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How Nanotechnology Can Change the

Concrete World Part Two of a Two-Port Series

Successfully mimicking nature's boffom-up construction


processes is one of the most promising directions.
Konstantin Soboiev nanoscopic phases of materials can be
Facultad de Ingenieria Civil measured.^''
Universidad Autonoma de Nuevo Leon
San Nicolas de los Garza, Mexico
Miguel Ferrada Gutierrez Atomic force microscopy (AFM) has been
Cognoscible Technologies applied to the investigation of the amor-
Santiago, Ct)ile phous C-S-H gel structure.This has led to
the discovery that this product has a highly
general overview of nano- ordered structure at the nanoscale (Fig. 6).^^
technology was present-
ed in part one of this two-
part series {see p i 4 in the Understanding of nanoscale structure
October issue). In this helps to influence important processes
part, potential applications of nanotech- related to production and use of construc-
nology to concrete are presented. tion materials, including strength develop-
ment, fracture, corrosion and tailoring of
desired properties. For instance, the devel-
How Nanotechnoloay Can Change opment of paints and finishing materials
that are self-cleaning, discoloration resist-
Construction Materials ant, antigraffiti protected, high scratch
The majority of recent nanotechnology resistant and wear resistant is extremely
research in construction has focused on important for facade and interior applica-
the structure of cement-based materials tions. Self-cleaning Hydrotect tile, windov^/
and their fracture mechanisms.'''^'^'^^'^^ New glass, and water-based paint have been
advanced equipment makes it possible to developed by TOTO based on photocata-
observe a structure at its atomic level. lyst technology.'^''''The self-cleaning effect
Moreover, the strength, hardness and related to decomposition of organic pollu-
other basic properties of microscopic and tants and gases is achieved when titania

November 2005
GSH crystallized Atomic resolution
2 X 2 pm 20 X 20 nm

Ultrafine fumed silica particles observed


using TEM.^^ Courtesy Andri Vital, EMPA
Mat'ls Testing & Research. Labaratary far
Higbly ordered structure of C-S-H gel (Ca/Si = 0.9} observed at a nonoscale.^^ High-Performance Ceramics, Duebendoif,
Courtesy Eric Lesniewska, Nanosciences Group, Physics lab. University of Bourgogne, France. Switzerland.

photocatalyst thin film is set on a be used as an additive for high-per- tubes) and improved dispersion and
surface to emit active oxygen under formance and self-compacting con- alignment of the individual nano-
ultraviolet light. crete that has improved workability tubes can increase the performance
and strength.^^"" Nanosilica has of composite fibers or decrease the
been proved to be an effective addi- volume of the nanotubes used.''"
Another aspect of self-cleaning is tive to polymers to improve
provided by the hydrophilicity of the strength, flexibility and
surface.This helps to rinse away dust Based on research conducted at the
and dirt. Other examples are related University of Texas-Dallas, Dalton et
to nanometer-thin coatings of con- Kang et al.^^ investigated epoxy al.^^'*' introduced a further break-
ducting polymers that protect car- composites filled with functionalized through related to SWNT-reinforced
bon steel against corrosion"*'^'^^ or nanosilica particles obtained using fibers.The composite fiber compris-
window glass covered with an invisi- the sol-gel process.The synthesized ing 60% of nanotubes and 40% of
ble silver nanolayer to enhance the uniform silica particles were either poly{vinyl alcohol) (PVA) produced
thermal insulation modified by substituting the surface by continuous spinning with a modi-
silanol groups by epoxide ring, amine fied coagulation method achieved
and isocyanate groups or by calcinat- strengths of >1.8 GPa.These fibers
Nanochemistry with Its bottom-up ing the nanosilica to remove surface matched the energy-absorbing
possibilities offers new products that silanol groups. It was found that mod- capacity of spider silk up to the
can be effectively applied in concrete ified particles could chemically bond breaking point of silk at 30% (165
technology. One example is related to epoxy matrix, which resulted in a J/g) and continued to absorb energy
to the development of new super- decrease in the coefficient of thermal until reaching a toughness of 570
plasticizers for concrete, such as poly- expansion (CTE) of the composites. J/g, as compared with 50 and 33 J/g
carboxylic ether (PCE) polymer-based With increased nanosilica content, the for Spectra and Kevlar fibers, respec-
Sky.This product has been developed composites exhibited an additional tively.^^ Application of these new
recently by Degussa.A nanodesign decrease in CTE, an increase in glass super fibers in composite materials is
approach helped to realize the transition temperature and a promising.
extended slump retention of decrease in damping.
concrete mixtures.^''
Concrete with Nanoparticles
The combination of carbon nano-
It has been proposed that nanopar- tubes and conventional polymer- Mechanical properties of cement
ticles can be incorporated into con- based fibers and films is another mortars with nano-iron-oxide and
ventional building materials.They challenge. For example, the incorpo- nanosilica were studied by Li et al.^^
then possess advanced or smart ration of 10% SWNTs into the Experimental results demonstrated
properties required for the construc- strongest artificial fiber, Zylon, results an increase in compressive and flex-
tion of high-rise, long-span or intelli- in a new material with 50% greater ural strengths of mortars that con-
gent civil and infrastructure strength.'*" It is expected that better tained nanoparticles. It was found
systems.'*'^'''^^'^^'^^ For example, silica exfoliation (separation of the bun- that increased nanosilica content
nanoparticles {nanosilica (Fig. 7)) can dles to release the individual nano- improved the strength of the mortars.

