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__________________________________________________________________________________________ UKIERI Concrete Congress - Innovations in Concrete Construction

Supradip Das Buildtech Products, India

ABSTRACT. With the advent of poly-carboxylate based superplasticiser, it has been possible to make Self-compacting concrete (SCC). Also known as self-consolidating concrete is a highly flowable, non-segregating concrete that can spread into place, fill formwork and encapsulate even the most congested reinforcement, all without any mechanical vibration. As a high-performance concrete, SCC delivers these attractive benefits while maintaining all of concrete's customary mechanical properties and durability characteristics This paper studies 3rd generation poly-carboxylate (PC) as superplasticiser & compares its properties with conventional superplastciser based on Napthalene Sulfonated Formaldehyde (SNF) as a case study. The paper also discusses various methods adopted for testing self compacting high performance concrete for an infrastructure building in NCR. PC based admixture has a powerful dispersion capability and flexibility in molecular design is far superior in achieving very high workable concrete. It has the capacity of producing concrete at a very low water-cement ratio that too with high workability. PC based admixtures specifically being used to cater to different challenging requirements, such as high strength, high durability, high workability and long workability retention, etc. The paper also discusses one case study where concrete to be in high workable condition to travel around 40 kilometer & requires very high slump retention to ease placing characteristics. The performance of polycarboxylate & SNF based superplasticizer were studied, analyzed and compared. Keywords: Poly-carboxylate, Self compacting concrete, Superplastisizer, Workability Supradip Das Supradip Das with thirty five years plus experience in the field of cement, concrete & related materials, has been the consultant to Buildtech Products for last seven years & is instrumental in introducing newer materials & technology to its portfolio of products. Supradip Das was also a member of TRAIs committee of energy conservation, CAPEXIL, CMA & many others. Email : /

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Concrete has clearly emerged as the primary material for the construction of larger variety of structures in the world today. With no other alternate material presently available to substitute concrete. It seems it will be the main construction material in the near future. It is basically a low cost durable product compared to contemporary material available for construction & its ability to withstand the condition for which it has been designed over a period of time without getting damaged or deteriorated, in other words durability of concrete is a function of performance of concrete. Between 1940 & 1970, the advancements in concrete technology took leaps & bound with the development of various grades of cement such as high strength cement, wider variety of admixtures such as superplasticisers & other concrete making materials. With the availability of high strength cements enabled the use of high water content in concrete mix that were easy to handle and hence speeds up construction. Still this was not sufficient to achieve better workability in the case of high performance concrete. Water/cement ratio of more than 0.45 was not capable of getting the desired result. This led to serious durability problem with the concrete especially those subjected to severe service environments. Repair & rehabilitation of concrete structures thus become a costly affair. In the earlier days concrete technology had very limited scope due to the absence of materials required to improve the workability at the expense of water & to enhance the performance of hardened concrete. However with the increasing trends of using concrete admixtures had provided sufficient relief and made it possible to produce concrete using less water without affecting the workability. Over a period of time these chemicals became the fifth ingredients of concrete & relevant specifications were drawn & made mandatory of specialized application or to make high performance concrete. These chemicals were not only contributing to the workability in the green concrete but also a part of improving enhanced performance of hardened concrete with sufficient workability. The application of concrete admixtures and the advancement of admixture technology have promoted the development of numerous new concrete technologies in the past few decades, such as high strength concrete, high early strength concrete, highly flowable / self-compacting concrete, highly durable concrete, and so on. Nowadays, admixture is an essential component in any modern concrete formula, and plays a significant role in the sustainable development of concrete technology in the future. Self-compacting concrete is a highly flowable, non-segregating concrete. It has the ability to flow under its weight to fill the formwork and encapsulate even the most congested reinforcement, all without any mechanical vibration. As a high-performance concrete, SCC delivers these attractive benefits while maintaining all of concrete's customary mechanical properties and durability characteristics. Adjustments to traditional mix designs and the use of superplasticizers creates flowing concrete that meets tough performance requirements. If needed, low dosages of viscosity modifiers are added to eliminate bleeding and segregation. Since its inception in the 1980s, the use of SCC has grown tremendously. The development of high performance polycarboxylate polymers and viscosity modifiers have made it possible to create flowing concrete without compromising durability, cohesiveness, or compressive strength. Since the concrete produced is flowing in nature, the flowability of SCC is measured at site by spread using a modified slump test (ASTM C 143). The spread (slump
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__________________________________________________________________________________________ UKIERI Concrete Congress - Innovations in Concrete Construction

flow) of SCC typically ranges from 455 to 810 mm depending on the requirements for the project (Figure 1).

