Sunday, 4 June 2017

CHEMICAL ADMIXTURES – THE FIFTH CONSTITUENT MATERIAL FOR DURABLE CONCRETE


CHEMICAL ADMIXTURES – THE FIFTH CONSTITUENT MATERIAL FOR DURABLE CONCRETE



Abstract :

Concrete is one of the most widely used construction materials from time immemorial.  Since the day of its advent, concrete has been undergoing changes as a material and technology.

Of late, due to the growing needs of the performance and the durability of concrete, there has been a continuous search for upgrading the properties of concrete.  High performance concrete, fibre reinforced concrete, self-compacting concrete are only a few examples for the outcome of the same.

In this paper, an attempt is made to find out as to how chemical admixtures have become the indispensable component of modern day concrete, their effect on its properties both in plastic and hardened states and durability aspects.  Besides, new developments in the field of chemical admixtures and expectations from the construction industry are also discussed.

Introduction:

The history of our civilisation reveals that concrete, in some form or the other was in use when man started ‘construction’.  As the time passed by, concrete has undergone different changes and the ‘evolution’ of concrete is still continuing.

The simple form of modern day concrete in use worldwide is a mixture of cement and water as binder materials and coarse and fine aggregates as filler materials.  But this simple form of concrete is no longer sufficient to cater the challenging needs of construction industry.  Newer and more effective materials are being developed.  Concrete admixtures are the results of such an innovation, which has become the integral part of today’s durable concrete.

Parameters for durability:

In simple terms concrete must be placeable and durable.  Durability includes consideration of appropriate mechanical properties at given environmental conditions.  Once the concrete is mixed and placed in the formwork in the structure, the focus shifts to the durability of concrete.  But durability cannot be achieved in the hardened concrete, if necessary attention is not paid in the mix design stage and the problems encountered in the placing stage are not solved.  Aspects of permeability long-term strength and shrinkage as well as other factors related to the materials used as the environment of the structures are all important.  In pursuit of high performance in one aspect must not compromise performance in others.  Properties such as cohesion, density, stiffening, shrinkage temperature rise and total cost may all need consideration.  Workability and water-cement ratio may affect the other properties.  The revised Bureau of Indian Standards code of practice IS: 456 also specify maximum water cement ratios for various exposure conditions, and minimum cement contents.  In order to achieve durability, a specification may require the use of a particular admixture type, for example a superplasticiser even though it may be possible to do the job with a normal plasticiser.

Aggressive exposure conditions:

Water is a material, which is essential to make and hydrate concrete.  But water, for reinforced concrete in the hardened state will be highly aggressive.  The other aggressive agents such as chlorides, sulphates, carbon di oxide, oxygen etc.  will become more aggressive in the presence of water.  Hence the specifications should be available to control these agents apart form other ingredients like alkali levels.

Water penetrates concrete and in so, doing may bring other dissolved materials with it.  If  it fully penetrates in concrete  then the structure will leak.  This can lead to leaching of other materials from the concrete.  Reducing water-cement ratio slows down the rate at which water penetrates the concrete, extending the life of the structure.

Carbon dioxide reacts with the alkalinity in concrete, neutralising it and reducing the pH.  As the carbonated layer penetrates deeper into the concrete, eventually the cover to the reinforcement will be fully carbonated and will no longer passivate the reinforcing steel, which will start to corrode.  Reducing water-cement ratio slows down the rate of penetration of the carbonation front, giving extended protection for the same depth of cover.

Sulphate ions also attack cement, reacting with the products of aluminate hydration.  This is an expansive reaction, which can disrupt the concrete matrix, causing crumbling and easier penetration by other aggressive materials.  Reducing water-cement ratio will reduce the rate of sulphate penetration, but cannot prevent sulphate attack.  The use of sulphate resisting cement or blends of Portland cement and cement replacement materials is advised in such cases by standards.  Sulphate resisting cements have very low levels of aluminate phases.  The problem of sulphate attack will only occur if the total expansion is above a certain limit.  The lower aluminate levels in sulphate resisting cement ensure that it will not produce enough expansion to be a problem, however much sulphate is present in the environment.

Chloride ions are detrimental to the steel reinforcement.  They can cause corrosion to start even if the pH of the surrounding concrete is still nominally high enough to maintain the steel in a passive state.  Reducing the water-cement ratio cuts down the rate of penetration and again increases the life of the structure.  Of course, if there is no embedded steel there is no risk of corrosion.

Use of Superplasticisers :

The principle purpose of using superplasticisers in the concrete mixes from the durability point of view are as follows either individually or collectively:

·                     To increase workability in order to achieve easy placeability
·                     To reduce the quantity of water in the mix without reducing the workability.  Reduced water cement ratio means increased strength and durability.
·                     To reduce both water and cement at a given workability and strength in order to save cement and reduce creep, shrinkage and thermal strains caused by heat of hydration.

