Hanus 2013

Progress in Materials Science 58 (2013) 1056–1102
Contents lists available at SciVerse ScienceDirect
Progress in Materials Science

journal homepage: www.elsevier.com/locate/pmatsci
Nanotechnology innovations for the construction

industry
Monica J. Hanus ⇑, Andrew T. Harris
Engineering Excellence Group, Laing O’Rourke, Level 2, 97 Rose Street, Chippendale, NSW 2008, Australia
School of Chemical and Biomolecular Engineering, Chemical Engineering Building (J01), University of Sydney, NSW 2006, Australia
a r t i c l e i n f o a b s t r a c t
Article history: A broad range of challenges faced by the construction industry,

Received 29 November 2012 ranging from the performance of the materials to environmental
Received in revised form 14 March 2013 and safety issues, relate to materials and their properties. Recent
Accepted 20 March 2013
developments in various areas of nanotechnology show significant
Available online 6 April 2013
promise in addressing many of these challenges. Research and
developments have demonstrated that the application of nanotech-
nology can improve the performance of traditional construction
materials, such as concrete and steel. Noteworthy improvements
in concrete strength, durability and sustainability are being
achieved with considered use of metal/metal oxide nanoparticles
and engineered nanoparticles (carbon nanotubes and carbon nano-
fibres), and environment-responsive anticorrosion coatings formed
using nanoencapsulation techniques are showing promise in labo-
ratory settings. Developments in nanotechnology are also improv-
ing the accuracy and commercial viability of sensor-based
structural health monitoring; a task rapidly gaining importance as
the structures that comprise many countries’ most expensive
investments near the end of their design life. As energy usage world-
wide continues to grow, a focus on the potential for nanotechnology
developments to reduce energy consumption has become evident.
Research demonstrates that nanotechnology can contribute to
novel cooling systems, and improve the functionality of solar cells
and insulation. A range of nanomaterials are also being used to
add new functionalities, such as self-cleaning properties, to tradi-
tional construction industry products, for example paint and
cement. First generation products are available on the market and
further advances are evident in the academic literature.
Ó 2013 Elsevier Ltd. All rights reserved.
⇑ Corresponding author at: Engineering Excellence Group, Laing O’Rourke, Level 2, 97 Rose Street, Chippendale, NSW 2008,
Australia.
E-mail addresses: mhan6382@uni.sydney.edu.au, mhanus@laingorourke.com.au (M.J. Hanus).
0079-6425/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.pmatsci.2013.04.001
M.J. Hanus, A.T. Harris / Progress in Materials Science 58 (2013) 1056–1102 1057
Nomenclature
AM1.5G air mass 1.5 global;

BOS balance-of-systems
CNF carbon nanofibre
CNT carbon nanotube
CH calcium hydroxide
C-S-H calcium silicate hydrate
C60 buckminsterfullerene
DNA deoxyribonucleic acid
e_ electron E. coli, Escherichia coli
EU European Union
h+ ‘‘hole’’ or electron vacancy IR, infrared
LEED Leadership in Energy and Environmental Design
MEMS microelectromechanical systems
MRSA methicillin-resistant Staphylococcus aureus
MWCNT multi-walled carbon nanotube
OPC ordinary Portland cement
PDMS polydimethylsiloxane; PICADA, Photocatalytic Innovative Coverings Application for
Depollution Assessment
ppb parts per billion ppm, parts per million
PTFE polytetrafluoroethylene
PVC polyvinyl chloride S. aureus, Staphylococcus aureus
SEM scanning electron microscope/microscopy
SWCNT single-walled carbon nanotube
TEM transmission electron microscope/microscopy
UV ultraviolet; VOC, volatile organic compound(s)
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
2. Concrete improvements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
2.1. Metal oxide nanoparticle additions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
2.2. Nanocarbon additions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
2.3. Utilisation of industrial waste products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
3. Structural health monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
3.1. Sensing devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1063
3.2. Self-sensing concrete. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
4. Antimicrobial surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
4.1. Antimicrobial metal and metal oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1066
4.1.1. Photocatalytic antimicrobial nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1066
4.1.2. The effect of metal/metal oxide physicochemical properties on antimicrobial activity 1067
4.1.3. Antimicrobial coatings from antimicrobial nanoparticles . . . . . . . . . . . . . . . . . . . . . . 1068
4.2. Antimicrobial engineered nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070
5. Self-cleaning surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1071
5.1. Superhydrophobic surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1072
5.2. Superhydrophilic surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1075
5.2.1. Applications of superhydrophilic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1077
6. Air purifying surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080
7. Evaporative cooling for building surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
8. Silica aerogel insulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
9. Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1090
10. Anticorrosion coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1093
1058 M.J. Hanus, A.T. Harris / Progress in Materials Science 58 (2013) 1056–1102
11. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094

Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1095
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1095
1. Introduction
Nanotechnology refers to the understanding and manipulation of materials on the nanoscale

(<100 nm). At the nanoscale, substance properties are dictated by quantum mechanics. Surface effects,
rather than bulk properties, dominate. This can lead to marked changes in material properties and can
result in improved performance and new functionality [1].
Nanotechnology has broad-reaching applications in the construction industry. Nanotechnology
may improve the primary properties of traditional construction materials (e.g. concrete), add func-
tionalities to existing materials (e.g. paints/coatings or glass may gain self-cleaning, antimicrobial
and pollution reducing properties) and introduce ‘‘new’’ materials to fill existing needs (e.g. silica
aerogels for thin and effective or transparent insulation, or nanoencapsulated corrosion inhibitors
for steel corrosion protection). Nanotechnology has the potential to reduce the environmental impact
and energy intensity of structures, as well as improve safety and decrease costs associated with civil
intrastructure. Many nanotechnology-based innovations have far-reaching and significant impacts
and are highly regarded during Leadership in Energy and Environmental Design (LEED), Green Star
(Australia) or similar accreditations [2].
Nanotechnology and nanomaterials with applications in the construction industry are at various
stages of development ranging from conceptual ideas to commercially available products. Awareness
of nanotechnology applications in construction among industrial personnel is, however, remarkably
low [3–5]. Failure to distinguish between what is available now and what is theoretically possible
in the future has been the cause of many misconceptions about nanotechnology [1,6]. A report by RI-
LEM suggested, based on responses by construction industry personnel to their surveys, that nano-
technology was perceived by the construction industry as expensive and too complex to explain to
clients who want a structure built as soon and as cheaply as possible [3]. This contrasts with the very
rapid growth in awareness and interest in nanotechnology utilisation in many other industrial sectors,
such as chemicals, automobiles and energy [3]. The negative perception within the construction
industry results in both current and future developments with potentially significant impact on both
the success of construction companies and the betterment of society being overlooked.
2. Concrete improvements
Concrete (alongside steel) is the cornerstone of the construction industry. It is estimated that
3.3 billion tonnes of cement, the binder in concrete, were produced worldwide in 2010. This is an al-
most 8% increase from 2009, and worldwide production of cement continues to increase, spurred on
by the growing demand in emerging economies such as China and India [7]. Cement manufacture is,
however, an energy intensive process and represents 7% of worldwide energy consumption and 4% of
worldwide industrial CO2 emissions [8]. The incorporation of nanomaterials can improve structural
efficiency, durability and strength of cementitious materials and can thereby assist in improving
the quality and longevity of structures. The use of nanoscale industrial waste-based cement replace-
ments can reduce carbon dioxide emissions associated with concrete production [4,5,8].
2.1. Metal oxide nanoparticle additions
The steel in reinforced concrete structures is susceptible to corrosion and degradation by ions in
the environment (e.g. chloride and sulfate ions), which may permeate through the concrete matrix
at rates dependent on the concrete structure. The addition of some metal oxide nanoparticles to
concretes can both reduce the permeability of concrete to ions and increase the strength of concrete,
thereby improving durability. The addition of TiO2 nanoparticles [9–11], Al2O3 nanoparticles [12–14],
ZrO2 nanoparticles [14], Fe2O3 nanoparticles [12,14–16], SiO2 nanoparticles [11,12,15–20] and metal
oxide containing nanoclays [21–24] have all been shown to improve concrete and/or cement mortar
properties. Metal oxide nanoparticle addition accelerates chemical reactions during initial hydration
thus strengthening cement composites. The metal oxide nanoparticles react with CaOH increasing
the amount of calcium silicate hydrate (C-S-H) produced, leading to a more compact microstructure,
thereby not only decreasing permeability but also improving mechanical properties [17] such as com-
pressive strength, flexural strength and abrasion resistance [18]. For example, Zhang and Li [11] found
that the addition of 1% (by weight of binder) of 15 nm diameter TiO2 to concrete refined the pore
structure and increased the resistance to chloride penetration by 31%. Shekari and Razzaghi [14] found
that the addition of 1.5% (by weight of cement-based material) of 10–25 nm ZrO2, TiO2, Al2O3 or Fe3O4
increased the compressive strength and reduced chloride penetration of the concrete by 20–80%. It is
important to examine the impact of these additions on the propensity of the concrete to undergo
early-age cracking. Early-age cracking has been shown to increase with the addition of fine pozzolans
such as silica fume: SiO2 particles with a mean particle size >100 nm [25,26]. Through-depth cracks, of
course, severely compromise improvements in impermeability.
Fig. 1. Strength assessment of self-compacting concrete containing no SiO2 nanoparticles or 4 wt.% SiO2 nanoparticles after 2, 7
and 28 days of curing, from [20].
The addition of SiO2 nanoparticles is widely reported to be an effective for strengthening concrete;
both normally vibrated concrete [19] and self-compacting concrete [20]. For example, Nazari and Ria-
hi [20] report that the compressive, split tensile and flexural strength of the 4 wt.% SiO2 nanoparticle
concrete is, respectively, 1.7, 2.2 and 1.6 times greater than that of the equivalent SiO2 nanoparticle-
free concrete after 28 days of curing (Fig. 1). Generally, cement-based materials containing SiO2 nano-
particles are stronger than those containing SiO2 fume [19]. This is attributed to the accelerated
cement hydration, increased pozzolanic activity, reduced pore size and improved interfacial bonding
between the hardened cement paste and aggregate that is associated with the decreased average par-
ticle size of the SiO2 [27]. Several cement-based products that contain SiO2 nanoparticles have been
commercially available in recent years, for example Gaia, which was developed by Cognoscible Tech-
nologies and Ulmen (Chile) to substitute for SiO2 fume at ready-mixed concrete facilities [28], and
NanodurÒ by Dykerhoff (Germany) [6,29].
2.2. Nanocarbon additions
Nanocarbons [30] (particularly carbon nanotubes (CNTs) and carbon nanofibres (CNFs)) have at-
tracted significant attention for the improvement of the strength of cement-based composites. Nano-
carbons possess remarkable properties. CNTs have a high tensile strength and Young’s modulus,
display elastic behaviour [31] and excellent thermal properties [32]. Indeed, the tensile strength and
Young’s modulus of CNTs are hundreds and tens of times that of steel, respectively, although their
weight per volume of CNTs is a mere fraction that of steel. CNTs reinforce concrete at the nanoscale
rather than the macro scale in the manner of traditional steel reinforcement bars. In the mesoporous
environment of concrete, nanoscale reinforcements can act as fillers to produce a denser, less porous
material. Nanoscale reinforcements can also inhibit crack growth in the initial stages (and thus pre-
vent crack propagation), enhance the quality of the paste-aggregate interface and increase the amount
of high stiffness C-S-H [30,33]. A scanning electron microscope image of CNTs bridging cracks in a hy-
drated OPC/CNT composite is shown in Fig. 2.
The predicted reinforcing potential of CNTs/CNFs in a concrete matrix (and indeed in CNT compos-
ites in general [34]) is proving difficult to achieve consistently in practice. There is no evidence of CNTs
in commercially available construction materials [5]. The results of mechanical testing of CNT/OPC and
CNT/concrete composites have been highly variable [30]. Some trials have shown significant improve-
ments in compressive strength, Young’s modulus and hardness, while others have shown insignificant
changes in compressive strength and decreases in Young’s modulus. Good concrete improvements
attributed to CNT addition include a 50% increase in compressive strength [35], >600% improvement
in Vickers’s hardness at early ages of hydration [36], and >200% increase in Young’s modulus [37]. Re-
sults to date have not convincingly shown improved flexural strength. The large variability in the
Fig. 2. CNT bundles crack bridging in a hydrated OPC/CNT composite, from [30].
performance of CNT/concrete and CNT/cement composites is considered a function of the difficulties

