Hello and thank you for being here.

The main theme of

today's speech is concrete, with its properties and possible
new formulations.

We will review the basics about concrete and its properties, mortars, aggregates,
hydraulic cements and their hydration.
We'll also explore the admixtures used by the industry, as well as the supplementary
cementitious materials,
the research already done regarding them and possible further research in our
laboratory.

Concrete is an extensively used building material. The most elementary concrete is made of a
binder (the cement paste) and a filler (the aggregates).
There are concretes with other binders than cement paste, but the basic concrete that is used
more often and for the most applications
is made with Portland cement paste.
For special properties, such as longevity, higher compressive and tensile strength,
concrete today is made by adding at least an admixture or a supplementary cementitious
material or a filler, in most cases both.
Concrete is prepared either on the site, or in concrete plants.
It can also be purchased as a ready mix that only needs water to be added, as well as other liquid
admixtures.
http://www.jdm-inc.com/concrete-vs-cement.php

The next five slides will show the most important properties of concrete that we would like to improve, as
well as the measurement techniques for some of these properties.
Bleeding is the appearance of a layer of water at the top or the surface of freshly placed concrete after it
has been consolidated and struck off, but before it has set.
A balanced bleed is beneficial to prevent surface cracking while the concrete dries.
In high density concrete mixes, such as the ones made with fillers or pozzolans, there is very little
bleeding.
The density of concrete varies between 2,200 and 2,400 kg per cubic meter in normal concrete, but for
concretes with special additives for particular applications,
it can get up to 6000 kg/m3.
The density of concrete varies with the amount and density of the aggregate, the amount of air entrapped
or entrained, the water and cement contents.
The alkali-silica reaction is a potentially harmful condition in concrete resulting from a chemical reaction
between some aggregate minerals and the highly alkaline pore solutions found in concrete.
The alkali-silica reactivity can be reduced by using nonreactive aggregates or by using pozzolans that react
with the excess calcium hydroxide.

Design and control of concrete mixtures

Integrated materials

Durability is a property that can be measured indirectly through other properties

The resistance to freeze-thaw damage can be measured through experiments, by using hundreds of freeze-thaw
cycles and exposure to various chemicals in higher concentrations than normally found in the environment.
The setting time influences early strength and the short-term durability.
The strength gain can be measured with different devices, such as the Gilmore needle or the Vicat needle.
The coefficient of thermal expansion of a particular concrete mix will influence the drying shrinkage, as well as the
possibility of cracking.
Permeability depends on the amount of interconnected air bubbles entrapped or entrained in the concrete. A low
water/cement ratio decreases the permeability.
Another important property, unrelated to durability, is the workability of the mix - it is assessed through a slump
measurement The higher the slump, the easier it is to work with the concrete, although increasing the w/c ratio will negatively
impact the other concrete properties.
When working with fillers or pozzolans, there will be a decrease in workability, which is why superplasticizers are
used in such cases.
http://www.aboutcivil.org/concrete-workability-factors.html
Design and control of concrete mixtures

Strength is another crucial property of concrete.

There are different amounts of stress that concrete can withstand: compressive, tensile, flexural,
torsional or shear stress.
Only the compression and flexural or bending strength are measured normally, with
standardized methods.
The compressive strength is much higher than the other kinds, although they are affected in the
same manner by:
the water/cement ratio - the higher it is, the lower the concrete strength;
and the amount of entrapped or entrained air - more air equals lower strength.

http://www.denizkaya.net/plastik-muhendisligi/loading/

The heat of hydration is an intrinsic property of all cement blends. The heat generated by the hydration
reactions has allowed us to divide hydration into the five phases (which will be discussed later).
There is more than one method for measuring the heat of hydration: thermal monitoring and adiabatic or
semi-adiabatic calorimetry.
There are two main peaks on a calorimetric curve, one generated by the initial reactions between
aluminate and calcium sulfate (the first wave of ettringite formation)
and the other one generated by the slower, but more intense, reactions between alite or belite and
water, plus a secondary wave of ettringite formation.
When using admixtures, the main peaks on the heat of hydration curves will move to the left (meaning a
faster set) or to the right (meaning that there will be a delayed set).
The temperature curve has only one peak, with a maximum between 10-20 hours from mixing. The
temperature varies according to the mix design (adding fillers will decrease the maximum temperature
and delay the peak) and quantity - larger blocks of concrete will have a higher temperature at the core
due to the insulation provided by the surrounding concrete.
Calorimetric Studies on Heat Evolution and Temperature Rise due to Hydration of Cementitious
Materials in Concrete using SemiAdiabatic Calorimeter. pofale
Isothermal calorimetry of cement - presentation
Integrated materials