Figure 1 Measurement of slump flow or spread at site The viscosity, as visually observed by the rate at which concrete spreads, is an important characteristic of plastic SCC and can be controlled when designing the mix to suit the type of application being constructed. The objective of this paper is to present a review of admixture technology development, kinetics and case studies of advanced admixture applications in high performance self compacting concrete for one its infrastructure construction in the region.


The use of first generation admixtures can be traced to 50s where derivative of wood lignin is used to achieve noticeable water reduction but presence of certain undesirable component such as sugar often had a detrimental effect on the performance. Normal water reducer based on lignosulphonates, hydrocarboxylic acids capable of reducing water requirement by 1015% was developed in 60s. By overdosing the same in the order to get better reduction results in undesirable effect on setting, bleeding, air content, segregation, reduction of compressive strength at ultimate age. A new class of water reducers completely different from the conventional water reducer capable of reducing water requirement by 30% as compared to 10-15% water reduction by normal water reducers was developed in Europe in way back in 70s. These new generation chemicals were called SUPERPLASTICIZER for its high plasticizing effect and were first introduced in Japan in 1964 and later in Germany in 1972. In this category, the first admixtures based on Napthalene Sulfonated formaldehyde condensates (SNF) was developed. Concurrently Melamine Sulfonated formaldehyde (SMF) was introduced. It has been observed that in India where the concrete is done in daytime with a temperature goes beyond 400C, the high loss of slump is not unusual. The selection of admixtures should be such that it can retain the slump for a considerable period of time without loosing its other
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behavior. Specially for infrastructure & road projects, Napthalene based superplasticizers has been found to be better in performance like retention of slump as compared to MSFC. But for higher strength concretes, it has been found that NSFC does not attribute to the slump retention for extended periods. Sometimes it becomes difficult to control & retain the initial slump for a longer period of time. Tendency of bleeding and segregation at high slump, low efficiency at low dosage are other disadvantages of NSFC. All these limitations have imposed great challenges for use of NSFC superplasticizers in high performance concrete applications with increasing need to maintain high fluidity of concrete with extended workability retention at very low water cement ratio, although NSFC based superplasticizers are still being widely used. In the 90s, a new generation of superplasticizers based on poly-carboxylate Ether (PC) copolymers was emerged in the market. These co-polymers, based on an entirely different chemistry compared to the commonly used NSFC, generally feature a poly-carboxylate backbone with attached polyoxyalkylene pedant groups and have much more powerful dispersing effect on cement than conventional NSFC superplasticizers. Compared to the dispersion mechanism of conventional water-reducing admixtures, which can be explained in terms of electrostatic repulsion between cement particles negatively charged by the absorption of the anionic polymer molecule onto the cement surface and is measured by the magnitude of zeta potential, the electrostatic repulsion force for PC based superplasticizers is only half of the value measured for SNF superplasticizers and the dispersion is due mainly to the very strong steric hindrance effect that pushes the particles of cement apart. This theory is explained in detail in the kinetics & mechanism of action.

Figure 2 Chemical structure of PC, PMS (melamine ) & BNS ( Napthalene ) Chemical structure of three main types of superplasticizer has given in Figure 2. PC based superplasticizers are partially cross linked copolymer of acrylic acid & Polyethylene glycol mono-alkyl ether (CLAP). According to Tanaka, CLAP is hydrolysed & converted to PC
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based polymer. The low slump loss effect of PC based admixture directly related to the increasing number of the protruding side chains of the acrylic polymer.

