GLA UNIVERSITY MATHURA

CIVIL ENGINEERING DEPARTMENT

NANO CONCRETE

NAME – MUKUL SRIVASTAVA

ROLL NO – 131000138 (36)
YEAR - III

DATE OF SUBMISSION

25/April/2016
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ACKNOWLEDGEMENT

Working on this project on “NANO CONCRETE” was a source of immense knowledge to me. I
would like to express my sincere gratitude to Mohit Kumar Sharma Faculty of Department for
the inspiration received from him and other faculty members and my colleagues. I would also
like to thank our parents for their love and support.

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TABLE OF CONTENT

1. ABSTRACT ……………………………………………………………………………….7
2. INTRODUCTION………………………………………………………………………….7
3. NANO CONCRETE………………………………………………………………………..8
a. WHY NANOTECHNOLOGY FOR CONCRETE? ....................................................9
b. BENEFITS OF NANO CONCRETE……………………………………………........9
4. STATE-OF-THE-ART……………………………………………………………………..9
a. CEMENT HYDRATION KINETICS CONCRETE AND NANOTECHNOLOGY...9
b. CEMENT REACTIVITY NANO STRUCTURE…………………………………….10
c. NANOSCALE SILICA FUME FOR IMPROVING CONCRETE PERFORMANCE11
d. ALKALI-SILICATE REACTION (ASR) STUDIES………………………………..11
e. FLY ASH REACTIVITY CHARACTERIZATION………………………………...11
f. SYNTHESIS OF CEMENT USING NANO-PARTICLES………………………….11
5. NANO MATERIALS……………………………………………………………………...12
a. CARBON NANO TUBES…………………………………………………………...12
i. Single Walled CNT and its Dimension…………………………………………….13
b. PROPERTIES………………………………………………………………………..13
i. CNTs Electrical Conductivity……………………………………………………....13
ii. CNTs Strength and Elasticity………………………………………………………13
iii. CNTs Thermal Conductivity and Expansion………………………………………13
6. NANO SILICA……………………………………………………………………………14
a. PROPERTIES……………………………………………………………………….15
i. Physical and Chemical Properties…………………………………………………15
ii. Fresh Properties…………………………………………………………………………...15
iii. Mechanical Properties…………………………………………………………….15
iv. Durability properties………………………………………………………………15
7. APPLICATIONS…………………………………………………………………………16
8. POLYCARBOXYLATES……………………………………………………………….17
a. Functions……………………………………………………………………………17
b. Chemical structure………………………………………………………………….18
c. Working mechanisms………………………………………………………………18
9. SOME OPPORTUNITIES AND CHALLENGES……………………………………..19
a. Cement composites…………………………………………………………………19
b. Future Directions…………………………………………………………………..19
10. CONCLUSION…………………………………………………………………………19
11. REFERENCES…………………………………………………………………………21

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LIST OF FIGURES

S.NO NAME OF THE FIGURE FIGURE NO. PAGE NO

1 The top down and bottom up approaches in Nano 1 8
technology
2 Scale of Various Constituents & a Typical Applications 2 10
3 Details of Hydrating cement Grain at Nano scale 3 10
4 Diagram of Carbon Nano Tubes 4 12
5 Nano Silica 5 14
6 Microscopic Image of Nano Silica 6 14
7 Comparison of the concrete density with or without silica 7 16
8 Molecular Diagram of Polycarboxylate 8 18

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LIST OF TABLES

S NO. NAME OF THE TABLE TABLE NO. PAGE NO.

1 Physical and chemical Properties of Nano 1 15
Silica
2 Mix Design of Concrete 2 17

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ABSTRACT

Everything on Earth is made up of atoms—the food we eat, the clothes we wear, the buildings
and houses we live in, and our own bodies. Nanotechnology is an emerging field of science
related to the understanding and control of matter at the Nano scale, i.e., at dimensions between
approximately 1 and 100 nm. Nano-technology is one of the most active research areas which
has wide applications in almost all the fields like electronics, bio-mechanics, coatings, civil
engineering and construction materials. Nanoscale particles are not new in either nature or
science. Matter can exhibit unusual physical, chemical, and biological properties at the
Nanoscale, differing in important ways from the properties of bulk materials and single atoms or
molecules. They may become more chemically reactive or reflect light better or change color as
their size or structure is altered.

