SBEIDCO 1st International Conference on Sustainable Built Environment Infrastructures in Developing Countries ENSET Oran (Algeria) - October 12-14,

, 2009

HOW NANOTECHNOLOGY CAN CHANGE CONCRETE INDUSTRY

Housing and Building National Research Centre, Cairo, Dokki, Egypt

S.I Zaki* and Khaled .S. Ragab

T. 2. Performance of materials ABSTRACT

In recent years, the world of science has started to produce new materials and to research their properties with nanotechnology. The use of nanotechnology has become wide spread in all branches of science. So, studies of nano-scale should be increased for concrete technology. In this study, the use of nano powders in concrete in the world have been summarized and evaluated. The influence of nano particles such as silicon dioxide added to polymers mixed in concrete was studied for both high-performance and self-compacted concrete with reference to normal size particle concrete. The progress from sulphonated polymers to polycarboxylate was studied and has resulted in higher water reduction and higher strength. Also, the influence of nano particles on the properties of fresh and hardened self-compacted concrete are studied in comparison with normal size ones. The morphology of nano particles was studied using Transmission Scanning Election Microscopy (TEM). Also, X-ray diffraction (XRD) of all the mineral additions was studied. The results indicated that the addition of nano particles improves the properties of concrete.

KEYWORDS:
Nano - composites, nano - SiO2, SCC, HPC, polycarboxylic

*Corresponding author: Saaid_Zaki@yahoo.com

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1. INTRODUCTION During the period of the second half of the previous century, the terms "nano-science" and "nonotechnology" were not yet familiarly used as today, however they were really practiced and successfully applied to the progress in the field of material science and technology. Concrete performance is strongly dependent on nano-size dimensions of solid material such as C-S-H particles or voids such as the gel porosity in the cement matrix and the transition zone at the interface of cement paste with aggregate or steel reinforcement, typical properties affected by nano-sized particles are strength, durability, shrinkage and steel-bond. The word nano means anything of size 10-9, nano particles is a solid particle of having size in the range 1 to 100 nm. The purpose of the present work is to study a new material in the dimension range between "micron " and " nano " size , this material is nano silica (Nano-SiO2) which added to new super plasticizer (polycarboxylic ether polymerd based PCE Sky) to improve workability , strength , flexibility and durability of high-performance and selfcompacted concrete. There are few studies on the application of nano-technology in concrete production summarized below: Collepardi S. et al., studied the influence of nano-sized mineral additions on performance of self-compacted concrete and found that Poly-functional super plasticizers are able to keep the initial slump for at least 1.0 hour without any retarding effect on the early strength and also reduce drying shrinkage. Soblev K. et al. used polycarboxylic ether polymer based PCE Sky mixed with nano Si02 to improve workability and strength of high-performance and self-compacted concrete. Ferrada M.G. Studied the use of commercial nano admixture for concrete called Gaia to substitute for silica fume at ready-mixed and achieved two fold increase in concrete compressive strength at the age of 7 and 28-days , he used cement content 460 kg/m3 at ambient temperature 20C. Sobolev K. and Ferrada M.G., studied the application of Gaia super plasticizer containing nano-SiO2 particles at a dosage of 1.3% by weight of cementitious materials and found that there is an increase in concrete compressive strength (100-150) % at the age of 7 and 28 days when used the above superplasticizer mixed with nano Si02 and this dependent on w/c ratio. Remzi S. and Meral O., made a literature review on the researches studied the effect of nano powders on cement paste, mortar and concrete and found that the use of nano powders in concrete technology affects the cement kinetics and accelerates hydration significantly due to larger surface area, stronger electrostatic forces of nano powders, and due to improvement in the microstructures of concrete having nano powders. Li G. studied the properties of high volume fly ash concrete incorporating nano-SiO2 and found that the addition of nano-SiO2 can activates fly ash, leads to an increase of both short-term and long term strength, and acts as an accelerating additive leading to more compact structure even at short curing times. Zhang G. studied the effect of blending CPE (carboxylic polymer ether) to nano-SiO2 and found that the addition of