American Ceramic Society Bulletin, Vol. 84, No, 11


CONCRETE NANDTECHNOLaGY

Table 1. Effect of Gaia on Performance of l - 2 % o f cementitious materials was The application of Gaia at a dosage
Concrete Mixtures^ used as a viscosity-modifying agent. of 1.3% (by weight, as a dry content)
A constant water/cement ratio {W/Q provides almost a twofold increase
Mixture parameters Plain With Goia of 0.58 was used for all mixtures, and in concrete compressive strength at
Ceinen1tvp6|EN-197) Il/A-P 42.SR tl/AP42.5R a slump flow of 780-800 mm was ages of 7 and 28 d.'^ The early
>fnenl content (kg/m^) 460 460 maintained by adjusting the dosage strength of the concrete with Gaia is
Admixture dosage (%) 1.3
of an acrylic-polymer-based super- 68.2 MPa, which is ~3 times higher
plasticizer.To maintain the specified than that of reference concrete
Air content (%) 2.7 1.1
slump flow, the superplasticizer (Table 1 and Fig. 8).The 28 d com-
Slump (mm)
dosage was increased b y - 0 . 2 1 % per pressive strength of the concrete
Alter 5 min 60 200 each percent of nanosilica used.The made with Gaia demonstrates a clas-
Alter 30 min 25 210 addition of natiosiiica made the con- sical dependence on W/C (Fig. 9)
After 60 min 15 160 crete mixture more cohesive and and, based on the available test data,
After 90 min 140 reduced bleeding and segregation. a single formula is proposed to pre-
Ambient temperature [°C) 20 20 At the same time, the nanosilica had dict the 28 d strength of the investi-
lompressive strength (MPo) little effect on the slump loss meas- gated concretes: f^g - 208.38e-3°s8iiv/c
At I d 11.1 6S.2 ured within the first 30 min. (at R^ = 97%).
At7d 32.7 77.3 Based on the available data, the
At2Ed 45.2 91.7 positive action of the nanoparticles
Although the nanosilica did not
iReferente 35. affect the compressive strength of on the microstructure and properties
the concrete that contained various of cement-based materials can be
Moreover, the strength of the forms of fly-ash, the compressive explained by the following
cement mortars with nanoparticles strength of the concrete that con-
was even higher than the strength of tained ground limestone was slightly •Well-dispersed nanoparticles
mortars with silica fume. SEM study decreased.The best performance
increase the viscosity of the liquid
proved that the nano-iron-oxide and was demonstrated by concrete with
nanosilica particles filled the pores phase, which helps to suspend the
ground fly-ash, 2% nanosilica and
and decreased the content of calcium cement grains and aggregates,
1.5% superplasticizer.This concrete
hydroxide within the hydration prod- had the highest compressive which, in turn, improves the segrega-
ucts. These effects resulted in the strength of 55 MPa at an age of 28 d tion resistance and workability of the
improvement of the mechanical with the desired behavior in the system.
properties of the cement mortars fresh state, i.e., low bleeding, perfect • Nanoparticles fill the voids
with nanopartictes. cohesiveness, better slump flow and between cement grains, which
little slump loss.The investigation results in the immobilization of free
also showed that nanosilica did not water (filler effect).
A laboratory study of high-volume affect concrete
fly-ash high-strength concrete that • Well-dispersed nanoparticles act as
incorporated nanosilica was per- centers of crystallization of cement
formed by Li.''^ investigation of the One of the first commercial hydrates, which accelerates the
hydration process confirmed that the nanoadmixtures for concrete, Gaia, hydration.
pozzolanic activity of fly-ash can be was developed by Ulmen S.A. and • Nanoparticles favor the formation
significantly improved by the applica- Cognoscible Technologies to substi- of small-sized crystals (such as calci-
tion of a nanosilica. It was concluded tute for silica fume at ready-mixed um hydroxide and AF^) and small-
that the use of nanosilica led to concrete facilities certified by ISO sized uniform clusters of C-S-H.
increased early age and ultimate 14001,"Environmental Management
strength of high-volume fly-ash con- Systems."This product is available in • Nanosilica participates in the poz-
crete.The developed concrete with liquid form that facilitates the satis- zolanic reactions, which results in the
nanosilica had a 3 d strength 81% factory distribution of nanosilica par- consumption of calcium hydroxide
higher compared with plain concrete. ticles in concrete.Gaia combines the and formation of an additional C-SH.
The 2-year strength of the developed effects of water reduction and slump • Nanoparticles improve the struc-
concrete was n5.9MPa (higher than increase.^^ According to Ferrada et
the strength of reference portland ture of the aggregate contact zone,
al.,^^ the concrete mixtures with Gaia
cement concrete of ~103.7 MPa). which results in a better bond
exhibit perfect workability without
segregation or bleeding.This makes between aggregates and cement
the design of self-compacting con- paste.
Collepardi et ai.^^'^'' investigated crete an extremely easy task. A • Crack arrest and interlocking effects
low-heat self-compacting concretes slump loss of 30% in 1.5 h at an between the slip planes provided by
with mineral additives (ground lime- ambient temperature of 20°C has nanoparticles improve the toughness,
stone, fly-ash and ground fly-ash). been reported for concrete mixtures shear, tensile strength andflexural
Nanosilica (5-50 nm) at a dosage of that include Gaia (Table 1). strength of cement-based materials.