In well known that in traditional admixtures, the actions are based only on Dispersion Effect where Electro static adsorption on the cement surface Negative charge on the cement granules that carry admixture chain With the progress of hydration process, the adsorptive molecules are covered by the C-S-H phases Electrostatic forces, existing among cement particles causes agglomeration & neutralized by the adsorption of anionic polymers negatively charged such as SNF OR SMF, for the presence of SO3 groups on the surface on the surface of the cement particles. The dispersion of cement particles would be related with the electrical repulsion produced by the negatively charged groups ( SO3 ) ( Fig 3 )

Figure 3 Schematic picture of sulfonated polymer (SNF) and its electrostatic repulsion effect on the dispersion of cement particles The dispersing effect of superplasticizers is generally ascribed to the development of some electro negative charges on the cement particles as determined by electro kinetic or zeta potential. Both adsorption and zeta potential increases by increasing the dosage with the same type of superplasticizer, same cement and same mixing procedure. Addition of superplasticizer causes reduction in zeta potential from 8mV TO 35mV (Figure 4).

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Z e t a p o t e n t ia l v s a d m ix t u r e c o n c e n t r a t i o n a t d i f fe r e n t
m o le c u l a r w e ig h t



) V m l a i t n e t o P a t e Z

35 30 25 20 15 10 5 0


Figure 4 Graph on the Effect on superplasticizer on zeta potential The dispersion mechanism performed by PC based super plasticizers could be related more to a steric hindrance effect (Produced by the presence of neutral side long graft chains) in addition to the presence of negatively charged anionic group (COO ) which are responsible for the adsorption of the polymers on the surface of cement particles. Maiti et al & Collparde has given a fair idea of the effect of PCE based admixture on cement grains (Figure 5).
Main polymer chain Graft chain Steric hinderance

Cement grains Side long graft chain Responsible for steric hindrance

Figure 5 Schematic picture of polycarboxylate superplasticizer (PCE) and its effect on the cement grain From the above it is clear that the two important properties Self Compacting Concrete are flowability and stability. The high flowability of SCC is generally attained by using PCE based admixtures capable of high water-reducing properties. The stability or resistance to segregation of the plastic concrete mixture is attained by introducing additional fine materials such as silica fumes/fly ash as viscosity modifier in the mix.

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Meeting any one of the above requirements in the field is a challenge to commercial ready mix concrete producers. There has been no previous job reference where all these requirements have been combined for a mega project. Difficulties in maintaining, uniform production quality, longer slump retention, self-compactability without segregation, excellent rheology are inevitable. So selection of right admixture, right type of concrete making material & its trial run is most important in achieving the desired result.

Transporting concrete from a RMC situated around 25km away from the construction site situated in the heart in New Delhi, the use of conventional admixture would have been very difficult, if not possible to meet the placement requirement at site. As a result new generation admixture was tested alongside with conventional one. This study was carried out primarily to ease the commercial implications. But this new generation admixtures have shown great advantages in application of such high performance concrete with excellent workability and extended workability retention & other parameters, thermal and drying shrinkage control, good strength development with 25% fly ash in total cementitious, and consistent quality control at low water-cement ratio in production. Transit time being too long coupled with heavy reinforcement element, the client & the consultant decided to go for self compacting concrete which needs very little vibration in fluid condition

Materials OPC Grade 53 conforming to IS: 12269 were used for making ready mixed concrete. Physical properties of cement tested as per IS : 4031 is given in Table 1. Table 1 Physical properties of cement tested as per IS : 4041 S. NO. 1. PROPERTIES 53 GRADE CEMENT OPC (AS PER IS : 12269)