INTRODUCTION

Of particular relevance for concrete is the greatly increased surface area of particles at the Nano
scale. As the surface area per mass of a material increases, a greater amount of the material can
come into contact with surrounding materials, thus affecting reactivity.

If cement with Nano-size particles can be manufactured and processed, it will open up a large
number of opportunities in the fields of ceramics, high strength composites and electronic
applications. This will elevate the status of Portland cement to a high tech material in addition to
its current status of the most widely used construction material. Very few inorganic cementing
materials can match the capabilities of Portland cement in terms of cost and availability.

Currently, the most active research areas dealing with cement and concrete are: understanding of
the hydration of cement particle sand the use of Nano-size ingredients such as alumina and silica
particles.

Nanotechnology considers two main approaches:

(a) the ‘‘top down” approach in which larger structures are reduced in size to the Nanoscale
while maintaining their original properties without atomic-level control (e.g., miniaturization in
the domain of electronics) or deconstructed from larger structures into their smaller composite
parts and

(b) The ‘‘bottom-up” approach, also called ‘‘molecular nanotechnology” or ‘‘molecular

manufacturing” in which materials are engineered from atoms or molecular components through
a process of assembly or self-assembly (Figure 1).

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Thus the basic concept behind Nano modification of materials is that of bottom-up engineering,
starting with engineered modifications to the molecular structure with an aim to affect the bulk
properties of the material. Conceptually, this is simply an imitation of nature. In practice, the
introduction of nanotechnology represents a revolution that is allowing for the development of
high-performance and long-lasting products and processes within an ideal context of sustainable
development.

NANO CONCRETE

Nano-concrete is defined as a concrete made with Portland cement particles that are less than
500 Nano-meters as the cementing agent. Currently cement particle sizes range from a few
Nano-meters to a maximum of about100 micro meters. In the case of micro-cement the average
particle size is reduced to 5 micrometers. An order of magnitude reduction is needed to produce
Nano-cement.

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WHY NANOTECHNOLOGY FOR CONCRETE?

1) Development of high-performance cement and concrete materials as measured by their

mechanical and durability properties;
2) Development of sustainable concrete materials and structures through engineering for
different adverse environments, reducing energy consumption during cement production,
and enhancing safety;
3) Development of intelligent concrete materials through the integration of nanotechnology-
based self-sensing and self-powered materials and cyber infrastructure technologies;
4) Development of novel concrete materials through nanotechnology-based innovative
processing of cement and cement paste; and
5) Development of fundamental multi scale model(s) for concrete through advanced
characterization and modeling of concrete at the Nano-, micro- and macro scales.
6) Improves the material’s bulk properties.
7) Ability to control or manipulate materials at the atomic scale.
8) To obtain thinner final products and faster setting time.
9) Cost effectiveness.
10) Lowered levels of environmental contamination.

BENEFITS OF NANO CONCRETE

1) Concrete is stronger, lighter and more durable.

2) Concrete with good workability.
3) Lower cost per building site.
4) Cessation of contamination caused by micro silica solid particles.
5) Concrete with high initial and final compressive and tensile strengths.
6) Cessation of super plasticizing utilization.
7) Cessation of silicosis risk.

STATE-OF-THE-ART

CONCRETE AND NANOTECHNOLOGY

One can claim that concrete utilizes nanotechnology because it contains Nano-particles as
ingredients including Nano-water particles and Nano-air voids. However, to claim the use of
nanotechnology, we should be able to control the amount and the locations of these Nano-
ingredients inside the final products. The scales of various constituent materials of concrete are
shown in Fig. 1. If we can create chemical or mechanical tools to control Nano-scale pores and
the placement of calcium-silicate hydration products then concrete becomes a product of
nanotechnology.

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Current research activities of nanotechnology in concrete include: characterization of cement

hydration, influence of the addition of Nano-size silica to concrete, synthesis of cement using
Nano-particles and coatings (that contain Nano-size particles) applied to protect concrete. These
activities are briefly described in the following sections.