nano-SiO2 to CPE polymer increases strength, flexibility and aging resistance since nano-SiO2 interpenetrates polymer networks. Hui Li studied the flexural fatigue performance of concrete containing nano- particles (nano-SiO2 and nano-TiO2) for pavements and found that the fatigue of concretes containing nano - particles follows the double parameter weibull distribution , the flexural fatigue performance of concretes containing nano-particles is improved significantly especially when contained nano-TiO2 in the amount of 1% by weight of binder, which is much better than that of concrete containing polypropylene fibers (PP) which has been extensively used to improve fatigue performance of concrete pavements. Sobolev K. carried out an investigation study nano materials and nanotechnology for high-performance cement composites and found that the major problem of nano-SiO2 application is strength loss at later ages due to the agglomeration of nano particles (30-100 nm) at the final drying stage of sol-gel method which can be solved using acrylic polymer based super plasticizer called Gaia at a dosage of 1.3% by weight of cementitious materials , also Sobolev K. found that high-temperature treatment at (400c or more) of nano-SiO2 concrete affects the performance of these additives and must be avoided. Jorge IV (10) carried out an investigation about Portland cement blended with nano particles and found that nanotechnology is a new topic in cement industry to produce high performance concretes , since there is mineralogy modifications of cement paste and mortars occurred due to the incorporation of nano particles like nano-SiO2, nano-Tio2. R. Abbas carried out an investigation to study the influence of Nano-Silica addition on properties of conventional and ultra-high performance concretes and found that nanoSilica (NS) concretes requires additional amount of water , since each kilogram of NS added required 0.4 kg of water to maintain the same workability, also nano-silica addition resulted in significant early increase in compressive, splitting and flexural strengths of concrete in case of high cement content and
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low w/c ratio . Also, addition of 5% nano-silica leads to an increase 50% in 7-day compressive strength and 40% in 28-day compressive strength when compared with the same concrete without nano-silica. 2. EXPERIMENTAL WORK In this work, the well known performance of concrete without nanoparticles was compared with that after the addition of nano-particles for both fresh and hardened states. 2.1. Materials The cementitious materials used during this study were OPC, silica fume, nano-silica. Ordinary Portland cement (OPC) was used of type (CE M1 42.5N) according to E.S.S. (4756-1-2006) obtained from Beni-Suef cement Factory in Egypt. Silica fume was obtained from Egyptian Company for Iron Foundries, while nano Silica was exported from Sigma-Aldrich Company in Germany through International Egyptian Center for Export. Polycaboxilate-based super plasticizer (30% in aqueous solution) was used in comparison with sulphonate naphthalene super plasticizer to produce self-compacting concrete (SCC) with relatively low water-cement ratio. 2.1.1. Ordinary Portland Cement (OPC). Chemical analysis of OPC is shown in Table (1). 2.1.2. Silica Fume. Silica fume is a very fine by-product powder obtained as a fume from the foundry process in the Egyptian Company for Iron Foundries. Figure (1) shows the morphology of SF by transmission scanning Electron Microscopy (TEM) carried out in the National Research Center. Table (2) shows the physical properties of used Silica fume. 2.1.3. Nano Silica. NSF is synthetic product with spherical particles in the range of 1-50 nanometers. It has already been studied as viscosity modifying agent in combination with super plasticizers in order to produce high performance SCC, the product used in this study is colloidal silica water emulsion (30% dry solid with particle size distribution of the solid material in the range of 5-15 nm. The chemical analysis shows that it consists mainly of pure silica (>99%) dispersed in an aqueous phase as shown in Table (1). Table (3) shows the physical properties of used NSF. Figure (2) shows the morphology of NSF. Figure (3) shows the XRD patterns of the mineral additions (SF and NSF). The X-ray diffraction patterns (XRD) indicated that the crystalline behavior of both nano-Si02 and silica fume is low and the used nano-Si02 is a highly amorphous material. Table 1.Chemical Composition of Cementitious Materials % Si02 A12O3 CaO MgO Fe2O3 Na2O K2O SO3 LOI , Loss of Ignition OPC 19.8 5.5 63 1.18 3.39 0.46 0.16 3.01 5.2 SF 93 0.2 0.3 0.1 2.0 NSF 99.1

Table 2.Properties of silica fume Description Particle Size (nm) Surface area (m2/gm) Density (g/ cm3) Results 34 14 2.22