Porosity is another important property of concrete. Depending on its values, the concrete can be stronger
or weaker and it can have high or low resistance to freeze-thaw damage.
There are a few methods for measuring porosity, but the downside to using them is that they can only be
used after a certain period of concrete densification (usually at 28 days) and their results depend on the
pore neck size rather than the actual pore size.
One such method is mercury porosimetry, which forces mercury through the pores and may destroy pore
walls due to the high pressure used.
Helium pycnometry and nitrogen adsorbtion are two other intrusive methods. The amount of adsorbed
nitrogen varies with the the interfacial area of the material and is dependent on pressure and
temperature.
Scanning electron microscopy is also used to assess porosity in various surfaces cut from the hardened
cement paste samples.
Compared to these methods, the NMR techniques we have access to can make an evaluation of the
distribution of pore sizes from the beginning of the hydration, right after mixing the cement pastes.
They show the evolution of the pores during the creation of the hydration products that fill the pores.
They also have access to closed pores (with water in them) and can be used to monitor the changes in
pore size distribution over a long period of time.
The influence of silanes on hydration and strength development of cementitious systems Xiang- Ming
Kong
http://www.dq.fct.unl.pt/en/nitrogen-gas-porosimetry
http://ciks.cbt.nist.gov/garbocz/bridges/node6.htm

Mortars are basic concretes, consisting of a mixture of portland cements or blended hydraulic
cement and plasticizing materials (such as limestone or hydrated or hydraulic lime),
together with other materials introduced to enhance one or more properties such as setting
time, workability, water retention and durability.
Mortar resistance is usually smaller than the concrete made with the same cement paste.
Resistance in normal concretes (for general purpose) comes from the large, stable aggregates.
With NMR, it is much easier to study the hydration of cement pastes and mortars, due to the
technical space limitations within the Minispec and the small sample sizes. Also, the aggregates
themselves have little to no influence on the hydration of the cement paste.
http://www.kilsaran.ie/uploaded/thumbnails/db_file_img_1510_filled_334x300.jpg - poza cu
mortarul
http://www.masonry-concrete.com/images/concrete-form.jpg - poza cu betonul

In concrete, the aggregates represent the filer held together by the cement paste.
They form the bulk of the concrete system; they can occupy up to 60-75% by volume or 75-80%
by mass.
For durable concrete, it is important that the aggregates be made up of chemically and
dimensionally stable rocks and minerals. These can be natural, like rounded riverbed gravel,
natural sand, or man-made like crushed stone.
For the best concrete properties, it is also recommended that the aggregates be well graded,
using a sieve system.
The fine aggregates have a range of sizes between 150 m and 9.5 mm, while the coarse ones
between 9.5 and 100 mm.
For a high quality concrete, the aggregates need to be dry on the surface, free of absorbed
chemicals or coatings of clay and other fine materials that could prevent the cement paste from
coating them properly.
http://test-sieves.com/test-sieves.jpg
http://docasphalt.files.wordpress.com/2013/04/sized.png
http://docasphalt.files.wordpress.com/2013/04/siv2.png

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The most used kind of cement in construction is Portland cement. There are five main
types of Portland Cement, although two of them are mostly utilized in industry, type
one, the normal portland cement, and type two, with moderate sulfate resistance.
The main properties of cement are:
- Particle Size and Fineness

- Soundness, meaning the ability of a hardened paste to retain its volume

- consistency and setting time, when it has already been mixed with water

http://www.nachi.org/constituent-materials-concrete.htm
http://megdmg.gov.in/photogallery.htmlnd cement.