CEMENT REACTIVITY NANO STRUCTURE

A collaborative research activity supported by Federal Highway Administration (FHWA) and

NSF is being conducted at University of Connecticut to study cement hydration at a Nano-scale
level. In this study US and German scientists are using nuclear resonance reaction analysis
(NRRA) to investigate what takes place on the surface of the cement particle as it hydrates. A
beam of nitrogen atoms is used to probe a reacting cement grain to locate hydrogen atoms, a
necessary component of water, or reaction by-products. Location of these hydrogen atoms are
used to create a hydrogen depth profile, which shows the rate of water penetration as well as the
arrangement of various surface layers formed during the reaction. The researchers identified four
components that are active during cement hydration, Fig.2. The following section provides a
short summary of their observations. The 20-nanometer-thick semi-permeable surface layer
allows water to enter the cement grain and leaches out calcium ions. The larger silicate ions in
the cement are trapped behind this layer. As the reaction continues, a silicate gel forms there,
causing swelling within the cement grain. This leads to eventual breakdown of the outermost
layer. The surface disintegration then releases accumulated silicate into the surrounding solution.
The silicate reacts with calcium ions to form a calcium-silicate hydrate gel, which binds cement
grains together and sets the concrete. The evolution of the hydrogen profile shows the timing of
the surface layer's breakdown. This information can be used to study the concrete setting process

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as a function of time, temperature, cement chemistry, and other factors. For example, researchers
used NRRA to determine that in cement hydrating at 30°C (86°F); the breakdown occurs at 1.5
hours.

NANO-SCALE SILICA FUME FOR IMPROVING CONCRETE PERFORMANCE

Ultra-fine amorphous colloidal silica was found to be much more efficient than micron sized
silica for improving the performance such as permeability, and subsequently, durability. In
addition, reduced amount of about 15 to 20 kg of Nano-silica was found to provide same strength
as 60 kg of regular or micro silica.

ALKALI-SILICATE REACTION (ASR) STUDIES

ASR results in the formation of alkali/silica gel, which expands and causes significant material
damage. The gel is formed due to the reaction between cement alkalis and a reactive form of
silica from aggregates or supplementary additions. FHWA researchers are using neutron
scattering and positron annihilation spectroscopy to measure Nano-scale changes in gel
microstructure as a function of gel chemistry, temperature and relative humidity.

FLY ASH REACTIVITY CHARACTERIZATION

FHWA is also funding a research study to examine interactions between fly ash and Portland
cement gel Nano-structure. Small-angle neutron scattering is being used to quantify the changes
on a Nano-scale as a function of time and fly ash composition.

CEMENT HYDRATION KINETICS

Conventional analytical methods are unable to provide an accurate model for the rate of cement's
reaction with water as a function of temperature, water/cement ratio, and grain size because the
reactions occur in the Nano-scale pores of the cement gel. Therefore, scientists from National
Institute for Standards & Technology's (NIST) Center for Cold Neutron Research and FHWA are
using neutron scattering methods to measure motions and reactions of water at a Nano-scale.
This study is expected to explain the effects of various factors on the rate of development of
cement's fractal Nano-scale structure.

SYNTHESIS OF CEMENT USING NANO-PARTICLES

In a project supported by National Science Foundation, it has been synthesized the components
of Portland cement Type I using Nano-particles and compared their properties with that of
commercial cement. Conglomerated Nano-particles with crystalline structures containing
quantities of tri- and di-calcium silicate compounds as well as copper oxide were found to be
present in the synthesized cement. Hydration tests indicated that the Nano-cement had a more
rapid hydration rate than Portland cement Types I(general purpose) and III(High early strength.
Compressive strength of the cement synthesized using Nano-particles was found to be less than
that of ordinary Portland cement.
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NANO MATERIALS

CARBON NANO TUBES

1. Nano tubes are the members of the fullerene structural family. They align themselves into
“ropes” held together by van der Waals forces.
2. Carbon nanotubes are molecular-scale tubes of graphitic carbon with outstanding properties.
3. They can be several millimeters in length and they can have one “layer” or wall (single
walled Nanotube) or more than one wall (multi walled Nanotube).