November 2005
Future Developments
91.7
Much progress in concrete science is
to be expected in coming years by
the adaptation of new knowledge
generated by a quickly growing field
of nanotechnology.The develop-
ment of the following concrete-relat-
ed nanoproducts can be anticipated:
• Catalysts for the low-temperature
synthesis of clinker and accelerated
hydration of conventional cements;
• Grinding aids for superfine grinding
and mechanochemical activation of
cements;
• Binders reinforced with nanoparti-
cles, nanorods, nanotubes (including
SWNTs), nanodampers, nanonets or
nanosprings; 28

• Binders with enhanced/nanoengi-


neered internal bond between the Strength development of concrete with Gaia.
hydration products;
• Binders modified by nanosized
polymer particles, their emulsions or and chemical admixtures; these systems, portland cement
polymeric nanofilms; • Materials with self-cleaning/air- component is used at its standard
• Biomaterials (including those imi- purifying features based on photo- dispersion to provide the integrity of
tating the structure and behavior of catalyst technology; composition. In contrast to DSP and
mollusk shells); MMCB, the nanobinder can be
• Materials with controlled electrical designed with a nanodispersed
• Cement-based composites rein- conductivity, deformative properties, cement component applied to fill
forced with new fibers that contain nonshrinking and low thermal the gaps between the particles of
nanotubes as well as with fibers cov- expansion; and mineral additives (including FGMA).
ered by nanolayers (to enhance the • Smart materials, such as tempera-
bond and corrosion resistance or to ture-, moisture- and stress-sensing or
introduce new properties, such as responding materials. In the nanobinder, the mineral addi-
electrical conductivity); tives (optionally, finely ground),
• Next-generation superplastlcizers which act as the main component,
Mechanochemistry and nanocata-
for total workability control and provide the structural stability of the
lysts could change the face of the
supreme water reduction; system.The microsized or nanosized
modern cement industry by the cementitious component (which also
• Cement-based materials with great decrease of clinkering temper- can contain the nanosized particles
supreme strength, ductility and ature and even realizing the possibil- other than portland cement) acts as
toughness; ity of cold sintering of clinker miner- a glue to bind less-reactive particles
• Binders with controlled internal als in mechanochemical reactors. of mineral additives together. Such
moisture supply to avoid/decrease Nanobinder can be proposed as a nanosized cementitous component
microcracking; logical extension of two concepts: can be obtained by the colloidal
densified system with ultrafine parti- milling of a conventional (or specially
• Cement-based materials with engi- cles (DSP)''^ and modified multicom- sintered/high C^S) portland cement
neered nanostructures and ponent binder (MMCB)""'^^ down to clinker (the top-down approach) or
microstructures that exhibit supreme the nanolevel (Fig. 10). by self-assembly, which uses
durability; mechanochemically induced
• Ecobinders modified by nanoparti- topochemical reactions (the bottom-
cles and produced with substantially In these systems, the densification up approach).
decreased volume of portland of binder is achieved with the help
cement component (down to of ultrafine particles: silica fume (SF)
10-15%) or binders based on the dispersed with superplasticizer (SP) Editor's Note
alternative systems (magnesia, phos- in DSP and finely ground mineral
phate, geopolymers and gypsum); The references as well as Figs. 9 and 10
additives (FGMA) and SF modified by can be found as part of the online
• Self-healing materials and repair SP in MMCB.These particles fill the version of the article at
technologies that use nanotubes gaps between cement grains. In www.ceramicbulletin.org.

American Ceramic Society Bulletin, Vol. 84, No. 11

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