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Table 3.Properties of Nano-silica Description Particle Size (nm) Surface area (m2/gm) Density (gm/cm3) Molecular Molecular weight Results 24 200 0.505 SiO2 60.08

2.1.4. Superplasticizer Sulphonated naphthalene base super plasticizer (Plastmix F) was used in the first part of the experimental work of this study , then polycarboxylic ether polymer based PCE SKY was used in the second part of this study ( Glenium ACE 30 and Glenium SKY 510). The first super plasticizer (Plastmix F) was obtained from Construction Chemicals Expertise Company in Egypt, while the second super plasticizer (Glenium) was obtained from BASF chemical company in Egypt. 2.1.5. Aggregates 2.2. Concrete Mix Design With And Without Nano Particles Self-Compacting concretes (SCC) have been manufactured with and without nano particles in order compare the well known performance of SCC without nano particles with that with nano ones. So , self-compacting concretes with a binder content of 550 kg/m3 were manufactured in all concrete mixes as shown in table (4-a) and (4-b) , the water binder ratio was the same for concrete mixes equal 0.39 for mixes M1 to M5 while 0.35 for mixes M6-M10. A proper dosage of super plasticizer 6 lit/m3 for mixes M1 to M5 as shown in table (4-a) and was 10 lit for mixes M6 to M9 as shown in Table (4-b). SCC was characterized in fresh state during this study using slump-flow and J-ring tests since the two theological measurements are suitable for both laboratory and site application. The composition of self-compacting concretes with and without NSF is shown in table (4-a) in case of using lignosulphonate super plasticizer. M1 is control mix No. (1) without SF or NSF , while M2 is control mix No.(2) in which 100 kg of cement was replaced with 100 kg of SF. Table (4-b) shows the same composition in case of using polycarboxyate super plasticizer. Nano-Silica was added in three percentages (0.5, 0.7and 1%) of weight of cementitious materials (cement and SF). Natural sand of size (0-4 mm) was obtained from pyramid quarry in Egypt, while the coarse aggregate was dolomite obtained from Attaka quarry in Egypt; two nominal maximum sizes were used during this study: Aggregate 1 of size (4-20) mm and Aggregate 2 of size (20-40) mm. Table 4-a.Composition and properties of SCC in the fresh state with and without NSF using lignosulphonate superplasticizer Description Control Nano zero% Nano 0.5% Nano 0.7% Nano 1% Mix. No M1 M2 M3 M5 M4 OPC kg/m3 550 450 450 427 450 SF 100 100 100 100 NSF 2.75 3.5 5.5 Sand 760 760 760 780 760 Dolomite 760 760 760 855 760 Water 211 220 220 190 220 Superplasticizer. 3.5 6 6 6 6 Slump flow(cm) 70 56 46 39 37 J-ring(cm) 56 50 44 35 32 T50 (sec.) 2 5 7 w/p 0.38 0.4 0.397 0.388 0.396