in achieving good CNT dispersion [38]. As with all composites, good dispersion of the nanoparticles in
the concrete or cement mortar matrix is vital for improvements in mechanical properties of the com-
posite; however, good dispersion is particularly difficult to achieve with nanomaterials with a large
aspect ratio such as CNTs due to their high surface energy and strong interparticle forces (e.g. Van
der Waals interactions) [20,39]. If not properly dispersed, the addition nanomaterials to cementitious
materials results in a decline in mechanical properties. The presence of aggregated nanoparticles can
result in voids or unreacted ‘‘pockets’’ (since the nanomaterials behave as an activator to promote poz-
zolanic reactions), and thus poor dispersion of nanoparticles can result in weak zones or potential
areas for concentrated stresses [20,39,40]. The intrinsically hydrophobic nature of CNTs results in poor
interaction of CNTs with the cement or concrete matrix and this impacts on the cement hydration pro-
cess [37]. This effect is exacerbated when the CNTs are bundled due to poorly dispersed.
Compounds that have been reported as suitable for the dispersion of CNTs in cement-based com-
posites include polycarboxylate, gum Arabic, sodium linear alkylbenzene sulfonate and polyacrylic
acid [35,37,41–44]. Polyacrylic acid is reported to act both as a plasticising agent for the cement paste
and a dispersing agent for the CNTs [44]. The use of nitrogen doped CNTs or prior functionalisation of
CNTs with carboxylic acid groups and sonication was also found to assist with dispersion when used in
conjunction with a suitable solvent [34,35,38,41]. Sonication of CNTs and OPC in isopropanol followed
by isopropanol removal by drying was found to be effective for dispersion; however, damage to ce-
ment grain surfaces and slowing of the initial hydration process was reported [36]. Variations in
CNT properties between synthesis batches, and even variations of CNT properties within synthesis
batches, are typical. As such, it is expected that the dispersion that can be achieved is affected by
the source of the CNT sample and the purification method used by the supplier [30,36]. This makes
comparisons and generalisations about the effectiveness of dispersion techniques difficult. It must also
be noted that techniques and methods that result in good dispersion of nanomaterials in cement
pastes may not necessarily achieve good dispersions if attempted with a concrete.
The cost of CNTs is currently prohibitively high to allow for the use of CNT/cement composites in
large concrete structures [30].
Note, however, that although technology used for large-scale CNT manufacture (such as fluidised
bed chemical vapour deposition) typically produces low quality CNTs, these are sufficient for achiev-
ing an improvement in concrete properties. Furthermore, the price of CNTs can be expected to con-
tinue to fall over the coming years as large-scale CNT manufacturing technology improves and
matures, and production of CNTs increases [32].
2.3. Utilisation of industrial waste products
The use of industrial waste product-based cement replacements, such as fly ash and sewage sludge,
have gained attention due to their potential to reduce the cost and environmental impact of cement-
based materials [45,46]. The effect of these replacements can also have either a positive or negative
effect on various concrete properties. For example, although the addition of fly ash to concrete im-
proves durability, reduces water requirements, improves finishability characteristics, etc. [47], the
early strength of high fly ash content concrete is low because the pozzolanic reaction of fly ash in
the mortar is slow [45]. In contrast, the addition of SiO2 nanoparticles can activate fly ash, increasing
pozzolanic activity significantly, which leads to an increase to both short-term and long-term
strength [45,48] such that the early age strength of the SiO2 nanoparticle/fly ash concrete matches
or exceeds that of normal concrete mixtures [6,49]. The SiO2 nanoparticle additive itself can also be
sourced from waste materials such as rice husk [50].
The addition of CNTs to fly ash-containing cement mortars has also been shown to compensate for
the loss of strength associated with fly ash addition. The addition of 1 wt.% CNTs to a 20 wt.% fly ash/
80 wt.% Ordinary Portland cement (OPC) mortar resulted in the compressive strength after 28 days of
curing to be 98% of the compressive strength of the OPC, whereas the compressive strength of the
20 wt.% fly ash cement mortar without CNTs was 90% of the compressive strength of the OPC [51]. Fur-
thermore, CNTs and CNFs have been grown directly on cement components, such as cement particles,
silica fume or fly-ash particles, whereby the cement or fly-ash was used as a catalyst for CNT and/or
CNF synthesis either directly or after impregnation of the cement component with a catalyst prior to
synthesis [52–54]. Synthesising CNTs/CNFs directly on cement components can improve the CNT/CNF
dispersion in a cement matrix. It can also reduce the number of steps required for CNT/CNF addition to
cement because, not only may the need for a CNT/CNF dispersion step be avoided, but the synthesised
CNTs/CNFs do not need to be removed from the substrate on which they form (as is otherwise typi-
cally required) [52]. A study by Nasibulin et al. [54] found that although the compressive strength
of a CNT/CNF and cement hybrid material (in which CNTs/CNFs were synthesised on the cement par-
ticles) was lower after 7 days of curing, the compression strength after 28 days of curing was double
that of the CNT/CNF-free cement.
3. Structural health monitoring
Civil infrastructures are generally a country’s most expensive investment, with concrete the most
widely used material. During the service life of a structure, concrete ages and deteriorates, leading to
substantial loss of structural integrity and potentially resulting in disasters such as highway bridge
collapses if deterioration is not accurately monitored and rectified. Over 50% of all bridges in the
USA were built before 1940 [55]. At this time, structural health monitoring – the process of imple-
menting damage detection and characterisation strategies for engineering structures – is, by and large,
done manually by visual inspection. Federal requirements in the USA necessitate local transport
authorities to visually inspect the entire inventory of well over 500,000 highway bridges biennially,
and other structures, such as buildings, as needed [56]. Examination of structures by visual inspection
is expensive, time-consuming and labour-intensive. It is also highly subjective and can only consider
damage that is visible on the surface of the structure [57]. Federal spending for the replacement of
structurally obsolete bridges in the USA is approximately $10 billion per year. The poor accuracy of
assessments by current methods results in the retrofitting or replacement of many bridges that, in
some cases, need not be retrofitted or replaced, and the possibility that some bridges needing engi-
neering renewal or replacement are not identified [58].
More advanced and accurate methods for structural health monitoring are available and continue
to be developed. More advanced structural health monitoring typically involves the analysis of a range
of measurements from sensors such as displacement transducers, accelerometers, strain gauges and
temperature sensors, which provide an array of real-time information that may be continuously
monitored from a central location to provide detailed insight into the state of a structure. Structural
health monitoring can be performed by: (i) attaching sensors to the surface of a concrete structure,
(ii) embedding sensors into concrete structures during construction or, (iii) by constructing structures
or parts of structures using an intrinsically ‘‘smart concrete’’ – a concrete containing a material that
allows self-monitoring of strain and/or other properties. Significant investments have been made into
the development of more effective structural health monitoring systems in recent years [42,59] and
structural health monitoring systems have been installed in some locations e.g. at the Ting Kau, Tsing
Ma and Kap Shui Mun bridges in Hong Kong [60], the Rion-Antirion bridge in Greece [61], the Huey P.
Long in the USA [62]. Nanotechnology plays an important role in progressing structural health mon-
itoring systems. It is expected that the implementation of advanced structural health monitoring sys-
tems will increase as the technology matures and associated costs decrease.
In the context of structural health monitoring, sensing typically refers to the ability to provide an
electrical or optical response to a stress or strain [42] and self-monitoring of structures is performed
by measuring the variation of an electrical property (usually electrical resistance) that is correlated to
the increase of stress or strain. Chen and Chung [63] give the following requirements for a structural
sensor:
(a) Wide stress/strain range of detection (from small strains up to failure).

(b) Reversible response upon stimulus removal (necessary for repeated use of the sensor).
(c) Ease of response measurement (without the need for expensive peripheral equipment).
(d) Presence of the sensor having no negative effect on the structural properties of the structure.
(e) Chemical stability and durability.
(f) Low cost.
3.1. Sensing devices
Commonly used sensors (e.g. optical fibres, piezoelectric sensors, strain gauges) all suffer from high
cost, poor durability and the need for expensive peripheral equipment, including electronics and la-
sers, and so the use of such sensors in civil structures is uncommon [16,42,63]. Nanotechnology-based
microelectromechanical systems (MEMS) sensors have shown some improvements on traditional sen-
sors. In general, MEMS technology has led to the development of sensors that are lower in cost, use
less power, are compact and easy to install [57]. Emerging nanotechnology-based MEMS sensors have
further improved capabilities and sensitivities. MEMS sensors can either be surface mounted [64] or
embedded in concrete structure itself [65] and the sensors can be used for continuous measurement
and monitoring of the strain in structures. Additionally, when embedded in concrete, the sensors can
provide accurate in situ measurements; however, the sensors must be able to withstand harsh condi-
tions, including an alkaline environment and internal and external stress present in the concrete.
Embedded MEMS sensors can be used for monitoring a range of concrete properties including temper-
ature, hydration and moisture, chloride ions, water-related degradation, carbon dioxide and
pH [8,65,66]. Ideally, hundreds to millions of these sensors would be embedded in concrete structures;
however, both the current state of technology of nanotechnology-based MEMS and cost are major lim-
iting factors. In 2008, Norris et al. [66] reported device cost to be $25/unit with the expectation that
this cost would decrease to $1 within a few years.
Nanotechnology used in MEMS sensors for structural health monitoring includes the use of nano-
polymer films and CNTs. Norris et al. [66] used a water vapour-sensitive nanopolymer film in a MEMS
sensor for the detection of temperature and moisture. CNTs have attracted attention for structural
health monitoring applications in surface mounted sensors, embedded sensors and smart concretes.
Lebental et al. [8] used highly aligned single-walled CNTs to produce a dense, ultra-thin membrane
for a capacitive micromachined ultrasonic transducer that could potentially allow in situ monitoring
of hydration and water-related degradation at the microscale (Fig. 3a).
CNT composite (e.g. CNT/cement or CNT/polymer) sensors display piezoelectric behav-
iour [43,65,67]. High sensitivity strain sensors (with a sensitivity of 0.004%) that could potentially
be mass produced have been reported [68]. When these sensors are subjected to mechanical strain
or temperature changes [69], the sensor deforms and its effective resistance changes, mainly due to
Fig. 3. Two types of CNT-based sensors for structural health monitoring. (a) A microtransducer containing a vibrating
membrane composed of aligned CNTs, from [8], and, (b) a sensor composed of cement containing CNTs for microcrack detection,
from [67].
changes in contact resistance at CNT junctions, where the thickness of the insulating films between
adjacent CNTs is altered due to the applied load. When microcracks develop in the cement matrix,
some percolation branches will be cut off, causing a sudden and sharp change in the electrical resis-
tance of the sensor [67]. Sensors containing randomly orientated CNTs, such as those typically pro-
duced by chemical vapour deposition (a common large-scale CNT synthesis method), allow for non-
directional specific measurements [70]. Saafi et al. [65,67] embedded CNT/cement sensors in concrete.
These wireless sensors allowed changes in the electrical resistance of the CNT network (which indi-
cated the progress of damage) to be detected and monitored (Fig. 3b). CNT sensors in concrete struc-
tures have, however, suffered some drawbacks such as susceptibility to damage by the alkaline
environment of concrete and high cost [67]. Norris et al. [66] discuss that nanotechnology and MEMS
could allow wireless, inexpensive, durable, compact and high-density information collection, process-
ing and storage devices for structural health monitoring; however, significant further investigation
and development of various aspects including peripheral equipment is required for this to be possible.
For example, improvements in the wireless interrogation system (e.g. signal processing, powering,
communication, location, orientation, data storage, computation capabilities) are required, as well
as studies of the long-term behaviour and repeatability of such sensors.
3.2. Self-sensing concrete
Additives proven to promote self-sensing in concretes (that is, additives in ‘‘smart concretes’’) are
typically nanoparticles such as Fe2O3 nanoparticles [16] and nanocarbons (e.g. CNFs [42]). When a
compressive force is applied to a mortar containing Fe2O3 nanoparticles, the band gap of Fe2O3 nano-
particles – a semiconducting material – is narrowed thereby improving conductivity. With the appli-
cation of compressive force, the nanoparticles are also compelled to approach each other, which
makes the tunneling current flows become more intense, and therefore the electrical conductivity
of the cement mortar increases gradually [16,71]. CNFs are more conductive than the concrete matrix
in with they are embedded, which provides potential for self-sensing. Howser et al. [42] found that
peaks and troughs in electrical resistance readings matched the peaks and troughs of the applied force
and concrete strain in reinforced, self-consolidating concrete containing well dispersed CNFs. This al-
lowed the level of damage to the reinforced concrete columns to be readily detected and assessed, and
provided real-time monitoring of the overall structural integrity. Orientations of the CNFs were ran-
dom, and it is reported that the CNFs do not have to touch one another for self-sensing to be possible.
The incorporation of carbon black nanoparticle-glass fibre reinforced polymer into concrete has also
been shown to produce a concrete that has self-monitoring characteristics, even during concrete cur-
ing [72]. Coppola et al. [43] produced a self-sensing mortar by adding CNTs to the mortar; however,
sensitivity was low because the CNT concentration used was insufficient for CNT networks to form.
Generally, self-sensing concretes produced by the addition of nanoparticles such as Fe2O3 nanopar-
ticles and CNFs address the requirements of structural sensors (as stipulated by Chen and Chung [63])
well. They allow a wide range of stresses/strains to be detected and the response is reversible. Mea-
surements can be performed easily without expensive peripheral equipment. Not only does the pres-
ence of the Fe2O3 nanoparticles and CNFs have no negative effect in structural properties, properties
such as compressive strength, flexural strength, and ductility can be enhanced (as was discussed in
Section 2).
4. Antimicrobial surfaces
Antimicrobial surfaces have applications in a range of infrastructure including in hospitals, child-