Mechanism of action:

Superplasticisers in concrete, cause uniform dispersion of cement particles avoiding the otherwise agglomerated particles of cement. Due to the dispersion, the workability of concrete increases.  The dispersion effect is attributed to the development of negative charges on the surface of cement particles.  These like charges repel each other and disperse the cement particles in the matrix breaking the agglomerates, releasing the water.  This water is effectively used in increasing the workability of the mix.

Cement-admixture incompatibility:

The cement-admixture incompatibility is a phenomenon in which the concrete with the admixture not exhibiting the intended effect with some cements.  The type of cement used influences the effect of plasticising admixture.  The chemical composition of cement is found to have direct relevance with the fluidizing effect of superplasticiser.  C3A content and the fineness of cement play a major role in the plasticising action of an admixture.  Higher the C3A content and the cement fineness, the lower the fluidizing effect.  The type of gypsum used in the cement performs much differently with some type of superplasticisers.  The fluidizing effect is much larger with dihydrate of gypsum than with hemihydrate.

Advantages:

Improving the effectiveness of water in concrete


The dispersion of cement particles in the concrete mix enables using the mixing water effectively in the mix.  The practical effect of this is that at any target workability a mix containing a plasticising admixture needs less water than a plain concrete.  How much less depends on the mix concerned and the type of admixture used.  Water reductions of up to a 30%, and sometimes higher, are possible.  Needing less water to get a particular workability means that less cement is needed for the same strength and durability.

Allowing workability to be obtained at a lower water content provides greater flexibility in mix design, allowing low water-cement ratios to be combined with good workability.  This higher workability brings benefits to concrete performance and profitability.  Using a higher starting workability means that the concrete is earlier to place, allowing the use of more efficient automated methods and lower labour costs.  Improved workability produces a greater ease of compaction, reducing the risk of defects in the structure such as honeycombing.  Finally, being able to start at a higher workability allows an extended working life to the concrete, providing a degree of protection against on-site delays and making a further contribution to efficient working.

Workability retention:

Unlike retardation, workability retention is not easily defined.  Mix workability drops with time because of the slow reduction in free water in the concrete, due to absorption into aggregate, evaporation loss or cement hydration.  Workability loss is important because concrete must have sufficient workability to be placed. If the workability is too low at the time of placing, then poor quality concrete will result.  The rate of workability loss is not the most important thing, what is needed is the right level of workability at a particular time.

Retardation slows cement hydration, but adding a pure retarding admixture has surprisingly little effect on workability loss.  Workability will typically fall at the same rate until a slump of approximately 50 to 75 mm is reached.  It is only at around this level and below that the retarder affects workability loss.  The greatest benefit comes from starting at a higher workability.  This increases the time before workability falls below the target value, because there is more workability to lose.  Adding more water to the initial mix will do this, but affects strengths or requires increased cement contents.  Addition of water reducing or superplasticising admixtures is a better method, allowing higher workabilities to be obtained for the same water content.  Specially formulated workability retention admixtures are available with optimised combinations of retarding, plasticising and other properties.  These materials can give the best solutions to problems of workability loss.

An alternative admixture-based solution may be appropriate, particularly for more extended working life requirements.  A combination retarding and water-reducing admixture is used at the concrete mixer.  The starting workability is adjusted to ensure that the concrete arrives at the place and time of use at typically 50 to 75mm slump.  A second, plasticising or superplasticising admixture is added to the concrete when it arrives and the concrete is re-mixed.  The dosage of the second admixtures is adjusted to give the desired level of workability.  When the second admixture is added the workability must be high enough for re-mixing, which must be continued until the concrete is homogeneous.  The second admixture should be a standard, non-retarding, type as there is no requirement for further retardation if the concrete is to be placed immediately.

Other methods can be used for more control over workability at the point of placing.  Controlled re-dosing of plasticising admixtures can be a very useful technique.  Temperature control for the concrete also often found to be beneficial.

Reducing shrinkage and cracking:

Reducing cement content reduces the cost of the concrete per cubic meter, an immediate contribution to better productivity, but there are further benefits.  Three of these are reductions in shrinkage, heat evolution and alkali content.  The latter is only really a problem if alkali aggregate reaction is a possibility.  The cement contributes the greatest levels of alkalis in a concrete mix, so reducing the cement content gives the greatest benefit.

The chemical reaction between cement and water creates heat and increases the temperature of the concrete.  The amount by which the temperature rises depends on the cement content and the degree of cooling experienced.  As the general environment does not gain temperature it has a cooling effect.  However, at the center of large blocks of concrete, such as foundation rafts, the temperature rise can approach 13 deg. C for every 100 kg of cement per cubic meter.  Large temperature rises, in rich mixes, create high temperature differentials between the interior and surface of the concrete.  This causes differential rates of expansion and contraction and can lead to severe cracking.  As has already been seen, the use of a plasticising admixture allows a particular combination of workability and strength to be obtained with less cement.  Therefore, there is less risk of temperature cracking.

The reaction between cement and water is the cause of further problems.  This is because the reaction productions are, on average, slightly denser than the original materials.  Therefore there is a loss in volume, or shrinkage, experienced as concrete sets.  Aggregate minimises this effect, just as it minimises temperature rise, but the more aggregate that can be included the more that the shrinkage can be reduced.  Again, the reduced cement content from the use of a plasticiser minimises the problem.