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Table 4-b.Composition and properties of SCC in the fresh state with and without NSF using polycarboxylate superplasticizer Description Control Nano zero% Nano 0.5% Nano1% Nano 0.7% Mix. No M6 M7 M8 M9 M10 OPC kg/m3 550 450 450 450 450 SF 100 100 100 100 NSF 2.75 5.5 3.5 Sand 575 575 575 575 575 Dolomite 1070 1075 1075 1075 1075 Water 192.5 192.5 192.5 192.5 192.5 Superplasticizer. 10 lit 10 10 10 10.0 Slump flow(cm) 53 57 J-ring(cm) T50 (sec.) w/p 0.35 0.35 0.35 0.35 0.35 2.2.1. Mixing Procedure. The cement , fine aggregate , coarse aggregate and silica fume were dry mixed in a rotary mixer for 30 sec. , then 80% of mixing water was added and mixed for 30 sec. , then a ready-mixed liquid including super plasticizer and nano-Si02 was added to the 20% remained water and then the liquid poured into the rotary mixer slowly . The concrete mixture was mixed wet for additional 1.5 min. 2.2.2 Testing Procedure. After mixing , slump flow and J-ring tests were carried out to measure the properties of self-compacted concrete (SCC) according to standard specifications for testing SCC (12) , then the well-mixed concrete mixture of each mix was poured into twelve standard cubes of dimensions 15x15x15 cm for each mix , Five concrete mixes were cast for both lignosnlphonate super plasticizer mixes (M1 to M5) , and polycarboxylate super plasticizer mixes (M6 to M10) , cubes were demolded after 24 hrs and then cured in standard curing tank until the age of testing , where , cubes were dried in air for one hour before testing and then tested three cubes after 7 , 28 , 90 and 365 days. 2.3. Scanning Electron Microscopy SEM Scanning Electron Microscopy was carried out in Natural Research Center at Physics Department for Transmission Scanning for powders (SF and NSF) and the data of microscope is :Transmission Electronic Microscopic type JEOL JEM 1230 of magnification up to 60000 made in Japan was used for powders (SF and NSF). It can be observed that nano-Si02 particles are represented by highly agglomerated clusters with the size of 24-32nm. Scanning Electron Microscopy was also carried out in the same National Research Center Central Laboratories for Services for concrete samples with and without nano Si02 using Electronic Microscope type JEOL JXA-840 A, OXFORD, of magnification 5000 and 6500. The specimens were cut directly from concrete cubes, the shape of specimens was regular and the surface was flat. Table 5-a.Properties of hardened concrete with and without nano particles using lignosulphonated superplasticizers. Compressive strength kg/cm2 Mix No. Mix description 7-day 28-day 90-day 1-year M1 Control 450 550 560 700 M2 nano SiO2 0.0% 501 566 600 740 M3 nano SiO2 0.5% 472 578 622 800 M4 nano SiO2 1.0% 442 467 580 644 M5 nano SiO2 0.7% 442 545 590 750

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Table 5-b.Properties of hardened concrete with and without nano particles using ploycarpoxylate superplasticizers. Compressive strength kg/cm2 Mix No. Mix description 7-day 28-day 90-day 1-year M6 Control 614 720 800 1000 M7 nano SiO2 0.0% 640 750 840 1050 M8 nano SiO2 0.5% 700 800 900 1150 M9 nano SiO2 1.0% 650 720 800 1020 M10 nano SiO2 0.7% 680 780 870 1100 Fig.6 (a, b) shows the electronic scanning photographs of control sample without nano-Si02 which magnify the microstructure 5000 and 6500 times. Fig. 7 (a, b) shows the electronic scanning photographs of nano-Si02 concrete samples which magnify the micro structure 5000 and 6500 times. 2.4. X-Ray Diffraction The particle size distribution of SF and NSF was measured in HBRC at Raw Building Materials Technology and Processing Research Institute Laboratories using diffraction scattering particle size distribution analyzer Horiba AL-950.

Figure 1. a, b. TEM micrograph of SF

Figure 2. a, b. TEM micrograph of NSF 3 ANALYSIS AND DISCUSSION OF TEST RESULTS 3.1. Compressive Strength Table (5-a) and Fig.(4) show the compressive strengths of concrete with and without nano-particles using lignosulphonated super plasticizer . It can be seen that compressive strength of concrete with nano-particles was improved at 28-days up to one-year and the optimum amount of nano-Si02 is 0.5% by weight of the cementitous material content. Table (5-b) and Fig.(5) show the compressive strengths of concrete with and without nano particles using polycarboxylate super plasticizer . It can be seen also that compressive strength of concrete with nano particles was improved at 28-days up to one-year and the optimum amount of nano-Si02 is 0.5% also, but the strength level for polycarboxylate nano concretes is (43-48) % higher than lignosulphonate nano concretes, this is due to improvement in the activity of nano-Si02 when polymcarboxylate super plasticizers are used.