care centres, nursing homes, etc., to assist in minimising the spread of disease and reducing the prev-
alence of illness and discomfort. Nosocomial infections (hospital-acquired infection) cases have been
increasing rapidly in recent decades, and the prevalence of antibiotic-resistant pathogens is of partic-
ular concern due to difficulties in treating these patients, and their high mortality rates. Two billion
people worldwide carry Staphylococcus aureus (S. aureus) and up to 53 million of these carry the resis-
tant form, methicillin-resistant S. aureus (MRSA) [73]. In 2005, in the USA alone, S. aureus-related
diseases were responsible for nearly 500,000 hospitalisations and 11,000 deaths (with approximately
58% of the hospitalisations and 5000 of the deaths attributed to a resistant strain) [74]. In the Euro-
pean Union (EU), the European Centre for Disease Prevention and Control reports that about 4 million
people acquire nosocomial infections annually (of which 5% are MRSA infections), and about 37,000
deaths occur annually as a result of nosocomial infections [75]. Nosocomial infections are estimated
to cost at approximately €5.5 billion per year in the EU [76]. The long periods of hospitalisation re-
quired by S. aureus-infected patients, in particular, represents a high cost to public and private health
insurance systems [77]. Walls, floors and other surfaces provide an easily accessible platform for path-
ogenic bacterial to settle and proliferate. Any surface, once touched by an infected person, serves as a
breeding ground for such pathogens [78]. It is estimated that 15% of nosocomial infections in the EU
occur due to transmission through inanimate objects [79].
Other often less severe but also prevalent illness and discomfort has also been linked to the growth
of microbes in buildings [80]. For example, ‘‘sick building syndrome’’, whereby building occupants
experience acute health and comfort effects that appear linked to time spent in a building, and ‘‘build-
ing related illness’’, whereby illnesses are attributed directly to airborne building contaminants [81].
There are many types of antimicrobial nanoparticles that can be used as the active agent in anti-
microbial coatings. Antimicrobial nanoparticles fall broadly into three categories [82]: naturally
occurring antimicrobial substances (e.g. chitin, chitosan and some peptides), metals/metal oxides
(e.g. Ag, TiO2, ZnO, Cu, CuO, MgO) and engineered nanomaterials (e.g. CNTs, fullerenes). Naturally
occurring antimicrobial substances are, however, generally reported in water treatment and food
preservation applications rather than in antimicrobial surfaces for infrastructure, and so are not ad-
dressed in this review. The antimicrobial activity of the nanoparticles can be achieved through a range
of different mechanisms. The nanoparticles can interact with microbial cells directly (e.g. by interrupt-
ing transmembrane electron transfer, disrupting/penetrating the cell envelope, or oxidising cell com-
ponents) and/or by producing secondary products that cause damage (e.g. reactive oxygen species or
dissolved heavy metal ions) [82]. The main antimicrobial mechanisms of antimicrobial nanoparticles
are shown in Fig. 4.
Nanoparticle-based antimicrobials can offer significant benefits over conventional chemical, pho-
tochemical or physical disinfection methods. Unlike some conventional antimicrobial agents, many
antimicrobial nanomaterials (e.g. Ag nanoparticles and Cu nanoparticles) exhibit strong toxicity to-
wards a broad range of microorganisms found in industrial processes [83] and the human body, but
a remarkably low toxicity to humans [84,85]. In contrast, many conventional disinfectants are toxic
to humans; for example, most antifungal chemicals are non-specific to the organism affected and
can be detrimental to the environment (toxic to plants and animals) [86]. It has also been suggested
that disinfection with some nanomaterial compounds (e.g. TiO2) can be more effective than conven-
tional disinfection (e.g. with chlorine) [87] and, particularly when supported in a substrate, some
nanoparticles have demonstrated good stability and long-term activity [84,88]. Opinions are divided
regarding the development of resistance by microbes to nanoparticle-based antimicrobial agents.
Fig. 4. The main antimicrobial mechanisms of nanomaterials, adapted from Li et al. [82].
Some studies report that there has been no evidence of microorganisms developing resistance to
nanoparticles and that the development of resistance is unlikely due to the different antimicrobial
mechanisms of nanoparticles when compared to that of many conventional antimicrobial
agents [84,88]. Others have suggested that silver resistance already occurs extensively, but it is not
recognised due to a lack of testing for silver resistance [89].
Many effective nanoparticle-based antimicrobial agents are confirmed, but few are used in the con-
struction industry for cost reasons. At present, Ag and TiO2 are the only commercially used antimicro-
bial nanomaterials [90] and Ag nanoparticles are the most widely used [82]. There are many Ag
nanoparticle-containing fabrics [91] and antimicrobial Ag nanoparticle-containing interior paints [92]
are available on the market. Many other commercial silver-based antimicrobial products on the mar-
ket currently utilise silver ions or other forms of silver [93]; however, the favourable properties of Ag
nanoparticles over other forms of Ag (e.g. enduring antimicrobial properties) may see the use of other
forms of Ag phased out in favour of Ag nanoparticles in some applications.
4.1. Antimicrobial metal and metal oxide nanoparticles
The antimicrobial properties of some metals and metal compounds have been known since ancient
times when, for example, Ag-based compounds were used for water treatment. In recent times, many
metal and metal oxide nanoparticles have been found to be particularly effective antimicrobials, more
so than the corresponding bulk materials due to their greater active surface area. Metal/metal oxide
nanoparticles reported to have antimicrobial properties include Ag [84], Cu [84], CuO [94],
ZnO [95,96], MgO [97], TiO2 [86]. The relative effectiveness of antimicrobial agents varies, but many
have proven to be effective against a broad range of bacteria (even antibiotic resistant strains), viruses,
fungi [86,89] and algae [83]. For example, the sensitivity of microbes to functional destruction by pho-
tocatalytic nanoparticles such as TiO2 is reported to follow the order: viruses > gram-negative bacte-
ria > gram-positive bacteria > endospores > yeasts > filamentous fungi [86]. The promising properties
have prompted scientists and engineers to find cost effective and efficient methods for synthesising
these antimicrobial nanoparticles and coatings from them.
4.1.1. Photocatalytic antimicrobial nanoparticles

The antimicrobial properties of photocatalytic nanoparticles such as ZnO and TiO2 nanopartices are
related, at least in part, to their phototcatalytic activity. When irradiated with light of energy greater
Fig. 5. Schematic diagram of the photocatalytic formation of e and h+ in TiO2 and the possible reaction pathways thereof, from
[98].
than or equal to the band gap of the photocatalytic material, an electron (e) is promoted from the
valence band to the conduction band resulting in the generation of a theoretical positively charged
‘‘hole’’ (h+; electron vacancy) in the conduction band. The equation for this process is shown in Eq. (1).
þ
photocatalyst þ hv ! photocatalyst þ e þ h ð1Þ
where electromagnetic radiation is expressed as the product of Planck’s constant, h, and frequency, m.
The h+ and e are powerful oxidising and reducing agents, respectively. The strong oxidising behav-
iour of h+ enables it to react with OH dissociated from water (Eq. (2)) to generate the highly oxidising
hydroxyl radical (OH) (Eq. (3)), while the liberated electrons can diffuse to the surface of the photo-
catalyst and reduce oxygen molecules adsorbed from the atmosphere to form reactive oxygen species.
The e reacts with molecular oxygen to form the superoxide anion, O 2 (Eq. (4)). The superoxide anion
further reacts with H+ dissociated from water to produce HO2 radicals (Eq. (5)). The reactive oxygen
species are capable of decomposing microbes into CO2 and H2O [96–98]. The generation of h+ and
e and their possible reaction pathways is demonstrated with TiO2 in Fig. 5.
H2 O $ Hþ þ OH ð2Þ
þ
h þ OH ! OH ð3Þ
e þ O2 ! O2 ð4Þ
Hþ þ O2 ! HO2 ð5Þ
Effective use of photocatalytic antimicrobial nanoparticles is limited to environments where there
is sufficient irradiation with light of the required wavelength (388 nm UVA light for TiO2, the cheapest
and most abundant photocatalyst). It is, however, noted that incidental irradiation from natural and
some artificial light sources can be sufficient for TiO2 activation [99]. Escherichia coli (E. coli, a common
type of bacteria) cells are deactivated after about 1 h under outdoor UV light intensity and the cells can
completely disappear after about 1 week of 1 mW/cm2 UV irradiation [100]. Typical indoor UV light
intensity is about several hundred nW/cm2; about three orders of magnitude less than outdoor UV
light intensity, and therefore photocatalytic degradation of microorganisms takes much longer in-
doors. Despite this, it has also been shown that a reduction in bacteria numbers can continue in the
dark following irradiation [101] and an anti-algal effect, although less than when irradiation was em-
ployed, was still observed even without irradiation [83]. This suggests that other antimicrobial mech-
anisms unrelated to photocatalysis also contribute to the antimicrobial activity of photocatalytic
nanoparticles. Interestingly, a greater inactivation of bacteria and virus has been observed when using
Ag+ irradiated with UV-C, UV-A or visible light than when using Ag+, UV-C, UV-A or visible light
alone [102]. This is suggestive of a synergistic effect between some antimicrobial agents and
irradiation.
Doping of TiO2 to decrease the band gap, thereby allowing visible light activated photocatalysis, is
an active area of research due to the greater indoor photocatalytic activity this promotes. Doping of
TiO2 with noble metals (Ag, Ni, Pt, Au, Ag, Cu, Rh, Pd) and oxides (ZnO, WO3, SiO2, CrO3) or non-metals
(C, N, S, P) have been found to be effective [86]. This doping does increase the cost of nanomaterials,
but visible light activated TiO2 is commercially available e.g. Kronos vlp 7000 [103] and new visible
light photocatalysts continue to be developed. A new EU research project, SELFCLEAN (Novel self-
cleaning, anti-bacterial coatings, preventing disease transmission on everyday touched surfaces) has
recently been established, with the aim of developing Sn–Ni matrix-based coatings that incorporate
doped-TiO2 nanoparticles to form visible light-activated antimicrobial surfaces suitable for use in pub-
lic places such as hospitals, schools, hotels and public transport [79].
Based on analysis by Future Markets Inc., the use of TiO2 nanoparticles in coatings and paints for
sanitisation and elimination of MRSA is considered to be at mature market stage of commercialisation,
while other TiO2 photocatalytic antibacterial nanocoatings are at the market entry stage [104].
4.1.2. The effect of metal/metal oxide physicochemical properties on antimicrobial activity

Common metal/metal oxide synthesis methods include chemical reduction (the most common
method for producing nano-Ag particles [89]), mechanochemical processing and physical vapour
synthesis (both used for commercial production of ZnO [96]). Other techniques, for example precipi-
tation, thermal decomposition, hydrothermal synthesis [96], may also be used. Conventional nanoma-
terial synthesis typically involves using hazardous chemicals, has low material conversion rates, high
energy requirements, and requires purification that results in the wasting of product [93]. Most novel
production methods are focused on ‘‘green synthesis’’, which aims to replace hazardous chemicals
with non-toxic chemicals, use environmentally benign solvents, and renewable materials [93,105].
The synthesis method and conditions have a major influence on nanoparticle size, shape, and
morphology [93].
Size and other physicochemical properties such as shape and crystallinity, have a significant effect
on the antimicrobial properties of metal/metal oxide nanoparticles [82,88,96,106]. The manufacture of
nanoparticles with a narrow size distribution, specific shape or crystalinity is therefore of great inter-
est. The antimicrobial activity of nanoparticles is inversely dependent on size which is representative
of reactive surface area [88,97]. For example, Ag nanoparticles of <10 nm are more toxic to bacteria
such as E. coli than larger particles, and Ag nanoparticles 1–10 nm in diameter have been shown to
inhibit certain viruses from binding to host cells [82]. Furthermore, triangular silver nanoplates were
found to be more toxic than Ag nanoparticle rods, spheres and Ag+ ions [82,107] because they contain
more h1 1 1i facets, which are highly reactive [89,107,108]. The crystal structure and phase of the
nanoparticles can also be of importance. For example, since the antimicrobial effect of TiO2 is due,
at least in part, to its photoactivity, the crystal phase used will affect its antimicrobial properties be-
cause the different crystal phases differ in their photocatalytic ability. It is worthwhile noting that
which TiO2 phase, or indeed which mixture of phases and in what ratio, is most photocatalytically ac-
tive is widely debated [86].
Nanoparticles must be stable in order to remain effective as antimicrobial agents. Long-term sta-
bility is of significant importance for antimicrobial nanoparticles used in applications such as paints
where enduring, long-term antimicrobial activity is highly desirable. As nanoparticles aggregate, their
effectiveness as an antimicrobial diminishes due to the decreased density of atoms available on the
putative surface [84,85,89,97]. Aggregation can be avoided by supporting nanoparticles on or in the
matrix of other materials e.g. zeolite [109], activated carbon fibres [110–112], CNTs [113–115], fibre
glass [116], Ag vanadate nanowires [77], SiO2 [84,117–120] or TiO2 [121,122]. (Supporting non-TiO2
antimicrobial nanoparticles on TiO2 is reported to enhance antimicrobial activity [123].) Many of these
support materials can be synthesised with a variety of morphologies – e.g. SiO2 can be made as an
amorphous xerogel, aerogel, fibres, monodisperse nanospheres, microparticles, etc. [84]; TiO2 can
be made as nanoparticles or nanotubes [121], etc. – and thus a morphology with properties suited
to a specific application may be selected.
4.1.3. Antimicrobial coatings from antimicrobial nanoparticles

