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Available online at www.sciencedirect.com ScienceDirect Procedia Materials Science 11 (2015 ) 594 599 5th International Biennial Conference on Ultrafine Grained and Nanostructured Materials, UFGNSM15 Investigation of Mechanical and Durability Properties of Concrete Influenced by Hybrid Nano Silica and Micro Zeolite H. Eskandari a, *, M. Vaghefi b, K. Kowsari c a Department of Mechanical Engineering, Persian Gulf University, Boushehr, Iran b Department of Civil Engineering, Persian Gulf University, Boushehr, Iran c Department of Civil Engineering, Boushehr Branch, Islamic Azad University, Boushehr, Iran Abstract Today, concrete is the most widely used construction material in the world, cement is major component of concrete. Consuming energy in cement industry is very high and CO2 emissions generated during the production of Portland cement has serious environmental threatens. Therefore utilize of pozzolanic material as a supplementary cementitious material has a direct relationship with sustainable development. In this investigation, 2% Nano Silica and 5, 8 and 10% Micro Zeolite (by weight percent) replaced Portland cement constitutes and standard cylindrical specimens were prepared from the mixture. Two types of concrete mixture with water to cementitious material ratio (W/(C + P)) of 0.45 and 0.4 were prepared and they were tested after aging for 7, 28 and 90 days. The effect of these additives on mechanical properties (compressive and tensile strength) and durability were investigated by Electrical Resistivity (ER) and Rapid Chloride Penetration Test (RCPT) at the ages 28 and 90 days. Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) revealed that nano particles could improve quality of concrete. As a result of the tests, increase of mechanical characteristics is not considerable but make significant decrease in penetration of chloride ion and increase electrical resistivity that are appropriate option for controlling of corrosion in reinforced concrete structures. 2015 Published The Authors. by Elsevier Published Ltd. This by is an Elsevier open access Ltd. article under the CC BY-NC-ND license Peer-review (http://creativecommons.org/licenses/by-nc-nd/4.0/). under responsibility of the organizing committee of UFGNSM15. Peer-review under responsibility of the organizing committee of UFGNSM15 Keywords: Nano Silica, Micro Zeolite, Strength, Durability, Concrete; * Corresponding author. Tel.: +9877334440484 E-mail address: Eskandari.ho@gmail.com 2211-8128 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of UFGNSM15 doi:10.1016/j.mspro.2015.11.084

H. Eskandari et al. / Procedia Materials Science 11 ( 2015 ) 594 599 595 1. Introduction Concrete is most important construction material in the world and it has important advantages, but environmental problems are arising from the manufacture of Portland cement as a component of concrete. For reducing the consumption of cement and enhancing the mechanical and durability characteristics of concrete, we need the pozzolanic material, Ahmadi et al. (2001), Najimi et al. (2012), Andrade et al. (1999), Byung-Wan et al. (2012), Quercia and Brouwers (2010). Mines of zeolite and silica in Iran are abundant and has a lot of potential for replacement with Portland cement. Natural zeolite, a hydrated aluminosilicate of alkali and alkaline earth cations with a three dimensional frame structure with nano size crystal has been widely utilized in constructions since ancient times, Ghourchian et al. (2005), Najimi et al. (2012), Ramezanianpour et al. (2011). By replacing pozzolans, hydroxide calcium in matrix of cement paste is consumed and it produces silica gel which combines with the cations to form strong bonds that reduce the porosity of concrete, Chan and Ji (1999), Taheri Shakib et al. (2012). In this investigation micronized zeolite powder and nano silica hybrid with various proportion, has been replaced cement and the mechanical and durability properties of concrete mixtures were tested. 2. Materials and Methods The utilized micro zeolite is a clinoptilolite type of natural zeolite manufactured by Semnan-Negin Powder Company. It has been micronized with the average size is 5 micron. In addition to micro zeolite, nano silica powder purchased from Fadak Industry Company, type II Portland cement purchased from Fars-Nov cement factory and fine (0-4.75 mm) and coarse (4.75-19 mm) aggregates meeting the requirements of ASTM C33 were used in this investigation. The chemical composition and mineralogical compounds of used materials in this study are presented in table 1. Table 1. Chemical Composition of Zeolite, Cement and Silica. Compound SiO 2 Al 2O 3 Fe 2O 3 CaO Na 2O K 2O MgO TiO 2 MnO P 2O 5 SO 3 L.O.I IR Micro zeolite 69.28 10.43 0.49 3.56 0.73 1.27 0.5 0.166 0.001 0.004 0.005 12.97 - Cement 20.26 5.2 3.9 60.12 0.34 0.75 2.55 - - - 2.6 0.95 3.23 Nano Silica 98-0.294 0.393 0.328 - - - - - - - - Chemical properties of natural Zeolite are compared with the requirements of ASTM C618 in table 2. As it can be seen, the summation of silica, alumina and iron oxide, which are considered to be responsible for pozzolanic activity, is 80.2% for this natural zeolite, exceeding the 70% minimum level for class N raw and calcined natural pozzolans specified in ASTM C618. Table 2. Chemical properties of Natural Zeolite according to ASTM C618. Requirements Class N, ASTM C618 Chemical requirements SiO 2 + Al 2O 3 + Fe 2O 3 (%) Min, 70.0 Sulfur trioxide (SO 3) (%) Max, 4.0 Moisture content (%) Max, 3.0 Loss on ignition (%) Max, 10.0