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3.2. Microstructure To verify the mechanism predicted by the compressive strength test, SEM examinations were performed. Additions of nano-Si02 particles were found to influence hydration behavior and lead to differences of the microstructure of hardened concrete Fig. (6) Shows SEM micrograph of control sample (without nano-Si02) after one-year with magnification of the microstructure 5000 times in fig.(6-a) and 6500 times in fig. (6-b). It can be seen that calcium silicate hydrate (C.S.H.) existed in isolated points surrounded by many needle-hydrates, on the other hand the microstructure of the mixture containing nano-Si02 of amount 0.5% by weight of cementitious materials revealed a dense , compact formation of hydration products (C-S-H) as shown in fig. (7)-(a) and (b) , since the texture of (C-S-H) of nano-Si02 concrete is very dense , compact and with big crystals.
Counts/s 40 30 20 10 0 SF

N-Si

40

20

0 10 20 30 Position [2Theta] 40 50

Figure 3. XRD patterns of the mineral additions (SF and NSF) (b) Silica Fume (a) Nano-SiO2

Figure 4. Development of concrete strength with time using lignosulphinated superplasticizer.

Figure 5. Development of concrete strength with time using polycarboxylate superplasticizer

(a) (b) Figure 6. SEM micrograph of control sample after one year.

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(a) Magnification 5000 (b) Magnification 6500 Figure 7. SEM micrograph of Nano SiO2 Concrete sample after one year.

4. Conclusions and Recommendations

The properties of concrete are improved by the use of nano powders, since nano particles fill the voids between cement grains and also consume a part of calcium hydroxide which results in additional formation of calcium silicate hydrate (C.S.H.) and more improvement of interface structure. The application of nano SiO2 particles with newly developed super plasticizer (polycarboxylic ether polymer based PCE sky) improved the workability and strength of high performance and selfcompacted concrete since nano-SiO2 interpenetrates polymer network, and causes the above improvements. The progress from sulphonated polymer to polycarboxylate has resulted in higher water reduction at a given workability, lower slump loss and (43-48) % higher compressive strengths, according to the indicated results. The efficiency of nano particles such as nano-Si02 depends on their morphology as well as the application of effective super plasticizers which help to disperse formation of agglomerates and improve concrete strength. Nan particles, such as nano silica dioxide (Nano-SiO2) were found to be very effective when mixed separately with super plasticizer (polycarboxylate base) and then added to the 20 % remained of mixing water as mentioned in mixing procedure. Nano-Silica concrete requires additional amount of water or super plasticizer to maintain the same workability level. Nano-Silica addition results in significant increase in concrete compressive strength after 28-days up to one year and the optimum amount of nano silica is 0.5% by weight of cementitious material. REFERENCES
Collepardi S.etal.,Influence of nano-sized Mineral additions on performance of SCC6th International Congress, Global Construction, Ultimate concrete Opportunities, Dundee, U.K., July 2005. Sobolev K., et al., "How Nano technology can change the concrete world", American Ceramic Society Bulletin, Vol. 84, No. 11, Nov. 2005. Ferrada M.G., et al., " U-Silice ISO 14001: Silice a Favor del Media Ambiente, " XIV Jornalas Chilenas del Hormigon, Valdivia, Chili, 2003. Sabolev K., and Ferrada M.G." Nano-technology of concrete, http:// www.nano-cement.50 webs.com Remzi S. and Meral Q, " New Materials for concrete Technology: Nano powders ", 33rd conference on our world in concrete & structures, Singapore, 25-27 August 2008, pp (399-406). Li, G "Properties of high-volume Fly ash concrete in corporating nano-SiO2" Cement and Concrete Research, vol. 34, No.6, Jun. 2004, pp 1043-1049. Zhang Q. et al.,"Study on the CPE / Nano SiO2 blends,"Journal of function polymer 15(3), 2002, pp 271-275. Hui Li et al., "Flexural Fatigue performance of concrete containing nano particles for pavement", International Journal of fatigue, Nov. 2006. Soblove K. et al., "Nano materials and Nano- technology for High-performance cement composites", Proceedings of ACI Session on "Nano technology of concrete", Nov. 2006, Denver, USA. Jorge IV et al., "Portland Cement Blended with Nano particles", Revista DYNA, Universidad Nacional de Colombia sede Medellin calle 59 A No. 63-20, 2006. R. Abbas , " Influence of Nano-Silica addition on properties of conventional and ultra-high performance concretes " , HBRC Journal , vol.20, No. 20, April 2009, p.p. (1-13). Egyptian Technical specifications for self-compacted concrete, Ministerial Decision no. 360, 2007.
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