Superplasticizers

The use of superplasticizers (high range water reducer) has become a quite common practice. This class of water reducers were originally developed in Japan and Germany in the early 1960s; they were introduced in the United States in the mid-1970s. Superplasticizers are linear polymers containing sulfonic acid groups attached to the polymer backbone at regular intervals (Verbeck 1968). Most of the commercial formulations belong to one of four families: Sulfonated melamine-formaldehyde condensates (SMF) Sulfonated naphthalene-formaldehyde condensates (SNF) Modified lignosulfonates (MLS) Polycarboxylate derivatives

The sulfonic acid groups are responsible for neutralizing the surface charges on the cement particles and causing dispersion, thus releasing the water tied up in the cement particle agglomerations and thereafter reducing the viscosity of the paste and concrete (Mindess and Young 1981). ASTM C 494 was modified to include high-range water-reducing admixtures in the edition published in July 1980. The admixtures were designated Type F water-reducing, high range admixtures and Type G water-reducing, high-range, and retarding admixtures (Mielenz 1984). Effect of Superplasticizers on Concrete Properties. The main purpose of using superplasticizers is to produce flowing concrete with very high slump in the range of 7-9 inches (175-225 mm) to be used in heavily reinforced structures and in placements where adequate consolidation by vibration cannot be readily achieved. The other major application is the production of high-strength concrete at w/c's ranging from 0.3 to 0.4 (Ramachandran and Malhotra 1984). The ability of superplasticizers to increase the slump of concrete depends on such factors as the type, dosage, and time of addition of superplasticizer; w/c; and the nature or amount of cement. It has been found that for most types of cement, superplasticizer improves the workability of concrete. For example, incorporation of 1.5% SMF to a concrete containing Type I, II and V cements increases the initial slump of 3 inches (76 mm) to 8.7, 8.5, and 9 inches (222, 216, and 229 mm), respectively. The capability of superplasticizers to reduce water requirements 12-25% without affecting the workability leads to production of high-strength concrete and lower permeability. Compressive strengths greater than 14,000 psi (96.5 MPa) at 28 days have been attained (Admixtures and ground slag 1990). Use of superplasticizers in air-entrained concrete can produce coarser-than-normal airvoid systems. The maximum recommended spacing factor for air-entrained concrete to resist freezing and thawing is 0.008 inch (0.2 mm). In superplasticized concrete, spacing factors in many cases exceed this limit (Malhotra 1989; Philleo 1986). Even though the spacing factor is relatively high, the durability factors are above 90 after 300 freeze-thaw cycles for the same cases (Malhotra 1989). A study conducted by Siebel (1987) indicated that high workability concrete containing superplasticizer can be made with a high freeze-thaw resistance, but air content must be increased relative to concrete without superplasticizer. This study also showed that the type of superplasticizer has nearly no influence on the air-void system. One problem associated with using a high range water reducer in concrete is slump loss. In a study of the behavior of fresh concrete containing conventional water reducers and high range water reducer, Whiting and Dziedzic (1989) found that slump loss with time is very rapid in spite of the fact that second-generation high range water reducer are claimed not to suffer as much from the slump loss phenomenon as the first-generation conventional water reducers do. However, slump loss of flowing concrete was found to be less severe, especially for newly developed admixtures based on copolymeric formulations.

The slump loss problem can be overcome by adding the admixture to the concrete just before the concrete is placed. However, there are disadvantages to such a procedure. The dosage control, for example, might not be adequate, and it requires ancillary equipment such as truck-mounted admixture tanks and dispensers. Adding admixtures at the batch plant, beside dosage control improvement, reduces wear of truck mixers and reduces the tendency to add water onsite (Wallace 1985). New admixtures now being marketed can be added at the batch plant and can hold the slump above 8 inches (204 mm) for more than 2 hours.

Recommendations
1. Verification tests should be performed on liquid admixtures to confirm that the material is the same as that which was approved. The identifying tests include chloride and solids content, ph and infrared spectrometry. 2. If transit mix trucks are used to mix high slump concrete, it is recommended that a 75 mm slump concrete be used at a full mixing capacity to ensure uniform concrete properties. 3. If transit mix trucks are used to mix low w/c ratio concrete, it is recommended that the load size be reduced to to 2/3 the mixing capacity to ensure uniform concrete properties. 4. If freeze-thaw testing as described by ASTM C 666 indicates this to be a problem, it is recommended that the air content be increased by 1 percent.

Use of high performance superplasticizer in concrete

PM NEWS BEURAU Thursday, September 23, 2010, 17:13 Hrs [IST]

The most important improvement in concrete technology during the last three decades has been the use of superplasticizers, says Mayank Rawal, Director Technical, Asian Laboratories, New Delhi. The development of new superplasticizers during the last decades has determined the most important progress in the field of concrete structures in term of higher strength, longer durability and low shrinkage. Multipurpose poly functional superplasticizers have been developed to fulfill the need of ready-mix plants. The most important improvement in concrete technology during the last three decades has been the use of superplasticizers. The reasons that superplasticizers are much more important then any other chemical admixture are the number of improvement which can be achieved by its use. Recently, advances in superplasticizers containing functional group based on the family of Polycarboxylate Polymer (PC) have been studied to reduce the slump loss drawback. Besides a lower slump loss, PC-based superplasticizer performs better than the traditional sulfonted polymers in term of higher water reduction and lower slump loss. The mechanism of action of superplasticizers has proved that the negatively charged anionic polymers such as SNF or SMF for the presence of SO3 groups on the surface of cement particular imparts strong dispersion effect. The dispersion mechanism performed by the PC-based superplasticizers could be related more to a steric hindrance effect (produced by the presence of neutral side long graft chains) rather than to the presence of negatively charged anionic group (COO-) which is responsible for the adsorption of the polymers as the surface of cement particles. CEMWET SP-3000(PCE) is an innovative superplasticizer based on polycarboxylate polymer. The product is specially engineered to provide high water reduction and slump retention for ready mix concrete simultaneously. Ready-mix concrete industry requires superplasticizers satisfying requirement of:

High water reduction (minimum 20-25 per cent) Faster hardening for rapid strength development (16-18 hours) Longer slump retention time for reliable transportation and placing (minimum 3 hours)

Self-compacting properties for easy form filling Can incorporate high volume fly ash without sacrificing early strength development.

Progress in slump retention: The adsorption of superplasticizer can be related to viscosity. It is found that the slump value increased as the amount of adsorption increased. The adsorption is also greater at higher w/c ratio. The amount of adsorption also related to the mol. wt. of the superplasticizer and the different chemical structures of the superplasticizers. Poly Carboxy Ether based superplasticizers gives maximum adsorption at 5.6x104 mol. wt. compared to 1.6x104 mol. Wt. for naphthalene formaldehyde condensate. The dosage of superplasticizer increases for equal workability once the mol. wt. is less or more than the optimum dosage as specified above. The fludifying effect for cement paste could be increased by reducing the content of monomer. The amount of absorption and the optional degrees of polymerization were different for admixture with different chemical structures. Ready-mix concrete producer, has to depend on the available aggregate fine and coarse for manufacturing dayto-day concrete. There are various mix design utilising different type of fillers, cement and binder together with the special concretes, such as coloured concrete. The PCbased admixture is more reliable and facilitates the production of concrete with low water/cement ratio extended workability for long time and use of high volume of fly ash. The cost saving in production may be realised through mix design optimisation for cement types and aggregate comparison satisfying the requirement of IS:456-2000. The consumption of PCE-based admixture compared to PNS-based admixture on solid basis is just half. The solid content present in PCE admixture is only 25-30 per cent compared to PNS based admixture which is 42-45 per cent. The flow properties of PCE admixture at low dosage is higher at low water/cement ratio compared to PNS admixture. The saturation point occurs at a PCE dosage of 0.25 per cent. Moreover, the transaction point roughly to the saturation point of mortar containing SNF occurs at a polymer dosage of about 0.4 per cent. Finally, it is noted that bleeding and segregation occurs if the polymer dosage is far beyond the saturation point. Conclusion: Superplasticizers are able to enhance the placing characteristics of concrete mixture by increasing the workability level at a given W/C. Therefore, they allow easy placement of concrete mixture even with low W/C as required by strength or durability reasons. CEMWET SP 3000(PCE), a new generation superplasticizer, offers manifold benefits to the ready-mix industry:

A single versatile admixture for all grades of concrete. Provides early strength development and maintains workability of the concrete for extended time at high temperature. Blended cement can be further incorporated with fly ash to reduce the cost of production per m3. An ideal admixture for the precast Industry. Surface finish improves without bug holes. Concrete segments of large size can be produced without honey combed surface. PCE being colourless improves the colour & texture of the concrete produced.

Chemistry
Oil Based Defoamers
Oil based defoamers have an oil carrier. The oil might be mineral oil, vegetable oil, white oil or any other oil that is insoluble in the foaming medium, except silicone oil. An oil based defoamer also contains a wax and/or hydrophobic silica to boost the performance. Typical waxes are ethylene bis stearamide EBS, paraffinic waxes, ester waxes and fatty alcohol waxes. These products might also have surfactants to improve emulsification and spreading in the foaming medium. These are heavy duty defoamers and are normally best at knocking down surface foam.

Powder Defoamers
Powder defoamers are in principle oil based defoamers on a pariculate carrier like silica. These are added to powdered products like cement, plaster and detergents.

Water Based Defoamers

Water based defoamers are different types of oils and waxes dispersed in a water base. The oils are often white oils or vegetable oils and the waxes are long chain fatty alcohol, fatty acid soaps or esters. These are normally best as deaerators, which means they are best at releasing entrained air.

Silicone Based Defoamers

Silicone based defoamers have a silicone compound as the active component. These might be delivered as an oil or a water based emulsion. The silicone compound consists of an hydrophobic silica dispersed in a silicone oil. Emulsifiers are added to ensure that the silicone spreads fast and well in the foaming medium. The silicone compound might also contain silicone glycols and other modified silicone fluids. These are also heavy duty defoamers and are good at both knocking down surface foam and releasing entrained air. Silicone based defoamers are also suitable in non-aquaous foaming systems like crude oil and oil refining. For very difficult systems flourosilicones may be suitable.

EO PO Based Defoamers
EO/PO based defoamers contain polyethylene glycol and polypropylene glycol copolymers. They are delivered as oils, water solutions, or water based emulsions. EO/PO copolymers normally have good dispersing properties and are often well suited when deposit problems are an issue.

Alkyl Polyacrylates
Alkyl polyacrylates are suitable for use as defoamers in non-aqueous systems where air release is more important than the breakdown of surface foam. These defoamers are often delivered in a solvent carrier like petroleum distillates.