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Construction and Building Materials 133 (2017) 91–97 Contents lists available at ScienceDirect Construction and Building Materials journal homepage: www.elsevier .com/locate /conbui ldmat Review Applications of using nano material in concrete: A review http://dx.doi.org/10.1016/j.conbuildmat.2016.12.005 0950-0618/� 2016 Elsevier Ltd. All rights reserved. ⇑ Corresponding author. E-mail addresses: norhasri@gmail.com (M.S.M. Norhasri), hmidsaman@yahoo. com (M.S. Hamidah), fadiil2013@yahoo.com (A.M. Fadzil). M.S. Muhd Norhasri a,⇑, M.S. Hamidah b, A. Mohd Fadzil c a Faculty of Civil Engineering, Universiti Teknologi MARA, Cawangan Pulau Pinang, Malaysia b Faculty of Civil Engineering, Universiti Teknologi MARA, Shah Alam, Malaysia c Institute of Infrastructure and Sustainable, Engineering and Management (IIESM), Universiti Teknologi MARA, Shah Alam, Malaysia h i g h l i g h t s � An overview from the past and current research highlights regarding nano materials in concrete. � Provide knowledge on the nano materials and application in enhancing human life. a r t i c l e i n f o Article history: Received 25 May 2016 Received in revised form 30 November 2016 Accepted 2 December 2016 Available online 23 December 2016 Keywords: Nano material Nano silica Nano alumina Nano kaolin Nano clay a b s t r a c t This review paper discussed on the nano materials in concrete. Nowadays, the application of nano mate- rials has received numerous attentions to enhance the conventional concrete properties. Eventually, the introduction of nano materials in concrete is to increase its strength and durability. Nano material is defined as material that contains particle size which less than 200 nm. For the purpose of concrete study, the application of nano materials must be at least 500 nm in size. The addition of ultrafine nano material will help to reduce the cement content by partially replacing cement on weight basis to improve the binding effect. The ultrafine particles of nano material will also help reduce the formation of micro pores by acting as a filler agent, producing a very dense concrete and automatically reduce the growth of micro pores in the UHPC structures. Moreover, this paper presents on the advantages and benefits to enhance the concrete by utilizing nano materials. � 2016 Elsevier Ltd. All rights reserved. Contents 1. Background of concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 2. Development of nano concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 3. Production of nano materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 4. Application of nano materials in UHPC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 5. Nano silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 6. Nano alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 7. Carbon nano tube (CNT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 8. Polycarboxylates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 9. Titanium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 10. Nano kaolin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 11. Nano clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 12. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 http://crossmark.crossref.org/dialog/?doi=10.1016/j.conbuildmat.2016.12.005&domain=pdf http://dx.doi.org/10.1016/j.conbuildmat.2016.12.005 mailto:norhasri@gmail.com mailto:hmidsaman@yahoo.com mailto:hmidsaman@yahoo.com mailto:fadiil2013@yahoo.com http://dx.doi.org/10.1016/j.conbuildmat.2016.12.005 http://www.sciencedirect.com/science/journal/09500618 http://www.elsevier.com/locate/conbuildmat 92 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 91–97 1. Background of concrete Evolution of concrete has started from normal grade concrete from grade 5–45 [1,2]. Those grades were popular in 1900’s for construction purposes and provide adequate strength for general application. To achieve the design, the mix proportion of normal grade concrete consists of cement less than 380 kg/m3, normal type of aggregates which is normally granite, medium water requirement and little dosage of superplasticizers [3]. Eventually, starting from 1960, when unique design of structure was created and most of the structure carries load more than 50 MPa up to 95 MPa [4,5]. Since then, a new technology for concrete was cre- ated like High Strength Concrete (HSC). HSC can withstand load capacity from 50 MPa until 90 MPa [6,7]. Prior to that, it can be seen that concrete has been utilised for high rise building, bridges and heavy load structures. In terms of mix proportion, HSC requires more cement, high content of aggregates, less water and adequate superplasticizer. To realise this, additives and supple- mentary materials such as silica fume, fly ash, metakaolin and other pozzolanic were implemented [8–10]. Silica fume was popu- lar in HSC mix due to its ability to increase strength at adequate percentage of cement replacement [10–14]. In contrary, fly ash (FA) addition in HSC mix increases flow ability and also act as nat- ural admixture. Other advantages of using FA in HSC mix is, FA can be an alternative to superplasticizer because it can be replaced at higher dosage and is cost effective [15–18]. Metakaolin (MK) as cement replacement material has started since early 90’s [19– 23]. Metakaolin is a secondary product of kaolin after undergone heat treatment. The unique feature of MK is it is clay based and allows low water penetration into concrete. Table 1 tabulated the different mix proportion between normal concrete, high strength concrete with silica fume inclusion and UHPC mix used in other studies. Obviously an increase in cement component is seen from those three different concretes. Furthermore, other properties which include aggregates, admixture, water to cement ration and slump are also different. 