596 H. Eskandari et al. / Procedia Materials Science 11 ( 2015 ) 594 599 3. Specimen preparation and testing The dry materials were mixed first, followed by the addition of water into the mixer. Then, the superplasticizer was added to the mixture to achieve a desirable workability. Immediately after mixing, the concrete mixtures were molded and consolidated by a vibrating table. The specimens were covered in the casting room for 24 h. The test samples were then demolded and moist cured at 23±1 ºC until the specified ages for each test. Table 3 summarizes the concrete mixture proportions. The reference concrete mixtures without additive (Z0S0) and three mixtures were made by replacing 2% of cement with nano silica and 5%, 8% and 10% of cement with micro zeolite; hereafter named as Z5S2, Z8S2 and Z10S2, respectively. The extension of 0.45 and 0.4 shows water/cement ratio. Use of natural zeolite decreased the workability of concrete which was compensated by using a commercially available Polycarboxilate superplasticizer. In this regard, the slump of the mixtures was maintained in the range of 80-100 mm. As shown in table 3, by increasing the replacement level from 5% to 10%, the superplasticizer consumption was increased. Table 3. Mixture proportions. Mixture Identification Water/Cement Ratio (W/C) Fine Aggregates (Kg/m 3 ) Coarse Aggregates (Kg/m 3 ) Cement (Kg/m 3 ) Micro Zeolite (%) Nano Silica Z0S0-0.45 0.45 899 727 378 - - 0. 3 Z0S0-0.4 0.4 881 886 430 - - 0. 4 Z5S2-0.45 0.45 899 727 378 5 2 0. 7 Z8S2-0.45 0.45 899 727 378 8 2 0. 9 Z10S2-0.45 0.45 899 727 378 10 2 0. 11 Z5S2-0.4 0.4 881 886 430 5 2 0. 9 Z8S2-0.4 0.4 881 886 430 8 2 1. 2 Z10S2-0.4 0.4 881 886 430 10 2 1. 4 (%) Superplasticizer (%) The compressive and tensile strength of the mixtures was measured on 300 150 mm cylindrical specimens according to ASTM C39-86 and ASTM C496-90 respectively. Compressive tests have done for ages 7, 28 and 90 days. Tensile, electrical resistivity and rapid chloride penetration tests were carried out on the 28 and 90 days aged specimens. The averages of the results are presented in table 4. Table 4. Results of mechanical and durability. Test Compressive Strength (MPa) Tensile Strength (MPa) Mixture ID Ages(Day) Z0S0-0.45 Z5S2-0.45 Z8S2-0.45 Z10S2-0.45 Z0S0-0.4 Z5S2-0.4 Z8S2-0.4 7 29.3 23.6 24.2 26.9 37.2 24.4 30.5 24.5 28 41 41.4 36.1 39.4 53.3 41 35.3 45.4 90 44.4 51 47 53 56 43 41 50.3 28 2.83 3.35 2.42 2.83 3.1 2.92 3.4 3.24 90 3.4 3.85 3.61 3.7 3.7 3.87 3.57 3.4 28 11.8 11.8 14 14.2 8.9 11.4 13.7 13.9 Z10S2-0.4