FINENESS Specific Surface (M/Kg) 325.00 2. SETTING TIME (Min.) i. Initial 110.00 ii. Final 190.00 3. COMPRESSIVE STRENGTH (MPa) a. 72 +/- 1h 39.00 b. 168 +/- 2h 49.00 c. 672 +/- 4h 58.00 The fine sand & coarse aggregate was taken from Yamunanagar. The aggregates were tested as per IS: 383 for various properties required for designing the mixes. Apart from physical properties, the aggregates were subjected to alkali silica reaction studies & found to be innocuous. The sand conforms to zone II. The table 1 contains the details of testing of aggregates required for mix design.
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Mix Design For M45 grade concrete, 1.2% of conventional SNF based admixture gave very little initial slump was not suitable for the requirement. Same mix design was used with both the admixture & is given in Table 2. Table 2 Mix Design For M45 Grade Concrete S. NO. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. INGREDIENTS Cement OPC Gr 53 Fly Ash Water/Cement Ratio Water Coarse Aggregate ( 20mm ) Coarse Aggregate ( 10mm ) Sand ( zone III ) Sand / total aggregate PCL based Superplasticizer + Viscosity modifier, % bwoc SNF based Superplasticizer for IInd study. % bwoc GRADE M 45 380 80 0.41 156 798 342 606 0.35 0.6 1.2

Admixture Both the admixture Buildplast Super (NSFC based) & Buildplast Super 3000 (PCE based) from Buildtech Products I Pvt. Ltd. Was used in both the cases. Properties of both the chemicals are given in Table 3. Table 3 Comparison of physical properties of both the admixtures S. NO. 1. 2. 3. 4. 5. 6. 7. PROPERTIES Type Colour Solid Content,% Specific Gravity pH Viscosity Na2SO4,% BUILDPLAST SUPER SNF Dark Brown 47 1.25 7.8 65 <8 BUILDPLAST SUPER 3000 PCE Light Yellow 30.1 1.13 7.2 150 ---

Performance Table 4 gives a comparative study of both the admixture used in M45 grade concrete as a trial mix at a RMC. The ambient temperature at the plant was around 360C. Both the mixes were cohesive. No bleeding segregation was noticed. Workability was tested by conventional slump test and not by modified slump or spread method. In fact concrete with PC based admixture remained in fluid state for almost 270minutes. High fluid concrete always has a tendency to bleed & segregate but using fly ash as mineral admixture or as viscosity modifier
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has greatly improved the consistency vis a vis reduction in bleeding Special attention was required to check that HPC is flowable, cohesive (no segregation) and self consolidating mixture that can be easily placed without external vibration. Another critical key property of high performance concrete is retention of workability. The concrete mixture must retain adequate workability until the tremie placement is completed. With inadequate retention of workability, the concrete may get stuck in the tremie which would lead to difficulty in tremie lifting, and consequently affect the integrity of concrete structures. Most importantly, the size of structures and volume of tremie concrete may differ from application to application, thus the fresh concrete performance requirements (e.g. flowability, workability retention and extension of set time) have to be specific to application. Table 4 Field Results of High Performance Durable Concrete S. No. PROPERTIES (As per IS : 1199) Slump, mm Control Slump Initial Slump After 30 min. After 2Hrs After 3 Hrs. Slump Flow Value, mm Compressive Strength (N/mm) 3 days 7days 28days BUILDPLAST SUPER 3000 ( PCE based ) 0.8% bwoc 0mm Collapse -Collapse Collapse 680 BUILDPLAST SUPER ( SNF based ) 1.2% bwoc -150 110 50 -N.A

1. i. ii. iii. 2. 3.

29.2 43.6 --

24.5 38.5 --

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Figure 6 Modified slump test at site

UKIERI __________________________________________________________________________________________ Concrete Congress - Innovations in Concrete Construction