2. Development of nano concrete Nano concrete is a concrete that utilises nano materials or a concretewith nano materials added in which the size of the nano particles is less than 500 nm [6,26–31]. It was believed that the addition of nano particles in concrete improve the strength of con- ventional concrete. Nano particle works in concrete by improving the bulk properties or also known as packing model structure. Ultra or nano particles can perform a superb filler effect by refining the intersectional zone in cement and producing more density con- crete. By acting as good filler, their manipulation or alteration in the cement matrix system occurs to provide a new nanoscale structure. Common discrepancies in concrete microstructure such as micro void, porosity and deterioration due to alkali silica reac- tion will be eliminated. Next, nano materials start to evolve when they become new binding agent which is smaller than cement par- ticles. This improves the structure of hydration gel providing a neat and solid hydration structure. In addition, through the combina- tion of filler and additional chemical reaction in hydration system, Table 1 A summary of concrete properties for different types of concrete obtained from past resea Compressive strength (MPa) Flexural str Normal concrete 10–40 1–10 High performance concrete (HPC) 41–100 11–20 Ultra high performance concrete (UHPC) 100 20–30 Nano concrete 70 12–20 a new concrete called nano concrete with durable and enhanced performance has been developed [5,32,33]. Implementation of nano technology in concrete has started since the early millennium in line with the increasing demand for UHPC. Conventional mix formulations of UHPC with the inclu- sion of silica fumes provide better durability and strength. How- ever, due to limited availability and also the high cost of silica fume makes UHPC technology declining and less demanding com- pared to HSC. Since then, emerging technology in nano production has developed an alternative to silica fume. By applying nano pro- duction concept, a common nanomaterial which mimics the action of silica fume is designed. Nano silica is one of the newest tech- nologies in nano process which has been used as an alternative to silica fume [34]. Since the breakthrough of nano silica, many nano based particles has been developed to be used in concrete. Nano alumina [35], titanium oxide [36], carbon nano tube [37] and polycarboxylates [38] are examples of nano materials used in nano concrete. The following sub-section explains on the production and application of nano materials. 3. Production of nano materials Since the emergence of nano technology in the late 60’s, the idea and concept of producing nano materials have also been developed. The nano size in nano particles produces a greater effect on filler as compared to micro based materials. Guterrez [39] reported that all materials can be transformed into nano par- ticles. The success of nano particle formation is when it can influ- ence the purity or basic chemical composition of parent materials. From that, two methods were developed. The first is top to down approach [40] and the second is bottom to up approach [41]. Selec- tion of those two methods is based on suitability, cost and exper- tise of nano behaviour [2,24,25]. One of the technique for top to down approach is using milling. The selection of milling technique is due to the availability of the milling machine and its feasibility as any modification can be applied directly without any chemical or electronic devices needed. The definition of top to down approach is, larger structures are reduced in size to nanoscale while maintaining their original properties or chemical composi- tion without any alteration on atomic level control [1,42]. In other words, bulk materials are broken down into nano particles by mechanical attrition and etching techniques. This method is uti- lised in massive industries. Nano particles produced are in high volume using milling technique since is cost effective and easy to be maintained as it involves more mechanical instruments and less chemical alteration. Another term used to describe top to down approach is contemporary method in nano fabrication. However, uniformity and quality of the final product are inconsistent in top to down approach. Although there are disadvantages in top to down approach, with modification on milling techniques which includes numbers of ball, types of ball, speed of milling and types of jar used, the quality of nano particles can be improved [40,43,44]. High energy ball millings are widely exploited in syn- thesising nano particles