EFFECT OF FLY ASH ON THE WHITE PORTLAND CEMENT HYDRATION CHARACTERISTICS

R K Singh, S Tripathi, S K Ananthakrishnan and H R Kapoor Aditya R&D Center-Birla White, Ultratech Cement Ltd., Jodhpur (RJ) India

Introduction This paper deals with the effect of mineral additive fly ash (FA) on the hydration of white Portland cement (WPC) keeping water to binder (w/b) ratio of 0.50. The samples of WPC with 10 wt% mineral additive (FA) were examined for 3, 7 & 28 days of hydration by X-ray diffraction analysis. The hydration reaction products in the WPC + FA system was found to be almost similar to that of normal white Portland cement hydration, except with the low quantity of Ca(OH) 2 formation. In the case of normal hydration of white Portland cement, larger amount of Ca(OH)2 were identified by X-ray diffraction patterns at all curing ages. The formation of Ettringite (AFt) phase has been seen during the initial hydration periods by XRD. Blended Portland cement, in which a major percentage of Portland cement (35%) is replaced by pozzolanic materials /waste materials, saves lot of energy. In addition, the blended Portland cements showed better performance over ordinary cement in many respects, such as reduced heat of hydration during early hydration, higher ultimate strength & better long term corrosion resistance to chemical attack [1]. The use of mineral additives such as fly ash, ground granulated blast furnace slag, silica fume etc in cement & concrete are gaining large acceptance all over the world and its contribution in total cement production is increasing day by day because of considerable enhancement in strength & durability properties and also towards sustainable development [2-3]. The mineral additives in blended cement give distinct changes of their paste composition. The cement paste of additives contains low Calcium hydroxide [Ca(OH)2], high C-S-H phase with continuous pores which lowers the permeability of cement mortar/concrete. Such properties provide high durability to blended cements in aggressive media. The use of pozzolanic material has been reported to effectively improve the resistance to sulfate attack in Portland cement. In the present investigation, x-ray diffraction techniques have been utilized to study in detail the hydration of cement with different percentages of FA. Chemical interaction between cement and additive system has been evidenced by the detection of changes in peaks intensity in the x-ray diffractogram. Experimental XRD studies of neat WPC & Hydrated with WPC additive The cement used was white Portland cement (WPC) taken from our Birla White plant as per IS-8042. FA was procured from Kota thermal power station. The White Portland cement (WPC), was mixed with 5 & 10% FA in a polythene bag keeping water cement ratio 0.50%. The bags were sealed after removing the air to avoid carbonation and were kept in an incubator maintained at 27oC for 3 days, 7 days & 28 days. Hydration reaction was stopped at different time intervals by using isopropyl alcohol. Hydrated samples were dried at 75oC for one hour and sealed in bag & then stored in desiccators for XRD analysis. Powder diffraction patterns of neat anhydrous, hydrated white cement and modified cement containing mineral additives (FA) were performed on BRUKER-AXS, Germany, model no.D8 ADVANCE X-ray diffractometer using Cu-K radiation. Intensity and d-values of observed peaks were compared with the values given in JCPDS cards for different mineral phases of cement [4].

X-ray Diffraction & Strength studies Diffraction patterns of white Portland cement (WPC) & cement mixed with 10% FA hydrated for 28 days along with anhydrous WPC are shown in figure 1. Anhydrous WPC showing the presence of normal white cement phases say C 3S, C2S, and C3A with gypsum [CaSO4.2H2O] & bassanite [CaSO4.1/2H2O] minerals. 28 days hydrated Cement samples XRD results shows an intense peak of calcium hydroxide [CH] at 2=18.05(4.90) & 34.10(2.62) respectively (figure 1). The calcium hydroxide [CH] peak intensity is recorded maximum in neat cement as compared to FA cement paste; On the addition of mineral additive in cement the relative intensities of the peaks corresponding to hydrated cement phases were altered and a few peaks were disappearance as the hydrations proceed because of interaction of CH, with the mineral compound of FA which may be causing the increase in strength. Calcium hydroxide cannot take part directly in the strength development to the cement paste, only after changed in to C-S-H gel by pozzolanic reaction with reactive mineral admixture.
CH

Results & discussions

C3/C2=C3S/C2S A=C3A G=CaSO4.2H2O B=CaSO4. 1/2H2O

CH=Ca(OH)2
CH

AFt= C3A.3CaSO4.32H2O CSH=5CaO.6SiO2. 5H2O

CSH/C3

C3 /C2 C3

C2 AFt
C3 /C2

NE AT W PC-28DH
C3

AFt

WPC+10% FA-28 DH

UNHYDROUS WPC
G B G
A

12

20

30

40

50

60

2-Theta - Scale

Figure-1: X-ray diffraction patterns of WPC paste & WPC mixed with 10 % of FA additive hydrated for 28 days Admixture has potential to consume CH & results in to secondary C-S-H gel, making microstructure denser. C-S-H has a huge specific surface which produces good amount of combination force inside the paste along with continuous structure (no interface) while CH is mainly found in crystal form & produce interfaces (weak combination) inside cement matrix. The more CSH was found formed in 10% FA modified cement because of the more of CH was absorbed, & higher the strength achieved.

Table 1 shows the value of compressive strength of cement mortars are 44.5, 58.2 and 68.7 MPa respectively cured for 7, 28 and 90 days. The effect of strength depends on the nature and the amount of additive mixed in cement. The variations in the strength of cement with 2.0 to 10.0% of FA are also shown in Table 4. The values of compressive strength increase with increasing concentration of FA up to 10% in cement, at all curing ages, while lower strength values were obtained with 2 to 10 % FA additive in cement at early ages (7 days) & strength values were found lower than the neat white cement. A higher value of FA modified cement recorded at latter ages (28 & 90 days) than the unmodified cement. Table-1: Strength of cement with different percentages of additive Name of additives Neat Cement Content (Mass %) 0 2 FA 5 10 Compressive Strength [MPa] (Age in days) 7 days 28 days 90 days 44.5 58.2 68.7 39.5 42.7 44.0 62.0 64.5 65.8 73.2 81.5 83.1

The addition of fly ash increases plasticity required for good mixing, which causes improvement in strength. In presence of additive, hydration of Portland cement is interfered with the interaction of cement hydration products and FA hydrated particles. Conclusions FA can react with CH liberated by cement hydration to produce secondary CSH gel inside the cement paste. The secondary formed CSH gel improves the compressive strength & microstructure of cement paste matrix, therefore, the phsico-mechanical property of modified cement increased. XRD analysis confirmed that less calcium hydroxide [CH] was consumed by FA additive as compared to neat cement.

Acknowledgement The authors are grateful to Sri Rahul Mohnot, Sr. President & Unit head, unit-BirlaWhite, UltraTech Cement Ltd. for giving permissions to publish. References [1] F. M. Lea, Pozzolanas & pozzolanic cements, Chemistry of cement and concrete, Edward Arnold, 1970, 414-453. [2] M. A. Caldrone, K. A. Gruber & R. G. Burg, High reactivity metakaoline: a new generation mineral admixture, Concrete International 16(1994) 37-40. [3] M. H. Malhotra, Characteristics of thermally activated alumino-silicate pozzolanic material and its [4] Powder diffraction file, cards nos. 31-0301, 33-0302, 38-1429, 44-1481, 461045, 05-0586 etc.

use in concrete, Cement & Concrete Research, 1995 25, No.8, 17-25.