica and
nanosilica particles has more substantial synergistic effects on the re­
sidual compressive strength of cement-based mortars when their con­
tents are similar [118]. In the case of the employment of nano-iron oxide
Fe2O3, NF, it is also suggested that this type of nanoparticles should be
produced by thermal decomposition of basic ferric acetate ([Fe3O(OAc)
L. Laím et al.
Fig. 15. Residual compressive strength of cementitious plasters as a function of
temperature [119].
6(H2O)3]CH3CO2) calcined at 275 ◦ C, which provided better results in
terms of residual strength of the respective mortars [115]. On the con­
trary, the effect of zinc oxide nanoparticles is nearly neglected at high
temperatures [112].
On the other hand, portland cementitious plasters replaced partially
by both of nano-metakaolin (with 48 m2/g Blaine surface area) and fly
ash (FA) has been shown an enormous impact on their residual prop­
erties. This could be noticed for mortar mixes containing both a
replacement ratio of cement of 10% NMK and 10% fly ash for which the
reduction in residual compressive strength value was only 16.67% at
800 ◦ C (from 36 to 30 MPa), whereas the ordinary Portland cement had
a reduction of 83% (from 30 to 5 MPa) [120]. It should be remembered
that NMK is produced from kaolinite clay by means of the calcination
process, which results in a thermally (at 800 ◦ C) activated
alumino-silicate. This makes the mortars hardener and with enhanced
fire behaviour.
Recent researches have also demonstrated that using nanoclay en­
hances the chloride penetration resistance, its permeability and me­
chanical strengths of cementitious materials [109]. Note that nanoclays
can be divided into several groups, including halloysite, kaolinite, and
montmorillonite [121]. It has been observed that the influence of
nanoclay in cement mortars was stronger in their residual mechanical
properties than at ambient temperature. As well as that the enhance­
ment in their tensile strength was higher than in their compressive
strength. From X-ray diffraction analysis, it was observed that calcium
Fig. 16. Residual elastic modules of cementitious plasters as a function of
temperature [110].
10
Journal of Building Engineering 35 (2021) 102008
silicate hydrate is produced at high temperatures (200–600 ◦ C) in the
presence of nanoclay, making it clear the beneficial effect of such
nanomaterials on the tensile strength of cement mortars under these
temperature conditions. The maximum relative improvement strength
was achieved with 2% nanoclay addition and at 400 ◦ C [122]. Nanoclay
particles in cementitious mortars decrease their density and the size of
microcracks.
5. Conclusions
5.1. Remarks
This paper reviewed the state-of-the-art of the potential of nano­
particles to improve the performance of cement based materials both for
structural purposes and for construction materials to be used as fire
protection. Adding nanoparticles to the cementitious materials can
affect them in four different main ways: i) decreasing porosity (filling up
air spaces); ii) increasing durability (by mean of the reduction of
penetration of water, and consequently preventing the harmful chloride
ions transport, for instance); iii) behaving as an activator to promote
pozzolanic reactions (transforming portlandite into CSH gel); and iv)
enhancing the microstructure of cement (consuming the portlandite
crystals by decreasing their orientation, reducing their size and thus
improving the interface structure). This will lead to a beneficial impact
on the physical properties of the material, especially on the mechanical
properties, namely its tensile and flexural strength with the highest ef­
fect at earlier ages. The use of different sizes of nanoparticles in such
materials in equal contents may even optimize their beneficial effect on
the mechanical properties of the materials, resulting in more compact,
dense and homogeneous microstructures.
5.2. Gaps and challenges
While nanoparticles in cement-based materials seem to have a
tremendous impact, nevertheless, there are several challenges that need
to be still overcome to accomplish its full potential (multiple parameters
involved), such as the understanding of the actual influence of different
binder types, cement particle sizes, nano size scales (poor dispersion
and/or high agglomeration of nanoparticles), the surface area-to-mass
ratio of the nanoparticles, nanoparticle types, nanoparticle contents,
nanoparticle production type, combinations between nano and micro
scale, material scales (retraction effect), mass densities of the composi­
tion (porosity – ultralight and light materials), supplementary materials,
aggregates, water contents, material structural class, mechanical
boundary conditions and their interactions. This is why the optimum
quantity of nanoparticles for cementitious materials cannot be yet fixed
with a certain percentage, but generally, it is around 1–3% by weight of
cement (as it can be briefly seen in Table 2). Implementation on a large
scale and lowering of the cost-to-benefit ratio is also great challenges
nowadays.
The few studies on the thermal and structural behaviour of cemen­
titious materials with nanoparticles under elevated temperatures make
still the full understanding of such materials for fire applications a great
challenge to researchers, as well. For instance, many issues remain un­
dressed, especially design guidelines for EN 1992-1-2 regarding strength
degradation with increasing temperature (within limits of application).
Besides, other parameters can be still evaluated, such as the influence of
higher heating rates, the load level applied on specimens under transient
state conditions, the use of refractory cement, as well as of different
configurations of nanoparticles (like mesoporous silica nanoparticles,
for instance) on the thermal properties of such materials.
Finally, there is a tremendous lack of understanding and knowledge
of the behaviour of such materials and/or structural members under
high temperatures, especially their fire resistance performance. It should
be highlighted that the concepts of elevated temperatures and fire
resistance are mostly misused in this scientific field. It must not be
L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Table 2
A summary of the influence of (nano/micro) particles on the strength of cementitious construction materials at ambient temperature.
Reference Aggregates Additives Replacement fc (OPC - Major findings
MPa)