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Portland cement is made by heating a mixture of limestone and clay, marl or shale (for
their content of silica, aluminates and iron oxide), up to a temperature of about 14501500C.
The temperature rises gradually, first the water from the feed evaporates, then at about
500C the limestone breaks up into calcium oxide and carbon dioxide, then the siliceous
and aluminosilicate fractions of the feed decompose.
During the last stage of heating, these fractions melt together partially, they react and
form the active silicates in cement (alite and belite), then they form nodules of clinker
through partial fusion.
After cooling , the clinker is mixed with a small quantity of gypsum (up to 5% of the
clinker mass) and finely ground to make the cement.
The gypsum controls the rate of set and appears in various hydrated forms, such as
dihydrate, hemihydrate or anhydrite.
http://www.cement.ie/about/cement-production/

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The clinker composition and the development of the crystals within the clinker have a
direct impact on the degree of hydration of the cement ground from the clinker.
These two tables show the reactions and evolution of the particles along the kiln, while
the temperature increases.
After calcination, all the water and carbon dioxide is lost and the silica and calcium oxide
start to react. The aluminate and calcium react and melt, making the particles and
forming crystals stick together.
Design and control of concrete mixtures

13

Crystals start to grow as the reactions continue, consuming the initial ingredients. Belite
forms first, then it reacts with excess calcium oxide to form alite.
The belite crystals are represented as round particles, while alite as angular ones.
Around 1400 degrees, the whole mass of calcium silicate crystals is incorporated into
nodules, bound together by the molten phase, composed of tricalcium aluminate and
ferrite.
The liquid phase will crystallize as well as the temperature goes down.

Design and control of concrete mixtures

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The main constituents of cement can be easily identified from an optical microscopy
photo of a polished, etched section of clinker.

Alite appears as brown, euhedral to subhedral crystals,

belite as blue, circular crystals exhibiting internal lamellar structure,
the interstitial phases ferrite appears white
and the aluminate appears gray.
http://ciks.cbt.nist.gov/~garbocz/TN1441/node1.htm

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Based on the evolution of the heat of hydration after the mixing of the concrete
constituents, there are 5 accepted stages in cement hydration:
1.
mixing = also known as preinduction - a very high amount of heat is released in
a very short time - it starts at the first contact between water and cement and
lasts up to 15 minutes
2.
dormancy - the concrete can be transported and handled during this period - it
takes 2 to 4 hours
3.
hardening - beginning with the initial set, the alite hydration products are
growing, generating a large amount of heat - it takes 2 to 4 hours
4.
cooling - the hydration reactions continue, but with less and less intensity and
heat
5.
densification - as long as there is water and any amount of unhydrated cement
grains, the hydration reactions continue

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In the beginning, calcium hydroxide dissolves in the solution, the calcium aluminate and
gypsum form ettringite
Then the alite reacts with water once the solution is saturated in calcium hydroxide
Belite is slower to react and will continue to hydrate for a long time
Given an excess of calcium aluminate, ettringite will react to form monosulphate
With an excess of calcium sulphate from the environment, secondary ettringite will form
from the monosulphate and manifest itself as sulphate atack
http://iti.northwestern.edu/cement/monograph/Monograph5_3.html

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The final products of hydration in cement are

calcium silicate hydrate with spiky, weak crystals - it is the most important component,
as the strength of the concrete depends mainly on its development
ettringite with elongated, well developed crystals that tend to occupy all the free
spaces
monosulphate, a secondary product based on ettringite and excess calcium aluminate
calcium hydroxide, with large, hexagonal and plane-like crystals
hydrated Fe and Al hydroxides

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All of these hydration products can be influenced by the concrete compositions. Some of the
chemical admixtures generally used, according to the EN 934 standard, are:
Normal plasticisers (water reducers)
Superplasticisers (high range water reducers)
Air Entraining , Accelerating, Retarding
Water resisting (waterproofing)
Corrosion inhibiting admixtures
Foamed concrete admixtures
Pumping admixtures
Viscosity modifying (segregation reducing) admixtures
Shrinkage reducing admixtures
Anti-washout underwater concrete admixtures

http://www.nachi.org/concrete-admixtures.htm
http://www.mapei.com/public/IT/references/big/3674_c.jpg
http://www.mapei.com/public/IT/references/big/3674_a.jpg