The addition of Ag nanoparticles to commercial paints imparts antimicrobial properties on the
paint, reportedly even when present in concentrations as low as parts-per-million, and without dete-
rioration of the colour of the final products [106,124]. It is reported that the addition of antimicrobial
nanoparticles to paints can actually protect the aesthetic appearance of painted surfaces by preventing
microbial growth that can stain paints and deteriorate paint properties [95]. The addition of 5 vol.%
30–40 nm ZnO [95] or 5 wt.% MgO nanoparticles [97] to an interior paint (aqueous acrylic dispersion
and modified phenylpropyl type paint, respectively) resulted in potent antibacterial and antifungal
properties. The actual antimicrobial effectiveness is influenced by paint properties including type of
acrylic dispersion, total pigment volume concentration, as well as the morphology of the surface [95].
Focusing on Ag and Cu nanoparticles, Zeilecka et al. [84] found that the addition of SiO2 particle-sup-
ported Ag or Cu nanoparticles to silicon acrylic emulsion paints improved the antifungal activity of the
paints (Fig. 6-I) and had a negligible effect on the wetability of a painted surface. Kumar et al. [125]
developed a potent antimicrobial vegetable oil-based paint with embedded Ag nanoparticles (Fig. 6-
II) that was produced in a single step at ambient conditions without using external reagents or large
amounts of energy. Holtz et al. [77] demonstrated that Ag nanoparticles supported on Ag vanadate
nanowires dispersed in a commercial water-based paint was effective against MRSA. This water-based
paint impregnated with 1% (m/v) nano-Ag particles supported on Ag vanadate nanowires showed a
4 mm exclusion zone of inhibition against the bacterial growth of MRSA stains (Fig. 6-III).
Fig. 6. I. (a) An SEM image of Cu nanoparticles immobilised on SiO2 particles (Cu/SiO2), (b) a photo showing that algae did not
grow on a surface coated with paint containing Cu/SiO2 (0.5 ppm Cu nanoparticles), and, (c) a photo showing that algae grew on
a surface coated with Cu/SiO2-free paint. Adapted from [84]. II. (a) A TEM image of Ag nanoparticles synthesised in drying oils,
(b–d) photographs of glass slides onto which aqueous suspensions of S. aureus were sprayed and each black dot corresponds to a
bacteria colony; (b) is an uncoated slide, (c) is a slide coated in only drying oil paint without nanoparticles, (d) is a slide coated
with drying oil paint Ag nanoparticles. Adapted from [125]. III. (a) A TEM image of Ag nanoparticles supported on Ag vanadate
nanowires, (b and (c) results of inhibition zone tests against MRSA for (b) a glass substrate painted with commercial water-
based paint, and, (c) a glass substrate painted with the same paint but with 1% (m/v) Ag vanadate nanowires added. Adapted
from [77].
Synthesis process scalability, cost, final product quality and workability are significant consider-
ations for the use of antimicrobial nanomaterials in civil structures. Cost effective, scalable synthesis
methods are required for the use of these materials to be commercially viable. Synthesis of SiO2–Al2O3
supported Ag nanoparticles in a fluidised-bed reactor – a scalable reactor style – has been reported;
however, the scalability and cost-effectiveness of this process is not explicitly discussed [126]. The
lower cost (and comparable antimicrobial activity) of non-Ag antimicrobial metal nanoparticles such
as Cu, Zn and Mg could attract commercial interest in these materials [90,97]. Effective antimicrobials
have also been formed from metal nanoparticles supported on common fillers such as vermiculites or
montmorillonites [90,127]. For example, Drelich et al. [90] found that the addition of vermiculite sup-
ported Cu nanoparticles improved the antibacterial properties of the paint. Vermiculite is an inexpen-
sive mineral extensively used as a filler in paints, plastics, fireproof material, and concrete, and thus it
is envisaged that the addition of vermiculite supported Cu nanoparticles would have a minimal det-
rimental impact on the properties of the paint (other than antimicrobial properties).
4.2. Antimicrobial engineered nanomaterials
Engineered nanocarbons such as buckminsterfullerenes (C60) and CNTs, are proven antibacterial
agents, and quantum dots (nanoparticles of a semiconductor material) [128] are also reported to dis-
play antimicrobial activity. There is debate regarding the antimicrobial mechanism of engineered
nanomaterials; however, particle size is reported to influence the effectiveness of engineered nanocar-
bons as antimicrobial agents.
Smaller aggregates of C60 exhibit relatively stronger antibacterial activity and Lyon et al. [129]
reported that the increase in toxicity was disproportionately higher than the associated increase in
putative surface area. Regarding the antibacterial mechanism of C60, photo-induced [130] and non-
photo-induced [131,132] generation of reactive oxygen species by C60 and its derivatives causing
damage such as DNA cleavage [133] and lipid peroxidation [134] have been suggested. Some, how-
ever, argue that photo-induced reactive oxygen species generation does not occur, but rather C60
exerts an oxidative effect (independent of reactive oxygen species) at the membrane interface which
hinders respiration [135,136] and antibacterial activity can occur in the absence of light and/or
oxygen [137].
The exact mechanism for bacterial inactivation in the presence of CNTs is also poorly understood
and subject to debate. Disruption of intracellular metabolic pathways, oxidative stress [138,139]
and physical membrane damage [140] have been discussed as possible mechanisms for CNT toxic-
ity [141]. CNT diameter is a key factor governing the antibacterial effects and single-walled carbon
nanotubes (SWCNTs) are much more toxic to bacterial cells than multi-walled carbon nanotubes
(MWCNTs) (Fig. 7) [141]. Highly purified SWCNTs exhibit strong antimicrobial activity. The likely
mechanism is cell membrane damage resulting from direct contact with SWCNT aggregates [140].
Kang et al. [141] state that the enhanced bacterial toxicity of SWCNTs may be attributed to: (i) a smal-
ler nanotube diameter that facilitates the partitioning and partial penetration of nanotubes into the
cell wall; (ii) a larger surface area for contact and interaction with the cell surface; and/or (iii) unique
chemical and electronic properties conveying greater chemical reactivity. Bactericidal cytotoxicity in-
creases with improvements in physicochemical properties that enhance CNT-cell contact opportuni-
ties [142,143]. For example, CNTs that were uncapped, unbundled, short and well-dispersed
displayed greater toxicity than capped, bundled, longer or less dispersed CNTs [143]. In contrast to
conventional antimicrobials, it is expected that microbes are unlikely to develop resistance against
antimicrobial nanomaterials that physically tear microbe membranes such as CNTs. Microbes develop
resistance against traditional antimicrobial agents by modifying the biochemical pathways targeted
by the drugs; however, it would be difficult for microbes to change the composition of their mem-
branes so that they could prevent physical damage by sharp nanomaterials [144].
Engineered nanocarbons such as CNTs are also being used as supports for the immobilisation of en-
zymes with antimicrobial properties, such as lysostaphin [78], laccase, and chloroperoxidase [145].
Lysostaphin enzymes bind to the cell wall of target bacteria and damage the cells [78]. Laccase and
chloroperoxidase generate, in a controlled manner, I2 and chlorine-containing compounds, respec-
tively. As opposed to the addition of halogens (a class of conventional, broad spectrum antimicrobial
agent which generally requires high concentrations of I2 or Cl2 and poses health and environmental
burdens), controlled enzymatic generation of I2 or chlorine-containing compounds offers a potentially
non-toxic, environmentally friendly alternative to chemical disinfection [145]. Immobilisation of the
enzymes on nanocarbons serves to stabilise the enzymes and prevent their release into the
Fig. 7. SEM images of E. coli cells exposed to CNTs; (a) cells incubated with MWCNTs for 60 min, and, (b) cells incubated with
SWCNTs for 60 min. From [141].
environment [78]. With respect to CNTs, the molecular curvature stabilises a wide range of en-
zymes [146], the high surface area-to-volume ratio enables high loadings without diffusional limita-
tions [147] and the large aspect ratio leads to efficient entanglement within the solid matrix,
thereby allowing enzymes to be retained [78,148].
Paints containing nanocarbon-supported enzymes can be applied to a broad range of surfaces and
make them sterile over extended operational times [145]. Pangule et al. [78] designed a lysostaphin-
MWCNT conjugate that, when incorporated into a paint, was stable during storage for up to 1 month
in dry conditions and was highly efficient at killing MRSA. Grover et al. [145] demonstrated that the
incorporation of laccase-discrete polyethylene glycol-MWCNT or chloroperoxidase-MWCNT conju-
gates into paint resulted in substantial bactericidal and fungicidal activity and the paints were stable
when stored for 1 week in dry form. Using a laccase-discrete polyethylene glycol-MWCNT paint com-
posite, >99.99% of S. aureus and E. coli were killed within 30 and 60 min, respectively, and >90% and
>99% of Bacillus cereus and Bacillus anthracis-DSterne spores were killed within 1 and 2 h, respectively.
No bactericidal activity occurred when using a laccase-free, paint formulation. The chloroperoxidase-
MWCNT paint composite killed >99.99% of bacteria (S. aureus and E. coli) within 30 min compared to
<30% in the additive-free control. The chloroperoxidase-MWCNT paint composite was ineffective in
killing fungal spores.
5. Self-cleaning surfaces
Self-cleaning surfaces have the potential to reduce costs associated with maintaining the clean
appearance of a range of surfaces found in civil infrastructure, including glass surfaces (e.g. glazing,
mirrors, lights), concrete surfaces (e.g. pavements and façades) and tiled surfaces (e.g. façades and
roofs). Self-cleaning surfaces can be classified into two broad categories: superhydrophobic surfaces
and superhydrophilic surfaces.
5.1. Superhydrophobic surfaces
Hydrophobic surfaces are defined as surfaces upon which a water droplet forms a contact angle of
>90°. Superhydrophobic surfaces are a subclass of hydrophobic surfaces upon which water droplets
form contact angles of >150°. Contact angle is defined as the angle between the solid surface and
the tangent line of the liquid phase at the interface of the solid, liquid and gas phases, as illustrated
in Fig. 8. In addition to being superhydrophobic, contact angle hysteresis must also be low
(<5–10° [149]) if the surface is to exhibit self-cleaning properties [150]. Contact angle hysteresis –
the difference between the advancing contact angle and the receding contact angle – represents
how easily a droplet will roll off a film. Superhydrophobicity coupled with low contact hysteresis en-
able self-cleaning because water beads and rolls off, removing dust and dirt as it does so.
The hydrophobicity of a surface is determined by its surface structure and the surface chemistry or
surface energy. There are many hydrophobic surfaces found in nature: some leaves [151–153] (such as
Fig. 8. The contact angle (h) of a hydrophobic and superhydrophobic surface, adapted from [151].
Fig. 9. SEM micrographs of superhydrophobic surfaces found in nature. The hierarchical structure of the surface of a lotus leaf at
(a) low, and, (b) high magnification with (inset) a photograph of the contact angle of water on the lotus leaf surface. The unitary
structure of the underside surface of a ramee leaf at (c) low, and, (d) high magnification with (inset) a photograph of the contact
angle of water on the surface. Adapted from [152].
the leaves of lotus, cabbage, rice, taro, ramee, silver ragwort, and Chinese watermelon plants); the
wings of butterflies [152]; and the legs of water striders [154]. Their surface structure is generally
either ‘‘hierarchical’’, with nanometer-scale features upon micron-scale features, or ‘‘unitary’’, where-
by the surface consists of a mat of micro- or nano-fibres [152] (Fig. 9). Man-made attempts to produce
hydrophobic surfaces are often strongly rooted in biomimicry [155] – the mimicking of hydrophobic
surfaces found in nature – and both hierarchical and unitary style surfaces have been produced. Syn-
thesis of hydrophobic surfaces typically entails either: (i) controlled surface roughening of a low sur-
face energy material to achieve a specified micro and nanostructure; or, (ii) producing surfaces with a
specified microstructure and nanostructure and then modifying the surface chemistry (e.g. with a
material possessing low surface energy) [152]. In both scenarios the superhydrophobicity is ultimately
achieved using a combination of high surface roughness and low surface energy.
As discussed in the review of self-cleaning coatings by Ganesh et al. [152], the surface chemistry of
materials with desirable micro/nanostructures can be chemically modified using a variety of tech-
niques including wet chemical reactions, hydrothermal reactions, electrochemical deposition, lithog-
raphy, self-assembly, layer-by-layer assembly, etching, chemical vapour deposition, sol–gel methods,
and polymerisation reactions. Common low surface energy materials used to produce hydrophobic
surfaces include silicones such as polydimethylsiloxane (PDMS) and fluorocarbons such as polytetra-
fluoroethylene (PTFE or Teflon), although low-density polyethylene, polystyrene, alkylketene, polycar-
bonate, polyamide and others have also been used.
Surface roughness increase surface area, which geometrically enhances hydrophobicity according
to the Wenzel model [156]. Surface roughness also facilitates the entrapment of air at the surface,
which allows water droplets to partially sit on air (air is considered to have a water contact angle
of 180° [157]) thus enhancing hydrophobicity in accordance with the Cassie-Baxter model [158]. Suit-
able surface micro/nanostructures for superhydrophobicity can be created using templates (biologi-
cal [153] or otherwise [159]), surface patterning techniques such as etching [160,161] and casting,
or by depositing nanoparticles on a surface.
Because particle size renders nanoparticles transparent in the visible spectrum, functionalised
nanoparticles have attracted significant attention in the development of transparent superhydropho-
bic coatings for self-cleaning glass [162]. Nanomaterials investigated include inorganic nanoparticles
(and/or nanotubes) such as SiO2 [163–165] and SiC [166], and engineered nanomaterials such as
CNTs [150,157]. The micrometer-scale roughness of superhydrophobic films typically leads to strong
light scattering [164,167]; however, careful placement of nanoparticles simultaneously achieve the
surface roughness required for superhydrophobicity and low contact angle hysteresis, while minimis-
ing light scattering [164]. Dip coating [162], layer-by-layer assembly [164,167] and spray coat-
ing [168] have all been demonstrated as simple and inexpensive techniques for the formation of
SiO2 nanoparticle-based superhydrophobic coatings over large areas.
The low refractive index of SiO2 nanoparticle-based coatings has also lead to anti-reflective prop-
erties when used on glass [164,167]. Bravo et al. [164] performed layer-by-layer deposition of SiO2
nanoparticles on a glass substrate to form superhydrophobic coatings with contact angle hysteresis
as low as <5° and optical transmission levels above 90% throughout most of visible region of the spec-
trum. Also using a layer-by layer technique on a glass substrate, Li et al. [167] formed silica nanopar-
ticle-based films that were initially superhydrophilic, but became superhydrophobic following
treatment using perfluorooctyltriethoxysilane. Transmittance of the perfluorooctyltriethoxysilane-
modified SiO2-coated glass was generally >90%, contact angle hysteresis was <1° and both the trans-
mittance and superhydrophobicity were reported to be stable under ambient conditions for over
2 months.
Dip coating produces a sparser nanoparticle coating than other nanoparticle coating preparation
techniques such as convective assembly [162]. This can result in a greater surface area, as shown in
Fig. 10, and superior hydrophobicity. Glass that was dip coated with unfunctionalised SiO2 nanopar-
ticles, and subsequently fluorinated and sintered, demonstrated superhydrophobicity, almost 100%
transparency in the visible light region and the ability to withstand wear [162].
CNTs are excellent for creating superhydrophobic surfaces. Controlling the density of the CNTs
allows control of surface roughness and the CNTs can be functionalised post-synthesis to obtain the
surface chemistry required [169]. Aligned CNTs can be grown directly on a glass substrate. Bu
Fig. 10. I. A schematic illustration of the larger surface area of the sparser SiO2 nanoparticle layer produced by (a) dip coating
than by (b) convective assembly. II. SEM images of the surfaces of functionalised SiO2 nanoparticle films produced by (a) dip
coating and (b) convective assembly. Higher resolution SEM images and photographs of a water droplet on the respective
surfaces (inset). III. (a) A photograph of the functionalised, SiO2 dip coated glass that demonstrated good transparency and
superhydrophobicity. Adapted from [162].
et al. [169] demonstrated that optical transmittance though a superhydrophobic surface consisting of
post-synthesis functionalised, aligned CNTs grown on a glass substrate can be increased by growing
shorter CNTs. Optical transmittance in the visible region when using the shorter (5 lm) CNTs was,
however, still low (<20%). Tang et al. produced a translucent superhydrophobic surface using a micro-
patterning technique on glass whereby a grid of CNTs were synthesised in 17 17 lm cells with
13 lm free space between cells containing CNTs, thereby forming a grid [170] (Fig. 11-I.a). While
light mainly passes through the free-space, the surface appears uniform with a transparency of
63% due to the 100 lm resolution of the human eye. Images viewed though the surface do, how-
ever, appear blurred at long distances because the micro-pattern array diffracts light (Fig. 11-I.b). Bet-
ter visible light transparency has been observed when using randomly orientated CNTs.
A superhydrophobic coating with a transparency of 79% in the visible light region was formed
with a low cost, one step spray coating method using polymer-functionalised randomly orientated
CNTs (Fig. 11-II) [168]. Han et al. [150] produced a transparent and conductive, hydrophobic film from
a mat of fluorinated silane solution/randomly orientated CNT hybrid film using a spray coating tech-
nique suitable for the treatment of large surface areas. Superior hydrophobicity and transmittance
(>150° and >90%, respectively) were observed with the addition of SiO2 nanoparticles (Fig. 11-III).
Meng et al. [157] used dip coating to produce a transparent, conductive superhydrophobic coating
from a fluorinated, randomly orientated CNT mat on glass. About seven coats proved optimal, achiev-
ing water contact angles of 160° and transmittance of 80% in the visible region.
Fig. 11. I. Micro-patterned CNTs on glass: (a) An SEM image of the surface and, (b) an optical microscope image of the
characters ‘En’ viewed through the micro-patterned CNT/glass surface, adapted from [170]. II. Polymer-functionalised,
randomly orientated CNTs film on glass: (a) an SEM image and, (b) a photograph of water droplets on the transparent,
superhydrophobic film, adapted from [168]. III. CNT/silane hybrid and SiO2 nanoparticle film spray coated glass: (a) an SEM
image and, (b) a photograph of water droplets on the transparent, superhydrophobic film, adapted from [150].
Self-cleaning hydrophobic paints are potentially valuable in the construction industry for the
reduction of costs associated with maintaining building walls and facades. A number of self-cleaning
paints are commercially available e.g. LotusanÒ [171] and Deletum 5000 [172]. Some self-cleaning
paints may also be employed as anti-graffiti paints. Hydrophobic surfaces can also be used to reduce
the accumulation of snow or eliminate the formation of ice on solid surfaces [152,173], which may
find applications on roads and windows in regions with sub-0 °C weather conditions; the anti-icing
effect allows the transparency of glass surfaces to be maintained.
5.2. Superhydrophilic surfaces
Hydrophilic surfaces have a water contact angle of <90° and superhydrophilic surfaces are those
with a contact angle that is close to 0° (Fig. 12). Materials used in hydrophilic surfaces are typically
Fig. 12. The contact angle (h) of a hydrophilic and superhydrophilic surface, adapted from [151].
Fig. 13. The mechanism for photoinduced hydrophilicity of TiO2 by the formation of surface hydroxide groups, from [175].
photocatalytic (e.g. TiO2). Photocatalytically generated h+ oxidise the lattice oxygen at the surface of
the material resulting in oxygen vacancies that can be filled by adsorbed water. This causes the forma-
tion of surface hydroxide groups, which increase the hydrophilicity of the surface, as shown for TiO2 in
Fig. 13. The static contact angle of a TiO2 surface can drop to almost 0° after UV irradiation [174].
Hydrophillic photocatalytic surfaces have a further benefit since they also facilitate the decompo-
sition a broad range of organic pollutants (aromatics, polymers, dyes, surfactants [155]) and many
compounds found in stains on outdoor surfaces when in the presence of oxygen. These stains are typ-
ically composite materials originating from atmospheric pollutants that adhere to surfaces by organic
binders such as hydrocarbons and fatty acids (for example, –COOH carboxylic groups bind with cal-
cium ions present in concrete), but can also trap atmospheric particles and dusts [175]. Self-cleaning
photocatalytic superhydrophilic coatings can also catalyse the degradation of oily substances to assist
removal [176,177]. This is a key benefit over many self-cleaning surfaces based on a hydrophobic ef-
fect since oily contaminants can lead to the loss of hydrophobicity in these [173,177]. The self-clean-
ing mechanism of photocatalytic surfaces are, therefore, twofold: many organic molecules are
decomposed to CO2 and H2O when irradiated with UV light; and, when water contacts the surface
it forms ‘sheets’ and carries away dirt and other contaminants. There is a dual effect whereby the hy-
droxyl groups that form on the surfaces not only contribute to superhydrophilicity, but also to the for-
mation of hydroxyl radicals that play an important role in the decomposition of organic
compounds [175]. It is noteworthy that the adsorption of organic contaminants can cause a photocat-
alytic superhydrophilic surface to become hydrophobic, and therefore sufficient photocatalytic degra-
dation of these contaminants may be a requirement for superhydrophilic properties to be
maintained [175]. By producing a photocatalytic surface with a roughness whereby air can intrude be-
tween the water droplet and the surface, the wettability of the surface (from hydrophobic to superhy-
drophilic) can be controlled by controlling irradiation [100] (Fig. 14). When sufficiently irradiated, the
surface is superhydrophilic due surface hydroxide groups formed as a result of the photocatalytic ef-
fect. When in the dark for a sufficient duration, the surface is hydrophobic (e.g. 120°) in accordance
with the Cassie-Baxter model, since the photocatalytic effect is not present.
TiO2 is well-suited to use in self-cleaning coatings. It is cheap and readily available, non-toxic (as a
bulk material – the toxicity of TiO2 nanoparticles is contended [138]), can be produced in a variety of
morphologies [176,177,179,180], easy to deposit as a thin film, chemically inert in the absence of UV
light and can easily reach the state of superhydrophobicity upon weak solar irradiation in an ambient
atmospheric environment [152,175]. Furthermore, although TiO2 has a high refractive index, even
antireflective self-cleaning coatings – a requirement for applications such as self-cleaning coatings
Fig. 14. A schematic diagram of the effect of UV irradiation on the contact angle of water on photocatalytic surfaces, from [178].
for solar panels – can be produced by supporting the TiO2 nanoparticles on SiO2 particles [181]. Super-
hydrophilicity also imparts anti-fogging characteristics which is useful in many applications where
glass is used. Since a thin film forms rather than droplets, the surfaces naturally dry out quickly
and prevent fogging up when in contact with steam or condensation [151,182].
Due to optical property requirements, the glazing industry typically use deposits of smooth, robust,
nanocrystalline TiO2 films. Nanoparticles also provide a relatively large surface area per unit volume,
which enhances light harvesting, facilitates the diffusion of charge carriers [176] and can be produced
using scalable techniques such as dip coating [183,184]. Transparent and photocatalytic, superhydro-
phobic films have been formed from TiO2 with nanoparticle or nanotube morphologies. Kim
et al. [176] produced a superhydrophilic nanoparticulate TiO2 layer with 60–90% transmittance in
the visible range. Mor et al. [185] and Tan et al. [179] produced aligned TiO2 nanotube based films
with 80–95% transmittance of visible light.
Nanoparticle size and film thickness are of considerable importance not only for transparency but
also for photocatalytic activity. A balance between these must be achieved to maximise superhydro-
philicity based on photocatalytic activity [152,155,186]: the small particles used to achieve large
effective surface areas and optical transparency will also have higher rates of electron–hole recombi-
nation. Thicker films (up to a few microns in thickness) have shown improved photocatalytic activity,
but optical clarity and durability are poor [152,155]. A nanotube TiO2 morphology can offer the ben-
efits of high surfaces area (since there are internal and external surfaces available), and the wall thick-
ness can be tailored to achieve optical transparency while minimising charge carrier recombination
[179]. As such, TiO2 nanotube arrays and even TiO2 nanoparticles demonstrate superior photocatalytic
performance to flat TiO2 surfaces [176,179].
Solution processed nanoparticulate TiO2 coatings are well suited for application to large areas, but
they are generally soft and have low abrasion resistance, which can make them unsuitable for outdoor
use [176]. A number of strategies to improve the abrasion resistance/surface hardness of TiO2 nano-
particle based coatings on glass have been examined. Kim et al.[176] used laser-induced local melting
of TiO2 nanoparticles onto the glass, which improved surface hardness. There was some reduction in
photocatalytic activity stemming from a reduction in particle surface area, but the films were super-
hydrophilic with 60–90% transmission in the visible light region. Yaghoubi et al.[183] achieved max-
imum film hardness using TiO2 nanoparticle on a soda glass surface by annealing at 300 °C. Annealing
causes sintering and chemical attachment of the nanoparticles, improves TiO2 crystallinity and facil-
itates the removal of volatile compounds that can impede photocatalytic activity for the desired pur-
pose. TiO2 films on glass are frequently annealed to a maximum of 500 °C due to the anatase to rutile
phase transition and substrate softening effects at higher temperatures; however, Yaghoubi
et al. [183] found that mechanical deterioration occurred when films were annealed at >300 °C, pos-
sibly due to Na inclusions into the film from the soda glass resulting in low strength Ti–O–Na–O–Ti
bonds at the neck between the grains. Notably, 300 °C is achievable using heat guns or other low cost
techniques and could therefore potentially be done on site, if necessary.
Since the superhydrophilicity of TiO2-based films is photoinduced, the superhydrophilicity of such
films can be unstable under some conditions. For example, the utility of superhydrophilic films is lim-
ited because their performance is gradually lost in the absence of UV light [187]. Superhydrophilicity
independent of UV irradiation can be achieved by tailoring TiO2 morphology and film structure such
that superhydrophilicity is no longer a function of photoactivity but structure. Films that maintained
superhydrophility even after 240 days in the absence of UV light were produced by Pan et al. [187]
from randomly orientated TiO2 nanofibre mats of various morphologies (belts, bead-pierced fibres, fi-
bres with pores) such that liquid not only spreads over the surface but penetrates the mat and diffuses
inside the material (Fig. 15-I). Chen et al. [188] showed that although a flat TiO2 film required UV irra-
diation to induce superhydrophilicity, a film consisting of nanotube arrays of anodic titanium oxide on
a the surface of thin films of anatase TiO2 had a capillary effect and were superhydrophilic even in the
absence of UV light (Fig. 15-II).
5.2.1. Applications of superhydrophilic surfaces