The addition of Nano fine particles can improve the properties of concrete due to the effect
increased surface area has on reactivity and through filling the Nano pores of the cement paste.
Nano silica and Nano titanium dioxide are probably the most reported additives used in Nano
modified concrete. Nanomaterial’s can improve the compressive strength and ductility of
concrete. Carbon Nanotubes or Nano fibers (CNT-CNF) have also been used to modify strength,
modulus and ductility of concretes. CNFs can act as bridges across voids and cracks that ensure

SINGLE WALLED CARBON NANO TUBES MULTI WALLED CARBON NANO TUBE

load transfer in tension. Durability of concretes can also be improved through reduced
permeability and improved shrinkage properties. These effects can be accomplished through
Nano modified cements or the use of Nano developed additives to the paste.

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Single Walled CNT and its Dimension

Single layer Nano-tube can be considered as the perfect thin walled cylinder because of the
uniformity in thickness, accurate geometry and linear elastic material behavior. The challenge is
to test them to obtain strength, stiffness and stability properties. A number of techniques are
being developed to use electro-mechanical devices to induce force and measure responses. The
forces are measured in Nano Newton’s and the displacements are measured in fractions of Nano
meters.

Transmission electron microscopy studies indicate that these tubes look like nested shells with an
interlayer spacing of about 0.34 nm. The equivalent diameter of the tubes is in the range of 10 to
50nm. The typical length varies from 100 to 1000nm. Single layer tube has a much smaller
diameter (1 to 3 nm) and length (about 300 nm).

PROPERTIES

CNTs Electrical Conductivity

There has been considerable practical interest in the conductivity of CNTs. CNTs with particular
combinations of N and M (structural parameters indicating how much the Nanotube is twisted)
can be highly conducting, and hence can be said to be metallic. Their conductivity has been
shown to be a function of their chirality (degree of twist), as well as their diameter. CNTs can be
either metallic or semi-conducting in their electrical behavior.

The conductivity and resistivity of ropes of SWNTs has been measured by placing electrodes at
different parts of the CNTs. The resistivity of the SWNT ropes was in the order of 10–4 ohm-cm
at 27°C. This means that SWNT ropes are the most conductive carbon fibers known. The
current density that was possible to achieve was 107 A/cm2.

CNTs Strength and Elasticity

The carbon atoms of a single (graphene) sheet of graphite form a planar honeycomb lattice, in
which each atom is connected via a strong chemical bond to three neighboring atoms. Because of
these strong bonds, the basal-plane elastic modulus of graphite is one of the largest of any known
material. For this reason, CNTs are expected to be the ultimate high-strength fibers. SWNTs are
stiffer than steel, and are very resistant to damage from physical forces. Pressing on the tip of a
Nanotube will cause it to bend, but without damage to the tip. When the force is removed, the
tip returns to its original state.

CNTs Thermal Conductivity and Expansion

New research from the University of Pennsylvania indicates that CNTs may be the best heat-
conducting material man has ever known. Ultra-small SWNTs have even been shown to exhibit
superconductivity below 20oK. Research suggests that these exotic strands, already heralded for
their unparalleled strength and unique ability to adopt the electrical properties of either
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Semiconductors or perfect metals, may someday also find applications as miniature heat conduits
in a host of devices and materials. The strong in-plane graphitic C-C bonds make them
exceptionally strong and stiff against axial strains.

NANO SILICA

Is the first Nano product that replaced the micro silica. The Nano silica powder is one of the
blended material. Studies have shown the existence of silica powder, in the early cement
hydration product Ca (OH) 2 content along with the growth of the age becoming less and less,
even complete reacted, generate new material which will jam channel, big pores will less,
cohesion between aggregate and plaster will be strengthen, compactness will be improved.

Advancement made by the study of concrete at Nano scale have proved Nano silica much better
than silica used in conventional concrete, but engineering experience shows that as with silicon
powder, also bring two problems, on the one hand is the cohesiveness increase of concrete to
construction cause certain difficult, on the other hand is shrinkage rate increases can lead early
crack.