[26] Sand SP Silica fume (SF) 25 (w/b = The replacement of 5% SF shows a significant enhancement in compressive
Surface area: 20 0.5) strength both at 7 (23%) and 28 days (38%).
m2/g In order to avoid tremendous desiccation and cracking, adjustments in SP and
Particle size: 100 water should be made in mixtures with high SF dosage.
nm
[26] Sand SP Nanosilica (NS) 25 (w/b = The replacement of 3% NS shows a significant enhancement in compressive
Surface area: 60 0.5) strength both at 7 and 28 days (around twice).
m2/g In order to avoid tremendous desiccation and cracking, adjustments in SP and
Particle size: 40 water should be made in mixtures with high NS dosage.
nm
[27] Sand – Silica fume (SF) 23.5 (w/b The replacement of 9% SF shows substantial enhancement in compressive strength
Surface area: 20 = 0.65) at 28 days (12.5%).
m2/g
Particle size: 100
nm
[27] Sand – Nano-SiO2 (NS) 23.5 (w/b The replacement of 9% NS shows significant enhancement in compressive strength
Surface area: 200 = 0.65) both at 7 (32%) and 28 days (24%).
m2/g
Particle size: 12
nm
[27] Sand – Nano-SiO2 (NS) 23.5 (w/b The replacement of 9% NS shows significant enhancement in compressive strength
Surface area: 50 = 0.65) both at 7 (74%) and 28 days (54%).
m2/g
Particle size: 40
nm
[33] Sand Nano-SiO2 (NS) – 45 (w/b = The addition of 2.25% NS shows significant enhancement in compressive strength
Particle size: 0.4) both at 7 (9%) and 28 days (4%).
10 nm
[34] Sand (Max. Size: 2.5 SP (2%) Fly ash (35%) 75 (w/b = The replacement of 3% NS shows a significant enhancement in compressive
mm) Nano-SiO2 (NS) 0.2) strength both at 7 (17.4%) and 28 days (23.1%).
Particle size: 20
nm
[35] Sand SP (0.4–0.55%) Copper slag (40%). 56.5 (w/b The replacement of 2% NS shows substantial enhancement in compressive and
Coarse aggregate (Max. Nano-SiO2 (NS) = 0.31) flexural strength both at 7 (40% and 37.7%) and 28 days (21% and 36.5%,
Size: 12.5 mm) Particle size: 5–40 respectively).
nm
[43] Sand SP Rice Husk Ash 38 (w/b = The replacement of 3% NT shows significant improvement in compressive
Coarse aggregate (Max. (10%). 0.41) strength both at 7 (17%) and 28 days (11%).
Size: 20 mm) Nano TiO2 (NT)
[50] Sand SP (≈1.5%) Nano-Fe2O3 (NF) 37.4 (w/b The replacement of 2% NF shows substantial enhancement in compressive
Fly ash (33%) Particle size: 60 = 0.4) strength at 28 days (12%).
nm
Surface area: 60
m2/g
[50] Sand SP (≈1.5%) Nano-CuO (NC) 37.4 (w/b The replacement of 3% NC shows significant enhancement in compressive
Fly ash (33%) Particle size: 15 = 0.4) strength both at 7 (18%) and 28 days (16%).
nm
Surface area: 200
m2/g
[51] Sand (Max. Size: 1.18 SP (2.2–3.6%) Nano-SiO2 (NS) 90.3 (w/b The replacement of 1% NS shows an enhancement in compressive strength at 28
mm) Particle size: 5–20 = 0.25) days of 7%.
nm
[51] Sand (Max. Size: 1.18 SP (0.3–1.7%) Nano-SiO2 (NS) 55.8 (w/b The replacement of 2% NS shows significant improvement in compressive strength
mm) Particle size: 5–20 = 0.40) both at 7 (36%) and 28 days (17%).
nm
[110] Sand SP (2%) Silica fume (5%) 55 (w/b = The replacement of 1% NA shows significant improvement in compressive
Nano-Al2O3 (NA) 0.35) strength at 28 days (16%).
Particle size: 13
nm
Surface area:
85–115 m2/g