Many self-cleaning products that work on the principle of hydrophilicity have been commercia-
lised for use in construction, with superhydrophillic self-cleaning surfaces available as tiles, glass,
Fig. 15. I. (a) A schematic diagram of the TiO2 nanofibre film wetting process, (b) a TiO2 nanofibre film with a beaded-pierced
fibre morphology, and (c) the 0° contact angle of water and oily substances on the TiO2 nanofibre films regardless of UV
irradiation, adapted from [187]. II. (a) An SEM image of the cross-section of nanotube arrays of anodic titanium oxide on the
surface of a thin film of anatase TiO2, (b) an SEM image of the top view of nanotube arrays of anodic titanium oxide on the
surface of a thin film of anatase TiO2 and, (c) the 0° contact angle of water on film in the absence of UV irradiation, adapted
from [188].
aluminium siding, plastic films, tent materials, cement, etc. [175,182]. Japan, in particular, has adopted
TiO2-based self-cleaning surfaces, with several thousand tall buildings covered in self-cleaning tiles,
widespread use of self-cleaning glass (e.g. 20,000 m2 of self-cleaning glass was used in the Central Ja-
pan International Airport), and self-cleaning tent materials used in bus and train stations, sport cen-
tres, sunshades in parks, etc. [182]. It is estimated that there are over 2000 companies making
photocatalytic products, mainly exterior construction materials, with the internal Japanese market
values at ¥30 billion in 2003 [189]. It is estimated that, in Europe, 1,000,000 m2 of photocatalytic ce-
ment based surface was produced in 2007 [2], and from December 2006 to March 2008 the number of
TiO2-based photocatalytic products (concrete tiles, cement plasters and paints, concrete slabs, etc.) on
the market in Italy increased from 44 to 69 [190].
Self-cleaning glass became available on the consumer market when Pilkington launched Activ™ in
2001 [174]. Many other glass manufacturers (e.g. Cardinal Glass Industries, Saint-Gobain, PPG Indus-
tries) have introduced other self-cleaning glass products since this time [152]. Pilkington Activ™ com-
prises of a hard, thin, transparent, mechanically robust photoactive film of 15 nm thick
nanocrystalline TiO2 that is applied to clear float glass using an online chemical vapour deposition
Fig. 16. (a) The Dives in Misericordia, a church constructed of TiO2-containing self-cleaning cement, and (b) the effect of TiO2 and
its particle size on the photobleaching of mortar surfaces using rhodamine dye as a staining agent from [191].
process [174]. At the time of its introduction, the use of such films was preferable to TiO2 particle-
based films which were not mechanically stable, nor was synthesis highly reproducible [174]. As seen
from the discussed studies, there have continued to be significant improvements in the properties and
preparation methods of films containing TiO2 nanoparticles, nanofibres and nanotubes since this time,
and such films may demonstrate greater activity.
There are limitations to using photocatalytic coatings on transparent organic materials such as
polyvinylchloride (PVC) because, unlike tiles and glass, it cannot withstand the high sintering temper-
atures required to anchor the photocatalytic layer. Additionally, an intermediate layer is required to
separate the photocatalyst from the PVC itself since photogenerated electrons and ‘‘holes’’ may de-
grade the PVC itself [175].
The addition of nanosized TiO2 to mortars and concretes can create self-cleaning mortars/concretes
that maintain their aesthetic characteristics, such as colour, even in harsh urban environ-
ments [175,191]. Structures exploiting these products on exterior surfaces include a school in Mortara,
Italy (completed in 1999), the music and art city hall Cité de la Musique in Chambéry, France (com-
pleted in 2000) and the Dives in Misericordia church in Rome, Italy (completed in 2003;
Fig. 16a) [191]. Long term monitoring shows the photoactive products are performing well. The facade
colour of the Cité de la Musique hall remained almost constant from 2000 to 2005. Only a slight change
in colour was observed during 6 years of monitoring the of the Dives in Misericordia church, and colour
variations from inorganic substances could be completely eliminated by washing with water [175].
The use of TiO2 nanoparticles (rather than larger TiO2 particles) substantially increases the photoac-
tivity of TiO2-containing cements (Fig. 16b) [191].
The market for TiO2 nanoparticle-based self-cleaning products, such as photocatalytic cement addi-
tives, and transparent self-cleaning coatings, are currently considered to be at the market entry stage
of commercialisation. This is expected to develop into a mature market within 3–5 years [104].
6. Air purifying surfaces
A number of directives have been established in recent decades to impose limit values on pollu-
tants such as sulfur oxides (SOx), nitrogen oxides (NOx), particulate matter and lead in ambient air.
Some pollution emission targets are being achieved, while other pollutants, such as NOx, which is gen-
erated during combustion, remain problematic [192–194]. In large cities, pollutant concentrations at
street level are often high because the dispersion of automobile exhaust is hindered by surrounding
tall buildings – the so called street canyon effect [195]. Indoor air pollution from substances including
NOx, carbon oxides (CO and CO2) and volatile organic compounds (VOCs) from combustion, construc-
tion materials and consumer products, is also a health concern. Indoor air pollution levels can exceed
those found outdoors. This is concerning because many modern societies spend long periods of time
indoors, where prolonged exposure to these pollutants have been linked to sick building syn-
drome [196]. Air purifying surfaces in the urban environment have consequently attracted attention.
The EU currently funds the LIGHT2CAT project [197], which aims to develop highly efficient visible
light-activated TiO2 for inclusion in concretes for use across Europe (even in areas with low natural
light intensities) for the improvement of ambient air quality.
Photocatalysts can decompose a broad range of oxides and organic compounds found in indoor and
outdoor environments that can cause or contribute to range of health and environmental issues [192].
The basic decomposition mechanism involves photocatalyst irradiation to generate radicals that sub-
sequently convert pollutants into innocuous compounds [192]. For example, the widely accepted reac-
tion pathway for the photocatalytic conversion of NOx compounds nitric oxide (NO) and nitrogen
dioxide (NO2), is as follows [175,198]. NO diffuses from the environment onto the photocatalyst sur-
face where it is oxidised by photocatalytically generated HO2 or OH (as described in Eqs. (1)–(5)) to
form NO2 (Eqs. (6) and (7)). NO2 (both photocatalytically generated and directly from the atmosphere)
also reacts with photocatalytically generated OH to form nitrate ions (NO 3 ) (Eq. (8)). These are harm-
less in the small quantities that form.
NO þ HO2 ! NO2 þ OH ð6Þ