NANO SILICA MICROSCOPIC IMAGE OF NANO SILICA

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PROPERTIES

Physical and Chemical Properties

Physical and Chemical Characteristics Unit Value

BET-surface area m2/g 170 – 230

pH, in 4% aqueous dispersion 3.8 – 4.3

Tamped density g/l ca. 40

Loss on drying (2 h at 105 C) % < 1.5

Sieve residue, acc. to Mocker >40 m % < 0.04

Fresh Properties

Reduced setting times were observed by various researchers on incorporation of Nano-silica in concrete
which is same as observed for pastes and mortar. Also, decrease in initial and final setting time was
observed on incorporation of nS in various quantities, with increase in viscosity and yield stress reported.

Mechanical Properties

Concrete strength is influenced by lots of factors like concrete ingredients, age, ratio of water to
cement materials, etc. Nano-silica incorporation into concrete resulted in higher compressive
strength than that of normal concrete to a considerable level. Li et al. (2004) reported 3-day
compressive strength increase by 81% and also at later stages, same trend was observed with 4%
Nano-silica in high volume fly ash concrete. Naji Givi, Abdul Rashid, Aziz, and Salleh (2010)
also reported higher compressive strength at all ages, for Nano-silica blended concretes up to
maximum limit of 2% with average particle size of 15 and 80 nm. Same results were obtained for
split tensile and flexural strength. An increase of about 23–38% and 7–14% at 7 days and 28
days, respectively, in compressive strength of Nano-silica concrete was reported, whereas low
increase of 9.4% (average) was reported for flexural strength.

Durability properties

Durability properties of concrete include aspects such as permeability, pore structure and particle
size distribution, resistance to chloride penetration, etc. Investigations on Nano-silica concrete

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for its permeability characteristics showed that the addition of Nano-silica in concrete resulted in
reduction in water absorption, capillary absorption, rate of water absorption, and coefficient of
water absorption and water permeability than normal concrete. The pore structure determines the
transport properties of cement paste, such as permeability and ion migration. Reduction in water
absorption, capillary absorption, rate of water absorption and water permeability has been
observed by various researchers (Li, 2004; Zhang & Li, 2011; Zhang et al., 2012).

APPLICATIONS

1. High compressive strength concretes.

2. High workability with reduced water/content ratio.
3. Use of super plasticizing additives is unnecessary.
4. Fills up all the micro pores and micro spaces.
5. Cement saving up to 35-40%.
6. As an additive for rubber and plastics
7. As a strengthening filler for concrete and other construction composites

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POLYCARBOXYLATES

Polycarboxylates or polymer based concrete admixtures are high range water reducing admixture
(HRWR) without affecting workability. Superplasticizers, also known as high range water
reducers, are chemical admixtures used where well-dispersed particle suspension is required.
These polymers are used as dispersants to avoid particle segregation (gravel, coarse and fine
sands), and to improve the flow characteristics (rheology) of suspensions such as in concrete
applications.

Functions

Their addition to concrete or mortar allows the reduction of the water to cement ratio, not
affecting the workability of the mixture, and enables the production of self-consolidating
concrete and high performance concrete. The strength of concrete increases when the water to
cement ratio decreases.

High range water reducing (HRWRA) / superplasticizing admixtures are synthetic, water-soluble
organic chemicals, usually polymers, which significantly reduce the amount of water required to
achieve a given consistency in plastic concrete. This effect can be utilized in two ways:

1. To reduce water content to achieve increased strength and reduced permeability/improved

durability.
2. To achieve increased workability at the same water content.

With a slightly higher admixture dosage, both these effects can often be achieved in the mix.
When high range water reducing admixtures are used to increase the workability or consistency
of the concrete they are usually termed 'Superplasticizing admixtures' but these names are
frequently interchanged.

High range water reducing admixtures function in a similar way to 'Normal Water Reducing
Admixtures' but are more powerful in their cement dispersing action and can be used at higher
dose without unwanted side effects such as air entrainment or retardation of set.
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Chemical structure

PCEs (Polycarboxylate ether superplasticizer) are composed by a methoxy-polyethylene glycol

copolymer (side chain) grafted with methacrylic acid copolymer (main chain). The carboxylate
group -COO-Na+ dissociates in water, providing a negative charge along the PCE backbone. The
polyethylene oxide (PEO or MPEG) group affords a not uniform distribution of electron cloud,
which gives a chemical polarity to the side chains. The number and the length of side chains are
flexible parameters that are easy to change. When the side chains have a huge amount of EO
units, they lower with their high molar mass the charge density of the polymer, which enables
poor performances on cement suspensions. To have both parameters on the same time, long side
chain and high charge density, one can keep the number of main-chain-units much higher than
the number of side-chain-units.