H. Eskandari et al. / Procedia Materials Science 11 ( 2015 ) 594 599 597 Electrical Resistivity (kω.cm) Rapid Chloride Penetration (Coulomb) 90 15.9 16.2 22.6 21.1 9.2 16.3 17.8 16.5 28 2953 2100 1627 1510 2181 1760 1773 2497 90 1704 1720 1570 1220 1960 716 791 1025 4. Results As it can be seen in Fig. 1, the compressive strength of specimens containing nano silica and micro zeolite, have been decreased and maximum decrease refer to Z8S2 specimen with both W/C ratio of 0.45 and 0.4. In term of compressive strength, it seems that natural zeolite performs better in blended cement composites with lower W/C ratios. For Z5S2, tensile strength increased insignificantly. The factors of durability were measured by electrical resistivity and rapid chloride penetration. Results show that incorporation of these mineral admixtures as pozzolanic materials have significant effects. Compressive 7 days 28 days 90 days Tensile 90 days 28da ys (a) (b) (c) (d) Fig. 1. The effect of the pozzolans; (a) Compressive strength; (b) Tensile strength; (c) Electrical resistivity; (d) Rapid Chloride Penetration. Hybrid nano silica and micro zeolite as replacement materials are not effective for mechanical characteristic. The XRD pattern (Fig. 2) confirms the high index of durability for specimens containing micro zeolite. Fig. 3 shows SEM image of specimens aged for 28 days that illustrate nano particle in cement paste in transition zone.

598 H. Eskandari et al. / Procedia Materials Science 11 ( 2015 ) 594 599 Fig. 2. XRD pattern. 5. Conclusion Fig. 3. SEM image transition zone. Based on the obtained results, the following conclusions can be drawn from this investigation: The compressive strengths of concretes containing additives were lower than the concrete without supplementary replacement at all ages. However, the percentages of reduction were lower for high ageing times, which can be attributed to lump in transition zone. Decrease rate of tensile strength is less than compressive strength in all ages. Also effectiveness of additives on strengths for mixtures with 0.45 W/C is less than 0.4 W/C, probably because of the lack of water, strength have been decreased. The optimized mixture for achieving high quality of durability is incorporation of 2% nano silica and 8% micro zeolite. The concrete contained 8% micro zeolite has high resistance for penetration chloride ion.

H. Eskandari et al. / Procedia Materials Science 11 ( 2015 ) 594 599 599 References Ahmadi, B., Shekarchi, M., Eftekharnejad, J., 2001. Improve concrete durability combined with zeolite, silica fume and fly ash. The Third Annual National Conference for Concrete. Tehran. Andrade, M., Castellote, C., Alonso, C., González., 1999. Relation between colorimetric chloride penetration depth and charge passed in migration tests of the type of standard ASTM C1202-91C. Cement and Concrete Research 29, 417 421. Byung-Wan, J., Ji-Sun, C., Kwang-Won, Y., Jung-Hoon, P., 2012. Material characteristics of zeolite cement mortar. Construction and Building Materials 36, 1059-1065. Chan, S.Y.N., Ji, X., 1999. Comparative study of the initial surface absorption and chloride diffusion of high performance zeolite, silica fume and PFA concretes. Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, Cement & Concrete Composites 21, 293-300. Ghourchian, S., Wyrzykowsk, M., Lura, P., Shekarchi, M., Ahmadi, B., 2013. An investigation on the use of zeolite aggregates for internal curing of concrete. Construction and Building Materials 40, 135 144. Nai-Qian Feng, A., Gai-Fei, P., 2005. Applications of natural zeolite to construction and building materials in China. Construction and Building Materials 19, 579-584. Najimi, M., Sobhani, J., Ahmadi, B., Shekarchi, M., 2012. An experimental study on durability properties of concrete containing zeolite as a highly reactive natural pozzolan. Construction and Building Materials 35, 1023-1033. Quercia, G., Brouwers, H.J.H., 2010. Application of nano-silica (ns) in concrete mixtures. 8th fib PhD Symposium in Kgs. Lyngby, Denmark. June 20-23. Ramezanianpour, A., Pilvar, A., Mahdikhani, M., Moodi, F., 2011. Practical evaluation of relationship between concrete resistivity, water penetration, rapid chloride penetration and compressive strength. Construction and Building Materials 25, 2472 2479. Taheri Shakib, J., Hosseini, S.A., Ghaderi, A., 2012. Cementing Operation Design by Considering both Surface and Underground Sulfate Waters in One of The Ahwaz Oil Field Wells. The 14thIranian National Chemical Engineering Congress (IChEC 2012), Sharif University of Technology. Tehran.