þ
NO þ OH ! NO2 þ H ð7Þ
NO2 þ OH ! NO3 þ Hþ ð8Þ
The above described reaction pathway and the final, stable products of NOx and those of other
photocatalytically degradable pollutants has been contended by some researches. Langridge
et al. [199] found that photoenhanced uptake of NO2 onto a TiO2-based self-cleaning window was
accompanied by the formation of gaseous nitrous acid (HONO). This is a harmful respiratory irritant
that is readily photolysed by solar irradiation to form OH together with the re-release of NOx as
NO. In contrast, Laufs et al. [200] observed that HONO formed on all paints (not just photocatalytic
ones) in the dark but the photocatalytic paints decomposed the HONO to HNO3 =NO 3 upon irradiation
whereas non-photocatalytic paints did not. Auvinen et al. [201], focusing on photocatalytic degrada-
tion of VOCs, suggested that although the end products of the chain reactions caused by photocatalyt-
ically generated radicals are carbon dioxide and water if complete mineralisation occurs, if complete
mineralisation does not occur, a great number of stable, harmful side products may form. These con-
tradictions demonstrate that further fundamental research on photocatalytic reaction pathways and
their products may be required. As part of EU project CLEAR-UP, Geiss et al. [202] found that photo-
catalyst-containing paints produce particular carbonyls through the photocatalytic breakdown of
paint constituents. These carbonyls may have adverse effects on health and comfort. This must be ta-
ken into consideration in indoor applications in particular, where the replacement rate of air is low.
The development of photocatalytic paints optimised to minimise the emission of harmful substances
has been suggested, particularly where photocatalytic paints are to be used indoors.
Fig. 17. An illustration of the removal of NOx from air by concrete containing photocatalytic particles.
Photocatalysts such as TiO2 can be incorporated into products, for example paints and cements.
These can easily be applied on internal walls and ceilings, external surfaces of buildings (walls and
roofs), roads, public outdoor furniture, footpaths, etc. thereby creating innovative air-purifying sur-
faces in our built environment [192,195]. In photocatalytic cements, the NO 3 formed reacts with cal-
cium in the cement to form calcium nitrate, a water soluble salt that can be removed by rainwater
(Fig. 17). Air pollutants at concentrations of 0.01 ppm to 10 ppm, which correspond to the range from
those in the ordinary environmental atmosphere to those in highway tunnels, can be efficiently re-
moved by such photocatalytic cementitious materials [182].
There are three main application techniques that have been suggested for producing photocatalytic
concrete pavements [203]: (i) application of a thin, photocatalyst-containing cementitious layer
where the photocatalyst is added as a powder or a suspension during cement making; (ii) application
of a photocatalyst-containing solution onto the concrete; or (iii) application by sprinkling the photo-
catalyst onto the fresh concrete. Each application method has advantages and disadvantages. The use
of a coating results in larger proportions of the TiO2 present being irradiated; however, the coated sur-
faces are susceptible to loss of TiO2 from wear [204,205]. Thin cementitious layers can be more dura-
ble, retaining photocatalytic activity after abrasion and wear [206]; however, the photocatalytic
activity of the embedded nano-sized TiO2 is significantly lower than if the TiO2 was applied as a
film [207]. The photocatalytic activity of TiO2 nanoparticles coated on cementitous materials is also
reported to be lower than the same TiO2 nanoparticles in suspension. This is possibly due to (i) the
reduced effective TiO2 surface area, since part of the nanoparticle surface is in contact with cementi-
tious material and hence not available for contact with pollutants; and (ii) the presence of ionic spe-
cies that contribute to charge recombination [208].
P25 by Degussa (Germany), a common TiO2 nanopowder that is used in commercially available
photocatalytic cementitious products [209]. Its excellent photocatalytically activity is attributed to
both the 70:30 mixture of anatase:rutile phase composition and small, 21 nm primary crystal size
[190,210]. As with all catalytic processes, TiO2 particles that are finely divided and well dispersed offer
the highest exposure to the surrounding environment, thereby improving photocatalytic effi-
ciency [211]. In fact, it has been demonstrated that TiO2 particle size can have a greater effect on
NOx degradation rate than the quantity of TiO2 in a cemetitious mortar [198]. However, photocatalyst
particle size cannot be optimised in isolation since the particle size also influences the pore structure
of cementitious materials.
A study of hardened TiO2-containing cement showed that, although both micrometer and nanome-
ter scale TiO2 particles tend to agglomerate, micrometer scale TiO2 particle agglomerates are smaller,
have bigger pores and are better dispersed than TiO2 nanoparticles (Fig. 18) [212]. As a result, active
photocatalytic surface area was dependent also on the size of the molecule to be degraded. For exam-
ple, NOx (which have relatively small dimensions of 100–200 pm) can easily penetrate both micron
and nano-sized TiO2 particle clusters and could therefore utilise the higher specific surface area of
Fig. 18. The structure of hardened cement containing (a) micrometer size TiO2 particles, and, (b) TiO2 nanoparticles, from [212].
nanoparticles to achieve higher rates of decomposition. In contrast, the much larger Rhodamine B
(1.6 nm molecular diameter) cannot utilise the high surface area of nano-sized TiO2 particle clusters
because it is unable to efficiently penetrate into the 8 nm pores. The larger micro TiO2 structures
therefore actually provided a larger effective surface area for the degradation of this particular
molecule.
Pore shrinkage during curing and the accumulation of contaminants, such as oil, dirt and deicing
salt, can see the performance of photocatalytic concrete decrease with time [213]. Relative humidity
also affects the performance of photocatalytic cementitous materials [193,194,198,203]. At very low
relative humidity, the absence of water molecules required for the photocatalytic generation of hydro-
xyl radicals hinders photocatalytic oxidation. Note, however, since pollution concentrations are typi-
cally only in the ppb range, only a very small concentration of hydroxyl radicals (and therefore very
low relative humidity) is required for degradation to proceed [214]. In contrast, at high relative
humidity, water molecules physically block contact of the pollutant with the TiO2 and therefore pol-
lutant degradation does not occur. As a general trend, NOx concentration reduction efficiency reduces
as relative humidity increases in the 10–80% relative humidity range [193,198,203], although Dylla
et al. [194] report that optimum relative humidity is near 25%. The effect of relative humidity on pho-
tocatalytic activity may restrict the geographical locations in which photocatalytic cementitious mate-
rials can be effectively utilised.
Reports regarding the effect of pigments on NOx degradation by photocatalytic cementitous mate-
rials vary. Some report that red pigments can be added to photocatalytic cementitous materials with
negligible influence on NOx degradation capabilities [198]; others report that red, yellow and blue pig-
ments cause NOx degradation to decrease [215]. There are also reports that the addition of metal oxi-
des (Fe2O3, Co3O4 and NiO) to TiO2 can, in fact, improve the adsorption of NOx molecules and their
catalytic degradation [190]. These conflicting data make it impossible to draw conclusions on the ef-
fect of pigment additives on the efficacy of cementitious photocatalytic materials.
There have been several pilot scale trials of photocatalytic cementitous materials on roads and in
model street canyons outdoors. From 2002 to 2005, a number of photocatalytic coatings (both mortars
and paints) were developed and tested in collaborations between research centres and industrial part-
ners as part of the €3.4 million, EU Photocatalytic Innovative Coverings Application for Depollution
Assessment (PICADA) project [216]. A mortar containing 3% TiO2 was spread on panels that were
placed on the walls of a model street canyon (2 m wide, 18.2 m long, 5.2 m high) in France and sub-
jected to a pollution source containing NOx, SO2, CO, CO2, O2, C6H6 and other VOCs [217] (Fig. 19). NOx
Fig. 19. (a) A schematic diagram of the set up for measuring the influence of the TiO2 content of mortar on NOx concentrations
in a model street canyon. Configuration 1 was used during monitoring the effect of TiO2 mortar on NOx concentrations.
Configuration 2 was used as a control, for monitoring the effect of TiO2-free mortar on NOx concentrations. Adapted from [217].
(b) A photograph of the model street canyon, from [216].
levels in the TiO2 mortar-treated model street canyon were 36.7–82% lower than in the equivalent
model street canyon treated with a TiO2-free mortar. In Japan, TiO2 cement coatings have been tested
on roads in more than 14 locations (Fig. 20). A 300 m2 test area on the 7th belt highway in Tokyo
removed 50–60 mg of NOx per day, estimated to correspond to NOx emissions from 1000 automobiles
passing by [182]. In China, a section of concrete road on federal highway G11 at Zhonghe Toll station
was coated with a solution containing TiO2 nanoparticles and activated carbon, which penetrated the
concrete [218]. Sampling was conducted under natural conditions over 3 months, and NO and NO2
degradation rates of >37% and >25.84%, respectively, were reported after artificial wearing of the road
surface.
Photocatalytic pavers have also been tested on roads in Italy, Belgium, England and the Nether-
lands. In Bermago, Italy, 12,000 m2 of treated road showed an average day time NOx reduction of
45% [175]. NOx abatement was demonstrated over a 10,000 m2 parking lane paved with photocatalytic
pavers in Antwerp, Belgium, and after washing with distilled water, the pavers showed no reduction in
photocatalytic efficiency after 2 years [175]. Photocatalytic paving trials in Saville Row, London saw
NOx concentrations drop from 110 ppb to 8 ppb [219]. In the 2009 trial on Castorweg Road (Hengelo,
Fig. 20. A photograph of a roadway with an area (the lighter coloured section of road) coated in a photocatalytic TiO2 material,
from [182].
Netherlands), NOx concentrations 0.5–1.5 m above the road were 25–50% lower over the 1000 m2 of
photocatalytic pavers than over normal pavers [220].
Photocatalytic nanoparticles may also been incorporated into indoor paints [214,221,222], com-
posites [223], wallpapers [224], or suspension sprays [225] for indoor air purification. The widely used
TiO2 nanoparticles, such as P25, are common in these applications [214,221,222]. Because ambient in-
door light may not be sufficient for photoactivity, indoor installations are commonly enhanced with
UV lamps [214,226]. There are also indoor paints containing doped TiO2 nanoparticles that are acti-
vated by the visible spectrum available [227]. Paint substrates face an additional complication over
cementitious materials because the photocatalysts may simultaneously degrade organic and poly-
meric paint constituents in addition to pollutants [201,222,228]. The selection of an appropriate paint
formulation is therefore very important in order to achieve both photocatalytic activity and paint
durability. For example, in a study of the photocatalytic activity of paint containing TiO2 nanoparticles
over the course of 1 year, Pirola et al. [222] found that a siloxane-based paint lost NOx conversion
activity in a regular way down to a fixed value (from >95% to 55%); however, a silicate-based paint
showed a critical loss in photoactivity after about 150 days, losing photocatalytic activity almost en-
tirely. Photocatalytic paint degradation is avoided in regular paints, which contain TiO2 for opacity and
whiteness, by using larger and thus less photoactive particles (see Fig. 21), and using alumina or silica
surface treatments.
Fig. 21. TEM images of, (a) pigmentary TiO2, and, (b) TiO2 nanoparticles from [219].
There are few published studies of photocatalyst-based indoor air purification under unsupple-
mented indoor light levels; however, there are studies of trials in real enclosed environments supple-
mented with UV lamps. Maggos et al. [226] report on the performance of a white acrylic
TiO2-containing paint, developed within the framework of the PICADA project, that was painted on
the 321.9 m2 of ceiling in an artificially closed car park. The closed area was fed with car exhaust gases
and illuminated with UV lamps for 5 h after a steady state was reached. The photocatalytic oxidation
of NOx was approximately 20%. This was less than the 90% reduction achieved with the same paint
under laboratory conditions where temperature, and relative humidity were controlled and other or-
ganic pollutants present in car exhaust (which can have an inhibitory effect) were absent. Neverthe-
less, 20% NOx abatement in a realistic environment is of practical significance. Guerrini from
photocatalytic product provider Italcement Group [229], report significant NOx concentration reduc-
tion after painting a 9000 m2 internal surface of the ‘‘Umberto I’’ tunnel in Rome, Italy with cement-
itous photocatalytic paint as part of tunnel refurbishment. The refurbishment included replacing
existing lighting with UV-A emitting lamps to maximise photocatalyst activation. These two changes
resulted in absolute NOx concentrations in the tunnel falling by >20%. However, a correction for higher
outdoor NOX concentrations during measurements following the refurbishment showed that NOx deg-
radation by the photocatalytic system was 50%. Similar trials have been performed in outdoor envi-
ronments where 300 m2 of wall at a school in London was painted with a silicate-based paint
containing 7.5 wt.% photocatalytic TiO2, which removed 4.5 g of NOx daily [221].
Some TiO2 nanoparticle-based products for air purification are commercially available. The market
is currently considered to be in its infancy, but a mature market is expected to emerge within the next
few years [104].
7. Evaporative cooling for building surfaces
An evaporative cooling system for buildings has been investigated by Irie et al. [230]. A TiO2 film
applied to the external surface of the building cause the building surface to become superhydrophilic
when irradiated by sunlight. Stored rainwater is sprayed onto the surface, where it form a very thin,
continuous film that evaporates to cool the building and local surroundings (Fig. 22). Note that the
Fig. 22. An evaporative cooling system: stored rainwater sprinkled over TiO2 coated building surfaces with evaporation driven
by solar energy, from [100].
cooling effect is not derived from the water itself, but by latent heat flux as water evaporates, so the
surface temperature achieved may be lower than that of the water itself.
The superhydrophilicity of the surfaces means that only a small amount of water is needed to pro-
duce a very thin, continuous film. This high surface area to volume ratio of the water provides the
greatest contact area for evaporative cooling with minimal water use. In fact, on a vertical building
surface with a UV irradiated TiO2 coating, a continuous water layer can form when water film thick-
ness is only 0.1 mm, and a water flow of 200 ml/min is sufficient to cover a 1 5 m wall.
The temperature drops observed depends on the surface material and its colour. Temperature
drops of 15 °C and 40–50 °C on window glass and black roof tile surfaces, respectively, have been re-
ported. Additionally, mold growth, common on damp surfaces, is avoided on such surfaces due to the
antimicrobial effect of the photocatalyst. The use of such surfaces can reduce air conditioner use and
the associated energy consumption, and also reduce heat island phenomena typical in cities and urban
areas.
8. Silica aerogel insulation
In 2005, buildings emitted 8.3 Gt of CO2/yr, accounting for approximately 18% of global greenhouse
gas emissions and 30% of greenhouse gas emissions in many developed countries [231]. Residential
and commercial retrofit insulation has been found to be one of the most cost effective actions for
the abatement of building greenhouse gas emissions [232,233] since up to 75% of residential dwellings
in 2050 have already been built [234]. However, simply increasing the thickness of traditional insula-
tion is often impractical due to increased complexity in building details, decreased net-to-gross floor
area and increased weight of load bearing constructions [235]. A new generation of versatile, efficient,
thin, and lightweight insulation is therefore desirable. The development of optically transparent insu-
lation is a particular focus. Up to 60% of the total energy loss from a building is from its windows [236]
and allowable thermal losses specified in building codes continue to be lowered as governments seek
to save energy and reduce emissions [236]. High performance, translucent insulation is also required
in solar walls and solar collectors; the adoption of which may prove important for countries to reach
their CO2 emission reduction targets [237]. Nanostructured silica aerogels show significant promise as
a suitable material for high performance insulation, even where optical transparency is required.
Silica aerogel consists of a cross-linked internal structure of SiO2 particle chains with a large num-
ber of air-filled pores, typically <100 nm in size depending on the purity and fabrication method
(Fig. 23) [235]. Derived from a gel in which the liquid component of the gel has been replaced with
a gas, the liquid component of the gel was traditionally extracted by supercritical drying. This allows
the liquid to be slowly drawn off without the solid matrix collapsing due to capillary action, as would
occur during conventional evaporation. However, the supercritical drying method does have cost and
safety limitations since high temperatures and pressures are needed to reach the critical point. Safer,
ambient pressure drying methods that utilise low-cost precursors for the production of silica aerogel
have been developed in consideration of commercial requirements [238–240].
Fig. 23. (a) A schematic drawing of the structure of silica aerogel, adapted from [241]. (b and c) SEM images of the structure of
silica aerogels, adapted from [242].
Fig. 24. A comparison of the thermal insulation properties of some commercially available insulation materials (PUR:
polyurethane foam; CFC: chloroflurohydrocarbons; EPS: expanded polystyrene; XPS: extruded polystyrene), from [248] cited
in [240].
Fig. 25. (a) Granular silica aerogel, from [233], and, (b) monolithic silica aerogel, from [250].
Silica aerogels have high compression strength (1.5–3 bar depending on the bulk of silica is 2200 kg/
m3, but the porous structure of silica aerogel results in the density of as low as 3 kg/m3 (just 2.5 times the
bulk density of air at ambient conditions). The density of commercially available aerogels for building
applications is, however, significantly higher, with overall density typically 70–150 kg/m3 [235].
Aerogels are also excellent insulators because they are composed primarily of gas, which is a poor
conductor. Silica aerogels are particularly insulative since the silica matrix itself is also a poor conduc-
tor. Convective heat transfer is also minimal because gas cannot easily circulate through the pore
structure of the aerogel lattice [235]. The thermal conductivity of aerogels can be further reduced
by (i) filling the aerogel with low conductivity gases (generally noble gases); (ii) decreasing the pore
size; or (iii) applying a vacuum to the aerogel [235]. The thermal conductivity of a silica aerogel can be
as low as 0.02 W/(m K) at ambient conditions when the pores contain air and <0.01 W/(m K) under
evacuated conditions (which is lower than a modern wall) [243–246]. Non-translucent silica aerogels
with 0.013 W/(m K) thermal conductivity are commercially available [235,247], and the best com-
mercially available translucent silica aerogel glazing products have 0.3 W/(m K) thermal conductivity
[236]. Fig. 24 shows a comparison of the thermal conductivity of silica aerogel with other commer-
cially available insulation material.
Two different groups of aerogel materials are noted for building applications [235]: (i) granular
aerogel-based translucent insulation materials and (ii) transparent monolithic aerogels (Fig. 25).
Fig. 26. (a) The transmittance of a silica aerogel in the ultraviolet, visible and near infrared spectrum, from [252] cited in [235]],
(b) a diagram of the cross section of translucent granular aerogel glazing, from [253], (c) translucent aerogel insulation as a high
performance thermal insulation solution for daylighting, from [254], and, (d) translucent insulation used as a curtain wall at the
Sculpture Building and Gallery, Yale University, from [255].
Monolithic aerogels generally posses superior thermal and optical properties, but are costly to pro-
duce, require long processing times and must be protected from tension and moisture [237,249].
Granular aerogels consequently dominate the commercial market, despite their inferior performance
because they are more robust and cheaper and easier to produce on a commercial scale [237,241].
Fig. 27. Examples of applications of silica aerogels in the building industry. (a) A passive solar collector concept, from [256].
Thermal insulation is provided by an aerogel layer sandwiched between two panes of glass. The wall of the house is covered
with a black absorptive material that converts the sun’s rays into heat. Because aerogel is a much better insulator than the wall,
most of the heat generated penetrates the wall and enters the house instead of escaping to the outside. In summer a shade could
be drawn over the absorber, (b) a house retrofitted with an aerogel solar collector, from [237], (c) 1 m2 of aerogel-based
rendering applied with 6 cm thickness in a single application, from [233], (d) commercial fibre-reinforced silica aerogel thermal
insulation for building applications, from [257].
Silica aerogels find a variety of applications in the field of civil infrastructure, including heat insu-
lation of buildings – particularly in areas short of space and in areas where optical transparency (e.g.
windows) or translucency (e.g. skylights) is required (Fig. 26)) – translucent heat insulators in solar