Working mechanisms

PCE's backbone, which is negatively charged, permits the adsorption on the positively charged colloidal
particles. As a consequence of PCE adsorption, the zeta potential of the suspended particles changes, due
to the adsorption of the COO- groups on the colloid surface. This displacement of the polymer on the
particle surface ensures to the side chains the possibility to exert repulsion forces, which disperse the
particles of the suspension and avoid friction. These forces can be directly detected by the use of the
atomic force microscopy (AFM), working with model substances in liquid environment.

MOLECULAR DIAGRAM OF POLYCABOXYLATE

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SOME OPPORTUNITIES AND CHALLENGES

Cement composites

If Portland cement can be formulated with Nano-size cement particles, it will open up a large
number of opportunities. For example, the cement can be used as an inorganic adhesive with
carbon fibers. Currently the micron size cement particles are not conducive for use with 7 micron
diameter carbon fibers. The cement will not only be more economical than organic polymers but
also will be fire resistant. In addition it will not emit any volatile organic compounds (voc) and
the composites can be attached to parent concrete substrate using a compatible adhesive. It will
be also very competitive with current inorganic composites because they have to be processed at
high temperature.

A number of investigations have been carried out for developing smart concrete using carbon
fibers. This will become a reality with Nano-cement because Nano-carbon tubes are much more
effective than carbon fibers. The thickness of the composite can be reduced to microns and hence
flexible and smart cement composite can be manufactured.

The primary challenge is to manufacture Nano-size cement particles. Chemical vapor deposition
shows promise. Other avenue is high tech grinding. The second challenge is the heat of
hydration. Special organic and inorganic additives need to be developed to control the setting
and heat of hydration. Even though this is a risky and tough venture, the authors believe that the
risk is worth taking.

Future Directions

Some of the potential areas of applications of Nano-based products as well as future direction are
listed below:

1. Engineered materials using nanotechnology that will allow maximum use of locally
available materials and avoid unnecessary transport. Design ductile, flexible, breathable,
permeable, or impermeable concrete properties on demand.
2. Design concrete mix that is resistance to freeze–thaw, corrosion, sulfate, ASR, and other
environmental attacks.
3. Develop specialty products such as products with blast resistance and conductive properties
as well as temperature-, moisture-, and stress-sensing abilities.

CONCLUSION

Large amounts of funds and effort are being utilized to develop nanotechnology. Even though
cement and concrete may constitute only a small part of this overall effort, research in this area
could pay enormous dividends in the areas of technological breakthroughs and economic
benefits.

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Current efforts are focused on understanding cement particle hydration, Nano-size silica and
sensors. Unique opportunity exists for the development of Nano-cement that can lead to major
long standing contributions.

1. Well dispersed Nano particles increase the viscosity of the liquid phase, improves the
segregation resistance and workability of the system.
2. Accelerates the hydration.
3. Better bond between aggregates and cement paste.
4. Improves the toughness, shear, tensile strength and flexural strength of concrete.

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REFERENCES

1. Mechanics properties of Nano silica Material concrete by Saloma1, Amrinsyah Nasution,

Iswandi Imran and Mikrajuddin Abdullah.
2. Zhand and Islam 2012; Zhang, Islam, & Peethamparan, 2012.
3. Nazi, Givi, Abdul Rashid, Aziz & Salleh (2010).
4. Strength and Shrinkage Property of Nano Silica Powder Concrete by Hongxia Yang
5. Heidari & Tavakoli (2013).
6. Li, 2004, Zhang & Li, 2011; Zhang Et al, 2012.
7. Cement admixtures Association www.admixtures.org.uk.
8. Wikipedia.
9. Silicon Dioxide, Silica (SiO2) Nanoparticles – Properties, Applications from
http://www.azonano.com/.
10. Nano Technology and Concrete research Opportunities: Perumalsamy Balaguru and Ken
Chong National Science Foundation, USA.

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