confused the difference between mechanical properties at elevated
temperatures (during fire exposure) and residual mechanical properties
(after fire exposure), as well as the difference between mechanical
properties and structural behaviour obtained from steady (fire-resistant)
and transient state tests (fire resistance).
5.3. Potential opportunities
In spite of the fact that studies concerning the effects of nanoparticles
on the thermal properties of cementitious materials containing high
volume replacements and/or lightweight aggregates (namely vermicu­
lite and perlite, for instance) are much more scarce, it has been observed
recently in a few studies that nanoparticles shows potential to increase
the fire performance of cementitious mortars [123], not only in terms of
thermal properties (especially when porous nanoparticles start being
used) but maybe also of bond strength in the fireproofing material
interface and in terms of maintaining the integrity of thick fire protec­
tion materials when exposed to high temperatures. For instance, owing
to their sole chemical and physical characteristics, nanomaterials have
been used for enhancing the residual properties of cementitious

11
L. Laím et al. Journal of Building Engineering 35 (2021) 102008

Table 3
A summary of the influence of nanoparticles on the residual strength of cementitious construction materials at high temperatures.
Reference Aggregates Additives Replacement fc (OPC - MPa) Heating rate Major findings
(◦ C/min)

[107] – – Nanosilica (NS) 54 (consistency = 5 The replacement of 1% NS shows an enhancement in compressive

Particle size: 15 nm 26.5%) strength of 11% after exposing to 450 ◦ C, comparing to OPC.
[107] – SP (1%) Nanosilica (NS) 60 (consistency = 5 The replacement of 1% NS shows an enhancement in compressive
Particle size: 15 nm 20%) strength of 26% after exposing to 450 ◦ C, comparing to OPC.
[110] Sand SP (2%) Silica Fume (5%) 55 (w/b = 0.35) 10 The replacement of 1% NA shows an enhancement in compressive
Nano-alumina strength of 28% after exposing to 400 ◦ C, comparing to OPC.
(NA)
Surface area: 100
m2/g
Particle size: 13 nm
[111] Sand SP (2%) Silica Fume (5%) 55 (w/b = 0.35) 10 The replacement of 2% NT shows an enhancement in compressive
Nanotitania (NT) strength of 42% after exposing to 400 ◦ C, comparing to OPC.
Surface area: 50
m2/g
Particle size: 21 nm
[114] Sand SP Nanosilica (NS) 56 (w/b = 0.4) 9 The replacement of 7.5% NS shows an enhancement in
Polypropylene compressive strength of 80% after exposing to 400 ◦ C, comparing
fiber to OPC.
[117] – – Nano-alumina 60 (consistency = 5 The replacement of 1% NA shows an enhancement in compressive
(NA) 26.5%) strength of 31% after exposing to 450 ◦ C, comparing to OPC.
Surface area: 165
m2/g
Particle size: 15 nm
[117] – SP (1%) Nano-alumina 78.5 (consistency 5 The replacement of 1% NA shows an enhancement in compressive
(NA) = 20%) strength of 46% after exposing to 450 ◦ C, comparing to OPC.
Surface area: 165
m2/g
Particle size: 15 nm
[119] – SP (2%) Nanomagnetite 51.5 (w/b = 0.45) 1 The replacement of 5% NF shows an enhancement in compressive
(NF) strength of 25% after exposing to 200 ◦ C, comparing to OPC.

materials. However, the optimum quantity of nanoparticles for such
applications is usually lower than for ambient temperature purposes,
since low density can have a negative effect on the fire behaviour of such
materials (usually 1%, as it can be seen briefly in Table 3). Furthermore,
note that the improvement in mechanical properties of such materials
without coarse aggregates (around 30% at 400 ◦ C), it may be only
considered for elevated temperature purposes, since that comparison
was done in relation to the reference composition (without nano­
particles) and not to its own composition (with nanoparticles) at
ambient temperatures. This means that nanoparticles may be more
profitable for non-structural cement-based fire protection materials than
for structural ones. Last but not least, it seems that superplasticizer and
polypropylene fibres may play an important role in the mechanical
behaviour of these materials, maximizing the beneficial effect of the
nanoparticles.
The fact that it is well known that concrete structures perform well
under high temperatures and consequently why cementitious materials
are quite widely used in building construction; new research, innovation
and technology on this topic should continue to be one of the most
exciting and privileged engineering fields of the structural fire safety
study.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors acknowledge to the FCT for its funding for the research
project PTDC/ECI-EGC/31850/2017 (NANOFIRE) and also to the Uni­
versity of Coimbra (UC) for their support under the Scientific Employ­
ment Stimulus Programme granted to the first author. The authors also
thank the European Social Fund, European Regional Development Fund,
FEDER (POCI-01-0145-FEDER-007633), Centro 2020 (ENTRO-01-0145-
FEDER-000006), and European Structural and Investment Funds for
their financial support. This work was also partly financed by FCT /
MCTES through National Funds (PIDDAC) under the R&D Unit Institute
for Sustainability and Innovation in Structural Engineering (ISISE),
under reference UIDB / 04029/2020.
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