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Types of Chemical admixtures are: Superplasticizers Air-entraining agents Accelerators Retarders AIR ENTRAINING ADMIXTURES Air entraining admixtures have a large use in Europe, North America, Japan and such countries in the higher latitudes. This is because of ensuring durability against repeated freezing and thawing Air entraining admixtures are made from: (i) Natural wood resins (ii) Synthetic detergents (iii) Salts of petroleum acids What is Air Entrainment? The production within the concrete mix of a large number of small bubbles of air. Normally these bubbles are less than 1mm in diameter. The bubbles must be stable and remain in the concrete as it is transported and placed so that they are still present in the hardened mass of concrete. To provide freeze thaw resistance the bubbles must be evenly spread throughout the concrete Chemistry of air entrainment Air entrainers are almost all anionic surfactants Natural wood resins Vinsol, Wood resins Animal and vegetable fats and oils oleic acid, coconut oil derivatives Synthetic materials alkyl/aryl sulphates and sulphonates Non ionic and cationic materials can be used but are usually not as stable. They may be useful in blends with particular objects. Mechanism of Entrainment Anionic surfactants have a hydrophobic and a hydrophilic end. This makes them collect at the air water interface with the hydrophobic end in the air. This reduces surface tension and allows the formation of a stable bubble The hydrophilic end is polar and is attracted by charges on the surface of cement and aggregate particles. This attaches the bubble to the surface and helps to produce a stable structure in the mix. Air is not added to the mix. The air that is already in the mix during the mixing process is made stable.

Combinations of materials are used to provide stability under different conditions and to produce a desired range of bubble sizes.

Air stabilization in concrete

Why air entrain concrete? Frequently, most consideration is given to the effects of air entrainment in hardened concrete, primarily freeze-thaw protection, but it must be remembered that there are considerable benefits to be gained in the fresh concrete. Freeze - Thaw resistance Increasing mix cohesion Improved mix workability Improved surface finish Increased mix volume - yield Many of these benefits can be obtained with only small increases in air content and do not necessarily require the addition of a specific air entraining admixture. Mix cohesion problems Cohesion problems occur when the internal structure in a concrete mix is insufficient to hold the mix together. This internal structure is partly due to physical support of the particles by each other and partly due to electrostatic interactions between the particles. If there is a lack of materials of a particular size in the grading of the aggregate then the physical support may not be complete. This can cause a separation of the mix Constituents. If there is insufficient attraction between the particles then there can be a separation

How air helps cohesion Typically 1 or 2 % additional air over that normally present in the mix will be sufficient to give improvements in cohesion. Air bulks the volume of the paste, allowing the other materials in the mix to be better covered. Air tends to form at the right size to replace any gaps in the sand grading. This means that the structure of the concrete mix is maintained properly, reducing the tendency to segregate. Electrostatic action between air bubbles and aggregate acts to hold mix components together, Air bubbles act as elastic buffers in the concrete mix, allowing mix components to move past each other more easily. This reduces the need to add more water to make the mix mobile and therefore reduces the tendency to bleed. Effect of air on bleed

Effects of improved Cohesion Segregation reduces, minimizing problems of settlement of aggregates. Water is held within the concrete, reducing bleed and cutting down surface finish problems Lack of excessive bleed water means that the surface is not weakened through having an increased water:cement ratio and does not have the same tendency to show shrinkage cracks. Reduction in strength 1% air will usually reduce compressive strength by 5 to 6% requiring an allowance to be made when designing the concrete mix. However, the increased workability and placeability of an air entrained mix will reduce the water content needed, which will have some counter effect on the drop in strength. Low cohesion or harshness in a mix may increase water demand as more water is added in an attempt to improve the compaction of the mix. Using air to improve