collectors, and high performance, insulative building render (Fig. 27). Granular aerogels have also been
noted as exceptional reflectors of sound and form excellent sound barrier materials [235,251]. For
example, Buratti et al. [251] reported that an aluminium framed, double glazed window with granular
aerogel in the 15 mm interspace reduced sound transmittance by 3 dB over a comparable window
with air in the interspace.
Silica aerogels have indeed shown superior performance to conventional glazing in window and
solar collector applications. Burrati et al. [251] reported that, compared to a conventional double
glazed window with a low-emittance layer, a 55% reduction in heat loss (and 25% reduction in light
transmittance) occurred when monolithic aerogel was placed in the interspace. Granular aerogel re-
sulted in a 25% reduction in heat loss and 66% reduction in light transmission, relative to the same
conventional window. Retrofitting of a 10 mm thick prototype panel, consisting of clear twin–wall
polycarbonate sheet filled with granular aerogel, over a single glazed window was found to reduce
heat loss by 80% (the equivalent of a triple glazed window) without detrimental reductions in light
transmission [250].
Dowson et al. [237] simulated and tested the in situ performance of a 5.4 m2 solar air collector con-
taining granular aerogel, which was incorporated into the external insulation of a mechanically
ventilated end terrace house in London, United Kingdom over a 7 day test period (Fig. 27b). Initial test
results for a 10 mm granular aerogel collector showed significant promise; their model predicted
operational efficiencies of up to 60% representing an annual energy output of 355 kW h/m2/yr and a
payback period a low as 4.5 years. Long-term evaluation (2 years) of a 40 mm thick granular aerogel
collector is now being monitored as part of the Retrofit for the Future project in the United
Kingdom [258].
A render containing granular silica aerogel (Fig. 27c) has been shown to have a thermal conductiv-
ity of 0.025 W/(m K) and a water vapour transmission resistance of 4 [233]. These are characteristics
that are unachievable using existing insulative renders.
Aerogel glazing entered the contemporary glazing market in 2006 as a granular aerogel encapsu-
lated between polycarbonate construction panels and weighed less than 20% of the equivalent glass
unit and had 200 times more impact strength [259]. Airglass AB (Sweden) produce transparent mono-
lithic aerogel in a pilot scale production plant [245,260]. Currently, the maximum size of a crack-free
monolithic aerogel tile is 0.58 m 0.58 m, limited by the size of the autoclave [245]. Jelle et al. [236]
present current summary of commercially available optically transparent and translucent silica aero-
gel products in their review of fenestration state-of-the-art. Despite the obvious potential for aerogel
products in glazing applications, commercially available products are limited.
In terms of the aerogel market in general (not just glazing products), the market is quickly devel-
oping. In the 5 years to 2008, the global market for aerogels tripled to $83 million, and is expected to
reach $646 million by 2012[261] cited in [235]], with major producers Aspen Aerogels (USA) [262],
Cabot Corporation (USA) [237,263] and others [236,237] targeting the civil infrastructure industry.
The price sensitivity of the building industry is a major factor affecting the adoption of aerogel
materials. Outside of applications that specifically require the outstanding thermal or acoustic insula-
tion along with the low weight and/or optical transmittance properties that silica aerogel can provide,
the prices of silica aerogel products are currently too high for widespread general adoption to occur.
Research must focus on producing silica aerogels with comparable or superior life-cycle costs to gain
market traction, and even then high capital cost can still be a negating factor where construct only
contracts are concerned. Research must also address the performance gap between laboratory-pro-
duced and commercially available aerogels since at present the thermal conductivity of commercial
aerogel products is about ten times higher than pristine, monolithic aerogels that are made in
laboratories.
9. Solar cells
Photovoltaic devices, such as solar cells, present a comparatively clean and renewable method of
supplying energy. Photovoltaics devices are a multi billion dollar industry that continues to grow,
spurred on by the concern of governments and individuals over fuel supplies and carbon emis-
sions [264]; however, significant advancements continue to be needed to make photovoltaics cost
competitive with established technologies for energy production [265]. Solar energy is only likely to
become truly mainstream when the associated costs are comparable to that of other energy sources.
Nanotechnology is envisaged to play a vital role in progressing towards this. It is estimated that in
2009, approximately 7 GW of photovoltaic solar capacity was installed at a cost of $39 billion, rising
to $82 billion in 2010 [266]. Conservative projections put worldwide annual photovoltaic solar
capacity at 200 GW in 2020 (others estimate as much as 300 GW), and the related estimated potential
market size for nanomaterials is $1.8 billion (in 2020) [266].
First generation solar cells made of bulk (single crystal or polycrystalline) silicon are costly but
have relatively high efficiencies (Fig. 28). First generation solar cells currently make up over 85% of
the global photovoltaic device market [267]. Second generation devices attempt to reduce cost by
using less material (e.g. utilising thin film absorbers or solution-phase deposition processes) without
Fig. 28. The cost of electrical power from photovoltaic systems as a function of the total upfront cost and the module power
conversion efficiency. MC, SP, SIII, SI are the manufacturing cost, average selling price, installed cost for a utility-scale system,
and installed cost for a residential system, respectively. Installed cost for a utility-scale system (SIII) includes ‘‘balance-of-
systems’’ (BOS) cost (which accounts for frames, inverters, battery storage, etc.) for an on-grid system. Installed cost for a
residential system (SI) includes BOS cost for on- and off-grid operation with battery storage. The $/Wp were converted to ¢/
kW h assuming a module lifetime of 20 years, a 5% cost of borrowing, a 1% yearly operating (maintenance) cost, and an average
solar insolation of 200 W/m2 (which is about 5 h of full intensity sunlight/day). Costs are based on 2009 data. The designation of
1st, 2nd, or 3rd generation is based on the manufacturing cost and potential module efficiency. From [267].
compromising efficiency. In theory, the efficiency of second generation devices may match that of first
generation devices (Fig. 28), but in practice the efficiency of second generation devices is often much
lower [267]. Nanotechnology already plays a key role in second generation devices [267], and thin film
technologies account for 6% of the photovoltaics market [264]. Theoretically, third generation solar
cells are efficient beyond that of first and second generation devices and are low cost (Fig. 28) and as
such, greater flexibility and applicability is foreseen for third generation devices. Third generation de-
vices are under development and not yet commercially available. The efficiency and cost of third gen-
eration devices that have been developed are not competitive with that of commercially available
solar cells at present; however, significant research and advancements continue in this area. Nanom-
aterials, such as quantum dots, carbon nanotubes, fullerenes and metal oxides, are likely to play an
important role in third generation devices.
In silicon solar cells, no more than one electron–hole pair is generated per photon absorbed, which
means quantum efficiency is <100%. Combined with other losses, the upper theoretical power conver-
sion efficiency for a non-concentrated cell limit is 33.7% (referred to as the Shockley–Queisser lim-
it) [267]. In practice, the maximum efficiency recorded for the most efficient single junction cells
under AM1.5G1 light is 25% [267]. One strategy being pursued to increase efficiency in third generation
solar devices is the exploitation of nanomaterials that can generate multiple excitons from the absorp-
tion of a single photon. This behaviour has been demonstrated in SWCNTs [269,270] and some quantum-
confined nanocrystals, such as inorganic semiconductor nanocrystals known as quantum dots [267].
These could theoretically achieve a power conversion efficiency conversion efficiency of 44% in a single
junction absorbe under unconcentrated AM1.5G. However the current experimental power conversion
efficiencies of colloidal quantum dot solar cells are about 5% [265,268], significantly lower than the effi-
ciency of commercially available crystalline silicon modules that typically have efficiencies of 12–
19% [267].
1
AM1.5G refers to air mass 1.5 global – a standard spectrum for testing which includes both direct and diffusive radiation and
aims to account for black body radiation from the sun at the earth’s surface to accounting for attenuation by ozone, moisture, dust
and other components in the atmosphere [268].
Fig. 29. A ‘‘solar paint’’ on an optically transparent electrode, from [272].
Despite the continued focus on improving efficiency, it is actually cost that is the major factor in
solar power adoption. As noted by Hillhouse et al. [267], on the free market, it is not necessarily effi-
ciency but rather the cost of the electricity produced that is important. The cost of first generation so-
lar cells continues to decrease, despite the rising cost of polysilicon, and market analysts have
forecasted that first generation solar cell manufacturers may soon achieve manufacturing costs of
$2/Wp.2 Second generation solar cells are now being manufactured at a cost of $0.98/Wp [267]. An in-
stalled cost of $1.6/Wp is required to beat grid-parity prices for large fractions of continental USA [267].
In the long term, as the cost of nanomaterials themselves decrease, the use of nanomaterials in
third generation devices are expected to lower costs relative to silicon-based systems because the
materials can be cheaply processed and applied using established techniques. For example, a solution
of quantum dots can be coated onto a wide variety of conductive substrates using drop casting, spin
coating and ink-jet printing [268]. The size, shape and spatial distribution of nanostructures, as well as
their surface termination and functionalisation with organic ligands can also often be controlled to a
high degree of accuracy and reproducibility [271]. There are also potentially additional technical and
efficiency benefits in using nanomaterials over bulk silicon, such as the ability to tune bandgap and the
absorption spectrum by changing the nanomaterial size, shape and surface termination; excition dis-
sociation without application of an external field; increased device efficiency due to efficient multiple
exciton generation upon absorption of a single high energy photon; a phonon bottleneck that hinders
carrier relaxation thereby potentially increasing open-circuit voltage, and the possibility of sub-band-
gap photon absorption [271]. It is the combination of these control, efficiency, and processing factors
that theoretically enable third generation solar panels to provide energy at high efficiencies and low
cost.
So-called, ‘‘solar paints’’ – pastes that can easily be applied to a conductive surface and, when ex-
posed to light, generate electricity – have also been formed as an alternative to a discrete solar panel
(Fig. 29). A solar paint containing TiO2 nanoparticles coated with CdS and CdSe quantum dots was re-
cently produced and tested by Genovese et al. [272]. Following application of the paste and annealing
at 200 °C, efficiencies of 1% were achieved. This is significantly lower than the highest efficiencies
achieved with other quantum dot solar cells (5%). However, preparation using a paint system is sig-
nificantly simpler, requiring hours rather than the 1–2 days for other quantum dot solar cells, and per-
formance is expected to improve as active particle structural parameters are optimised. Of course,
even with the advent of a solar paint that is efficient, cheap and easy to apply, the need for suitable
device architecture will limit where such paints may be applied. For instance, to function as a device,
an economically viable, suitable conductive surface, methods of attaching electrodes and a suitable
covering will be required.
Nanotechnology is also utilised in solar cell glazing. This is glazing that combines the transparent/
translucent properties of glass and the solar energy harvesting properties of solar cells. This is dis-
cussed in more detail by Jelle et al. [236], but, in brief, the glazing is sprayed with a coating of silicon
nanoparticles that act as solar cells. These products are commercially available from Abakus Solar AG
(Germany), PV Glaze (UK), Sapa Building System (Belgium) and others. It is important to note that
these products have a trade off between visible light transmittance and energy production because
the latter uses the incoming photons. Electrochromic windows actually benefit from this occurrence
because they can maximise energy production when in an opaque state and visible light transmission
2
Dollars per watt peak – a measure that accounts for total upfront cost and module efficiency.
is not required. More advanced nanoparticle-based solar glazing products selectively redirect only UV
and IR light to traditional solar cells located in the window frames are also under development
[273,274].
10. Anticorrosion coatings
The corrosion of materials is reported to cost Western countries approximately 4% of their gross
domestic product, and the corrosion of steel used in construction forms a significant proportion of this
cost [275]. Corrosion prevention strategies often utilise coatings; however, even the best commer-
cially available coatings allow oxygen to slowly diffuse to the metal beneath, causing corrosion and
ultimately, delamination of the coating. Microscopic nicks or pits in the surface also accelerate corro-
sion and delamination due to the formation of redox circuits [276].
Anticorrosion coatings traditionally contained hexavalent chromium compounds. Although very
effective corrosion inhibitors, hexavalent chromium compounds are also toxic carcinogens that can
leach from the coating into the environment. Chromate use has subsequently been banned in many
countries – the EU has banned its use in electrical, electronic and automotive industries in the EU since
2006/2007 [277] – prompting research into other effective anticorrosion coatings. A range of nanopar-
ticles is being explored for use in both passive and active anti-corrosion coatings.
Improvements in corrosion inhibition have been seen when SiO2, Zn, Fe2O3, and halloysite nanoclay
nanoparticles have been added to inorganic (e.g. Ni–W coatings [278]), organic coatings (e.g.
epoxy [279,280]), and intrinsically conductive polymer coatings [281]. Epoxy coatings in particular
are widely used to protect steel reinforcement in concrete structures from corrosion. Significant
improvements in corrosion inhibition have been observed when small quantities of nanoparticles
are well-dispersed in epoxy coatings. The homogeneity of the coatings improve and the porosity of
the coating decreases, as does diffusion (e.g. of O2 and H2O) through the coating [282]. The improved
barrier performance is caused by increased cross-linking, decreased total free volume and the more
compact, hydrophobic polymer network formed [279,280]. The integrity of the coating is enhanced
as the nanoparticles fill cavities, assist in crack bridging, crack deflection and crack bowing [279].
The adherence of the coating to the underlying substrate also improves [279].
Li et al. [280] reported an improvement in the anticorrosion performance of an epoxy coating on
mild steel when 2 wt.% SiO2 nanoparticles were added to the coating. When >2 wt.% SiO2 nanoparticles
was added, the number of pores in the coatings was reported to increase, which had a negative impact
on corrosion inhibition. Shi et al. [279] reported that in 0.3 wt.% and 3 wt.% NaCl solution, corrosion
inhibition with an epoxy coating containing 1 wt.% SiO2, Zn, Fe2O3, or halloysite clay nanoparticles
is, respectively, 638–2365 times and 11–910 times that of epoxy alone. The addition of SiO2 and Zn
nanoparticles also improved the Young’s modulus of the coating by 1000% and 30%, respectively,
although Fe2O3 and halloysite addition resulted in a decrease of 25% and 30%, relative to pure
epoxy.
Active self-healing coatings, produced by adding a corrosion-inhibiting compound that is encapsu-
lated in a ‘nanocontainer’ into a passive protective film, are also in development. In addition to pro-
viding passive corrosion protection, these coatings can rapidly respond to various internal and/or
external corrosion triggers such as mechanical damage and pH changes. These triggers cause the
‘nanocontainers’ in the immediate vicinity to rupture and release corrosion inhibiting agents directly
into the damaged area to nullify the corrosive attack (Fig. 30a). The ‘nanocontainers’ must be less than
300–400 nm in size so that the passive protective properties of the coating are maintained even when
some ‘nanocontainers’ rupture [283]. Because the active materials are only released when triggered,
consumption is minimised and leakage into the environment may be prevented. This system has been
experimentally shown to be more effective than coatings doped directly with corrosion inhibitor
where consumption of the inhibitor occurs continuously (Fig. 30b).
The ‘nanocontainers’ can be formed by a variety of techniques [283], including: (i) the use of self-
organising block copolymers and lipids that can entrap hydrophobic active materials within their
core; (ii) layer-by-layer assembly with polycations, polyanions and nanoparticles as constituents of
the ‘nanocontainer’; and (iii) the use of ultrasonic waves whereby bubble cavitation interfaces are em-
Fig. 30. (a) A schematic diagram of the self-healing effects of a coating containing nanoencapsulated corrosion inhibitor,
adapted from [283]. (b) Photographs of an aluminium alloy coated with; (top) a ZrOx/SiOx sol–gel film directly doped with
benzotriazole after 14 days in 0.005 M NaCl, and, (bottom) a ZrOx/SiOx sol–gel film impregnated with benzotriazole-loaded SiO2
nanocontainers after 14 days in 0.5 M NaCl, from [284].
ployed as reaction zones for the formation of the sensitive shells from organic precursors or preformed
nanoparticles via polycondensation, polymerisation and particle melting. A range of materials have
been explored as prospective nanocontainers for corrosion inhibitors, including mixed-oxide nanopar-
ticles (e.g. ZrO2/CeO2), b-cyclodextrin-inhibitor complexes, hollow polypropylene fibres, conducting
polyaniline, polyelectrolyte layer-by layer coated SiO2 nanoparticles and halloysite clay
nanotubes [283,285].
Information on the required active ingredient loading suggests the concentration of corrosion
inhibitor should lie in the 20 and 97 wt.% range (Patent 6383271 [286]). At <20 wt.%, a sufficient anti-
corrosion effects is not achieved, while at >97 wt.% the polymer material that forms the passive com-
ponent of the coating will not be able to form a continuous matrix [287].
11. Conclusion
The construction industry is generally very conservative, favouring traditional materials and tech-
nologies. However, traditional materials and technologies cannot satisfy the continued drive by gov-
ernments and stakeholders towards the improved safety, sustainability, and performance of buildings
and infrastructure.
Nanotechnology can play an important role in meeting requirements by improving the primary
properties of materials, such as improving the strength of concrete and improving the thermal insu-
lation properties of insulation materials. Nanotechnology can also add new functionalities to existing
materials and products, as illustrated by antimicrobial, self-cleaning and air-purifying paints and opti-
cally transparent insulation.
Nanotechnology can also play a significant role in improving the safety of structures and in reduc-
ing the environmental impact and energy intensity associated with buildings and infrastructure. For
example, metal oxide nanoparticles or CNTs additives can mitigate the adverse effects that ‘environ-
mentally friendly’ industrial waste-based cement replacements can have on the physical properties of
concrete. This increases the range of applications in which these more environmentally friendly
concretes may be used. Nanotechnology-based sensors may supersede traditional visual inspection
methods to improve the accuracy of structural health monitoring and reduce labour costs. Nanotech-
nology based solar cells, paints, and glazing may broaden the range of areas where solar energy
harvesting technology may be applied, and may reduce the cost and improve the efficiency of more
traditional solar cell products. Nanotechnology may also play a role in improving the physical prop-
erties and effectiveness of anticorrosion coatings, and reducing the levels of toxic compounds leaching
from coatings into the surrounding environment.
Nanotechnology-based products and solutions for the construction industry are in various stages of
development, ranging from conceptual ideas to commercially available products. The leap from labo-
ratory-scale successes to a real-world suitability is often a difficult and expensive engineering chal-
lenge. Of those that do reach the commercial market, adoption is often hampered by limited
product awareness within the industry, the conservatism of the construction industry, and the com-
monplace focus on up-front build costs over long-term cost, performance, sustainability and safety.
Nevertheless, it is clear that the construction industry will be compelled to embrace new technologies
in order to deliver the safer, more sustainable, and better performing buildings and infrastructure de-
manded by stakeholders and this will drive continued research into the development of suitable nano-
technologies for the construction industry.
Acknowledgement
The authors wish to acknowledge and thank Dr. Kieran Mackenzie (Engineering Excellence Group,
Laing O’Rourke and School of Chemical and Biomolecular Engineering, University of Sydney) for proof
reading this manuscript.
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Progress in Materials Science 58 (2013) 1056–1102