Figure 7 Self compacting concrete being pored

Figure 8 Self compacting concrete It has been observed that in India where the concrete is done in daytime with a temperature goes beyond 400C, the high loss of slump is not unusual. The selection of admixtures should be such that it can retain the slump for a considerable period of time without loosing its other behavior. Specially for road projects, Napthalene based superplasticizers has been found to be better in performance like retention of slump, superior finish & strength achievements. For this project, a specially blended superplasticizer based on Napthalene formaldehyde was used.
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Self compacting concrete (SCC) is relatively a new concept for Indian construction sccenario. With the prevailing construction boom in the country, there is sudden increase in demand for high performance self compacting concrete vis a vis it has also generated a demand for PC based ivth generation superplasticizers SCC being a special concrete needs BIS code of practice as most of the parameters are different from the existing code ( IS 456 ). Till we have a new code it is suggested to adopt ASTM or EFNARC codes. The other main constraints of using new generation admixtures are the price which is costlier by three times as compared to the conventional superplasticisers. Indian construction industry being very competitive & complex in nature, it will be a hard selling for the admixture manufacturer. In the present study consumption of PC based admixture was almost the half of the dosage of conventional SNF based admixture. The flow properties at low water cement ratio using half of the dosage has been very high as compared to SNF based superplasticiser. The P.C. based admixtures coupled with VMA facilitate the production of cohesive concrete free from bleeding & segregation. Fly ash concrete with low water/cement ratio with extended workability and using high volume fly ash. In achieving very cohesive & uniform concrete, high volume of viscosity modifier such as fly ash was used. Blast furnace Slag also can be used as another alternate VMA. Fly ash or slag produced in our country is not of good quality as compared to the developed countries where high volume of VMA is added. The advancement in admixture technology has played a significant role in the development of concrete technology. The advanced PC co-polymer based admixtures have demonstrated various performance benefits and technical advantages over conventional superplasticizers in meeting the diversified challenging technical requirements of various high performance concrete technologies for infrastructure construction.

1. 2. 3. MEHTA P K, Advancements in Concrete Technology, Concrete International, Vol 21, No 6, pp. 69-76. MALHOTRA V M, Superplasticizer: their effect on fresh and hardened concrete, Concrete International, Vol 3, No 5, pp. 61-81. JEKNAVORIAN J J ET AL, Use of polycarboxylate based high range water reducers in commercial concrete, Proceedings of the European Ready-Mix Conference, Lisban, 1998

4. RAMACHANDRAN V S, Concrete Admixture Handbook, Properties, Science & Technology, Second Edition, Noyes Publications, N.J., pp. 428-434. 5. JEKNAVORIAN J J ET AL, Condensed Polycyclic Acid-Aminated Polyester Polymers as Superplasticizer for concrete, 5th CANMET/ACI International Conference on
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Superplasticizers and Other Chemical Admixtures in Concrete, ACI SP-173, Ed. Malhotra. 6. MAITI S C AND MAYANK RAWAL, Use of High Performance Super Plasticizer in Concrete ICI Innovative World of Concrete 2008. 7. VERMA AJAY AND SHANKAR KUMAR SAHA, Brief summary on self compacting concrete ( A new generation concrete ) - study report made at Maneri Bhali Hydro electric project 2005. 8. JOHANN PLANK AND CHRISTIAN HIRSCH, Impact of zeta potential on early cement hydration phase on superplasticizer adsorption, Cement & Concrete Research, 2007, Vol. 37, pp 537-542. 9. MARIO COLLEPARDI, Enco, Engineering Concrete, Ponzano Veneto (Italy), Admixture Enhancing Concrete Performance, 6th International Congress, Global Construction, Ultimate Concrete Opportunities, Dundee, U.K. 5-7 July 2005.

10. DAS SUPRADIP, Superplasticizer The new generation Chemical Admixture Construction Journal of India, Feb 2003, pp 24 25. 11. DAS SUPRADIP Construction Chemicals The recent trends, Construction journal of India, 2002, pp31 - 38. 12. RIXOM M R AND MAILAVAGANAM N P, Chemical Admixture for concrete 2nd edition. 13. DHAIR R K & MCCARTHY M J, Admixture for High Performance Concrete, pp. 291300. 14. TANAKA Y, OHTA A, SUGIYAMA T, PolycarboxylateBased Advanced Superplasticizers for High Performance Concrete. Proceedings of the International RILEM Conference, The Role of Admixtures in High Performance Concrete, Monterrey, Mexico, March 1999, pp.135143. 15. IS : 9103-2003 Specification of admixture for concrete. 16. EFNARC, Specification & Guidelines of Self Compacting Concrete, Feb 2002.

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