Reducing water permeability:

Durability specifications require low water-cement ratios.  Without the use of admixtures, concrete to meet these specifications must have high cement contents and still tends to be fairly low in workability and difficult to place.  Using admixtures, water-cement ratios of well below 0.40 are obtainable without excessive cement contents and still usable workabilities.  At these levels of water-cement ratio, most requirements for durability can be met.

Typical values from measurements of water penetration under pressure show the level of improvement in permeability coefficient that can be obtained through reductions in water-cement ratio. The test method uses disks of concrete, 100mm in diameter and 50mm thick.  These are cured for 28 days and then dried to constant weight at 35% humidity.

Water at a pressure of 10 bar is applied and the time taken for the water to fully penetrate the sample is measured.  This time is used to calculate the permeability coefficient by the Valenta method.  The rate of flow of water is then measured and used to calculate a value for the permeability coefficient use Darcy’s equation.  At low water-cement ratios it may take a considerable time for water to fully penetrate the specimen.  In this case the sample can be broken open and the depth of penetration measured and used in the Valenta calculation.

Using accelerating and retarding admixtures:

The term acceleration and retardation can often be confusing.  There are great differences between an extension of the workable life of a concrete mix and a delay in its stiffening time.  However, the term retardation is often used for either effect, particularly at higher temperatures.  At lower temperatures there can be similar confusion between acceleration of stiffening time and early strength gain.

When retardation and acceleration are referred to in admixture standards, it mainly concerns effects on stiffening rate.  This does not mean that the other areas are less important. Indeed, often workability retention or early strength gain is really what is needed on site.  When specifications are drawn up or enquiries made all parties must be aware of the properties needed.   Too often two sides understand different things.

Stiffening:

Retardation is measured by the time taken for concrete to reach a particular value of penetration resistance.  It is therefore a measure of the development of internal structure in the concrete.  Also important is that retardation is the difference between the stiffening rate of a control mix and a mix containing the admixture.

Stiffening does not start until the workability of the concrete has ended.  Obviously, the working life of the concrete will affect the stiffening time, but it will not automatically have the same effect in all mixes.  Changes to stiffening time may be desirable for a number of reasons.  In large volume of concrete, cold joints between adjoining truckloads cannot be accepted. Retardation of stiffening can avoid this problem.  Scheduling requirements, such as in floor finishing or slip forming, may also require acceleration or retardation of stiffening.

Changes in temperature change the rate at which plain concrete stiffens.  Accelerating or retarding admixtures are used to offset these effects and produce a setting time that meets the requirements of the overall construction process.  Dosages can be varied for the desired effect.  Retarders are not restricted to use in summer months, nor are accelerators to winter.  They are suitable for use whenever the rate of stiffening needs changing.  Retarders may be used to control the rate of stiffening of individual loads in a mass pour so that it gains and loses temperature as a whole, minimising temperature differential even in the cooler months.

Retarders do not reduce the peak temperature at the center of a concrete pour, as this depends on the cement content.  They delay the start of the main heat evolution, but once started it continues at a fairly constant rate.  Accelerators, in contrast, slightly increase the peak temperature because they cause the hydration reaction to occur more rapidly, leaving less time for heat to be dissipated.  If the peak temperature must be reduced, cement replacement materials can be used or water-reducing admixtures can reduce cement content.

Strength acceleration:

After concrete has stiffened, it develops strength.  Although it is possible to consider retardation of strength development, in practice this is virtually never required.  Once concrete has hardened, compressive strength is usually wanted quickly.

Accelerators, as defined in international standards, will increase early age strengths.  However, in many situations, superplasticisers used to produce low water-cement ratios may be more cost effective and give further benefits of improved durability and long term strengths.

It may not be possible to predict exactly whether an accelerator or superplasticiser will be the best solution in a given situation.  Where acceleration of both strength and stiffening is needed, accelerating admixtures must be used, possibly in combination with superplasticisers.  Usually, superplasticisers are more effective at ages beyond 12 to 15 hours.  Accelerators may be preferable at early ages and low temperatures.  Even in these situations, careful selection of a combination of steam curing and use of a superplasticiser may still produce better-precast results.

Conclusions:

The advent of admixture has become an indispensable ingredient of the modern reinforced concrete. The multifold advantage of concrete admixture not only help in manufacturing and placing a good quality and high performing concrete, but also enhance the durability of the r.c. structures. The technology is in the developing phase and new break through in terms of high performing admixtures is foreseen.

References:


1.                  Neville AM (1981), “Properties of concrete”, ECBS Publications.

2.                  Peter J Egan, “Economy and Durability with Admixture”, Fosroc International Limited, UK

3.                  S Collepardi, L et al. “Superplasticisers – Types, Composition and Properties”

4.                  V M Malhotra and V S Ramachandran (1995), “Superplasticisers” in Concrete admixture handbook properties, types and technology.





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