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Of these,
the Air-entraining admixtures are used to stabilize microscopic bubbles in the concrete, which
can provide freeze/thaw resistance and improves the resistance to deicer salt scaling.
the Water-reducing admixtures can reduce the water content by 5 to 10%, while maintaining
slump characteristics.
the Mid-range water reducers are used to reduce the water content by 6 to 12%, while
maintaining slump and avoiding retardation.
the High-range water reducers will reduce the water content by 12 to 30%, while maintaining
slump.
the Retarders decrease the rate of hydration of cement.
and the Accelerators increases the rate of hydration of cement.
The curves show the evolution of the heat development of portland cement pastes with added
sulfonated melamine formaldehyde as a superplasticizer. It is obvious how much the 4%
addition prolongs the dormancy stage. Normally, superplasticizers are added to a concentration
of up to 1.5% of the cement mass.
Ramachandran 1997

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The Supplementary Cementitious Materials are natural or synthetic materials used in

conjunction with portland cement to contribute to the properties of concrete through hydraulic
or pozzolanic activity (or both).
they are used to improve a particular concrete property, like resistance to alkali-aggregate
reactivity, strength, permeability to water, chloride or chemical resistance,
or they can act as fillers.
Hydraulic materials will set and harden when mixed with water.
Pozzolanic materials require a source of calcium hydroxide to react, usually supplied by
hydrating portland cement.
The most used are: ground, granulated blast-furnace slag, fly ash, silica fume or colloidal silica
nanoparticles, natural volcanic ash.

http://geoinfo.nmt.edu/labs/microprobe/description/sem.html
http://www.intechopen.com/books/strontium-aluminate-cement-fundamentals-manufacturinghydration-setting-behaviour-and-applications/blended-and-multicomponent-cements-based-onstrontium-aluminate

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The pulverized fuel ash, also known as fly ash, acts as a pozzolan, while it also has
hydraulic properties, especially the class C fly ash. It can act as a replacement for cement
in concrete.
The ground, granulated blast furnace slag can also act as a replacement in concrete and
has mainly hydraulic properties.
There are natural pozzolans, such as volcanic ash and calcined clay, shale or metakaolin.
Silica fume has mainly pozzolanic properties. It also acts as a filler due to the very small
particle size.
http://www.ce.memphis.edu/1101/notes/concrete/PCA_manual/Chap03.pdf
Huang & Feldman 1985

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Silica fume, also referred to as microsilica or condensed silica fume, is a byproduct of the
silicon or ferrosilicone industries.
The product is the vapor that rises from electric arc furnaces used to reduce high purity
quartz with coal.
When it cools, it condenses and is collected in cloth bags, then processed to remove
impurities.
The particles have sizes ranging from 10 to 100 nm, up to 100 times smaller than the
cement grains (15-40 m). The particles are mainly in the form of glassy spheres of
silicon oxide.
Silica nanoparticles, on the other hand, are synthesized in laboratories and have a very
uniform size distribution. There are small deviations throughout the samples, since they
are made in carefully controlled chemical and physical conditions. They can also range in
size from 10 to 100 nm.
Silica nanoparticles are useful for studying the effect of various sizes of particles on the
particle packing in the cement paste and concrete, as well as the effect on pore size
distribution and cement hydration.
Hou 2015
Ramachandran concrete admixtures handbook

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Adding silica fume or nanoparticles to concrete leads to decreased workability, thus

requiring a water reducing agent in order to keep a low water-cement ratio, for
increased strength.
They act like pozzolans, by reacting with the Ca(OH)2 resulting from the hydration
process. This reaction creates additional C-S-H and increases the strength of the
concrete over time.
Silica fume and silica nanoparticles can be treated through silanization, thus modifying
the properties of the concretes that they are made with.
The modified silica fume increased the workability of the concrete, besides contributing
to strength, density and porosity, like the original silica fume. In my own samples, the
workability was visibly improved when using treated nanosilica.

Own research
Land

Improving silica fume cement by using silane Xu

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The implications of adding nanoparticles to concrete are just beginning to be studied on

a micro level. Furthermore, the influence of
modified surfaces is even less known and it is a great opportunity for research,
especially with NMR techniques and in parallel with other, better known techniques.

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