Contents lists available at SciVerse ScienceDirect

Progress in Materials Science

Nanotechnology innovations for the construction

Article history: A broad range of challenges faced by the construction industry,

AM1.5G air mass 1.5 global;

11. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1094

Nanotechnology refers to the understanding and manipulation of materials on the nanoscale

2.1. Metal oxide nanoparticle additions

2.2. Nanocarbon additions

performance of CNT/concrete and CNT/cement composites is considered a function of the difﬁculties

2.3. Utilisation of industrial waste products

3. Structural health monitoring

(a) Wide stress/strain range of detection (from small strains up to failure).

3.1. Sensing devices

3.2. Self-sensing concrete

Antimicrobial surfaces have applications in a range of infrastructure including in hospitals, child-

4.1. Antimicrobial metal and metal oxide nanoparticles

4.1.1. Photocatalytic antimicrobial nanoparticles

4.1.2. The effect of metal/metal oxide physicochemical properties on antimicrobial activity

4.1.3. Antimicrobial coatings from antimicrobial nanoparticles

4.2. Antimicrobial engineered nanomaterials

5.1. Superhydrophobic surfaces

5.2. Superhydrophilic surfaces

5.2.1. Applications of superhydrophilic surfaces

6. Air purifying surfaces

NO þ HO2 ! NO2 þ OH ð6Þ

7. Evaporative cooling for building surfaces

8. Silica aerogel insulation

Fig. 29. A ‘‘solar paint’’ on an optically transparent electrode, from [272].

10. Anticorrosion coatings

[171] Lotusan. http://www.lotusan.de/ (in German).

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NO þ HO2 ! NO2 þ OH ð6Þ