cohesion reduces the need for extra water and therefore may not actually reduce compressive strength as much as would otherwise be expected Admixtures and setting and hydration control (Accelerators / Retarders) Reasons for retardation To overcome the faster set of concrete at higher temperatures To allow for longer delivery and placing times To allow later deliveries of concrete to be added without causing cold joints To meet the needs of particular construction methods, Such as slipforming. Reasons for acceleration To overcome the slower setting of concrete at low temperatures To meet the needs of particular construction methods, such as floor finishing To produce rapid early strength gain To allow rapid turnover of moulds NOTE : If the strength gain is the only criterion then often the use of a superplasticiser to obtain a high level of water reduction, combined with the use of steam curing if necessary, will produce better strength gain than the the use of an accelerator. Chemicals used Retarders - mostly organic chemicals Carbohydrates Hydroxycarboxylic acids and salts Phosphates Accelerators - mostly inorganic chemicals Calcium chloride, Formates, Nitrates Thiocyanates Silicates Aluminates Calcium chloride is the most effective accelerator. However it will cause corrosion of embedded steel and must not be used where reinforcement is present What is Affected? Cement hydration Setting time Working life Strength gain Although retardation and acceleration are primarily affecting the chemistry of the hydration reaction, it is usually the physical results of this that are required.

The effect of retarders and accelerators on the hydration curve

The effect of retarders and accelerators on temperature rise

Four hours retardation The concrete is to be placed after four hours Possible four hour journey to site Four hours more workability than a normal mix is required Flowing concrete is needed for four hours The concrete is not to set for four hours Setting delayed by four hours from control mix is required

Only one of these (the last) relates to a definition of retardation which will be found in admixture standards, but all of them might be the need of the customer. It is important that the exact needs are determined before and attempt at a solution made.

Other effects The exact level of retardation or acceleration obtained in a particular mix will depend on a number of factors, including: Level of admixture Increased dosages will have increased effects but this is usually not a straight line effect. Temperature Cement chemistry Starting workability EFFECTS OF CHEMICAL ADMIXTURES ON FRESH CONCRETE Water reducers/ plasticizers. Improvement in workability when used as plasticizer Better appearance, and uniformity Better finishing characteristics Less bleeding; greater pumpability Some retardation of setting times. High range water reducers/ super plasticizers Whatever is true of plasticizers more of that with superplasticizers, generally Higher dosages; greater benefits in properties of fresh concrete Air entraining agents Workability increases Mixes are more cohesive, Finishability better. Freeze- Thaw resistance. EFFECTS OF CHEMICAL ADMIXTURES ON HARDENED CONCRETE Water reducer / Plasticizer when used as plasticizer no significant effect on 28 day strength, modulus of elasticity or permeability When used as water reducer- reduced creep and shrinkage. Other properties are unaffected. When W/C is reduced enhanced strength, higher modulus of elasticity and all round improvement in all properties including permeability. High range water reducer/ superplasticizer whatever is true for water reducer it is true for high range water reducer as well

On a statistical basis the concrete is always more uniform, better compacted and variability of strength is loss Long term gain in strength and other properties often noted.

Air entraining agents Lead to lower unit weight of concrete, inversely proportional to air entrained At the same W/C ratio, compressive strength, flexural and tensile strengths are reduced Approximately, for every 1% air entrained (by volume), 5% loss of strength Loss of strength overcome by a small reduction in W/C ratio made possible by reducing water content to a small extent Durability is better since capillary absorption of water is blocked by air bubbles Freeze-Thaw resistance, Resistance to aggressive solutions Can chemical admixtures be trusted? An usual question. Especially when the marketing pressures are high. The answer is yes, but.., The but arises from a need of the user to ensure compatibility of a commercial product with the cement he has at hand. This is done not only by going through chemical manufacturers technical information but also testing. Testing is done on cement, mortar and concrete with and without chemical admixture. IS 9103 prescribes physical requirements. The bigger the job the more elaborate can be the tests, including chemical tests on the cement itself. Whose responsibility? This is that of the Site/Project Engineer, the same person who is responsible for concrete quality. Contractor should assist in carrying out the necessary tests Who pays? It is in the interest of contractor to use admixtures in order to produce better and more uniform concrete He can ensure that the cost is recouped either in labour saving, or in placement costs or in cement saving. He is the ultimate beneficiary as well as the owner Reference: 1. Properties of Concrete, A.M. Neville, Fourth Edition, Pearson Education Asia pvt., Ltd., 2000. 2. Concrete- Microstructure, Properties and Materials, P.K. Mehta and Palulo J.M. Monteiro, Tata Mcgraw Hill., 2006. 3. Concrete Technolgy Theory and Practice, M.S. Shetty, S. Chand and Company Ltd.,, 2005. 4. Current Literature.., 7