which involves nanomaterials, nanograins, nanoalloy, nanocomposites and nano quasicrystalline materials. The pioneer of milling technique was John Benjamin in producing rchers. ength (MPa) Porosity (%) Water absorption (%) Remark <30 <30 Mehta and Monteiro [3] 12–25 12–25 Hamid, Yusof [49], [50,51] <10 <12 Hartmann [52], [53,54] <10 <12 Aïtcin [26], Chong [28] M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 91–97 93 oxide particles in nickel superalloys (1970). His first attempt using milling was when he altered and strengthened alloy component for application in high thermal structure [45]. During milling, plastic deformation, cold welding and fracture are the factors influencing the deformation and transforming process of materials into required shape. Milling does not only breaking materials into smal- ler parts but also blending several particles or materials and trans- forming them into new phases of material composition. Normally, the final product of milling technique is flakes in shape but refine- ment can be done depending on the selection of ball and type of milling. However, most of nano materials such as nano silica, nano alumina, nano clay which were used in concrete are produced by using bottom to up approach. Bottom to up approach is adopted when materials are engineered from atoms or molecular compo- nents through a process of assembly or self-assembly. It also known as molecular nanotechnology or molecular manufacturing process which involves more indirect applications such as synthe- sis and chemical formulation [24]. Nano particle size and shape created by using bottom to up approach can be designed and con- trolled using chemical synthesis technique. The difference in this method as compared to top to down is the bottom to up approach will produce more uniform and neat structure of nano particles. In other words, bottom to up also produces new nanocrystals because the atom or molecules are perfectly ordered or crystalline. The techniques involved are electronic conductivity, optical absorption and chemical reactivity [25,46]. By using bottom to up technique, reduction in size and neat surface atom formation can be achieved and imparts a huge change in surface energies and morphologies. Normally, by using this technique, application of nanomaterials can be widely adapted in conditions such as improving in catalytic capability, sensing wave ability, new pigments and paint with self- healing and cleaning features. However, the disadvantage of bot- tom to up approach is its expensive operational cost, expertise requirement in chemical applications and limited suitability as it meant for laboratory only [39,47,48]. However, nanoparticles har- vested using this method is also best for advance applications such as in electronic component and biotechnology. As a conclusion, apart from evaluating the effects of nano mate- rials, two (2) different approaches of producing kaolin as nano materials to be utilised in UHPC were also discussed. Thus, it is evi- dent that there are two different methods of producing nano mate- rials in developing new UHPC. 4. Application of nano materials in UHPC Since the breakthrough of nanotechnology in the field of con- struction, various nano materials have been adopted in concrete. As mentioned in earlier sections, improvement in enhancing per- formance and durability of concrete can be achieved by using nano materials. In this sub sections, discussionon the nano materials reported by previous researchers and its use in UHPC will be fur- ther elaborated. 5. Nano silica Nano silica is a breakthrough in nanomaterials that has been applied in UHPC. In general, nano silica was produced from micro based silica. The positive reactions created by nano silica in UHPC are similar to silica fume or micro silica which are in terms of per- formance strength and durability enhancement [55–57]. Studies by Qing, Zenan [56], showed that concrete with addition of nano silica gained early strength as compared to that of silica fume. It was also revealed that the addition of nano silica in concrete improved workability of concrete while the addition of superplas- ticizers is at a minimum dosage. The reason behind the workability improvement is the round shape of nano silica which provides a ball bearing manoeuvre in cement particles. Furthermore, size of nano silica which in nano particles acts as ultra-filler in concrete. Micro voids in concrete will be densified and refined to provide neat concrete microstructure [58,59]. Other advantages of nano sil- ica are the water to cement ratio can be controlled and targeted strength can be modified easily with controlled dosage. Another report by Quercia. G, Hüsken. G [60] revealed that the addition of nano silica at certain dosage just not improved strength of HSC but also acted as cement replacement material. About 20%–30% of cement content can be reduced by nano silica. Thus, nano silica can be an alternative material to cement. However, the disadvan- tage of nano silica is its price and availability in certain countries. Some countries have to import nano silica to be used in concrete industry [4]. 6. Nano alumina Silica and alumina are two (2) major chemicals involves in cement hydration. The function of silica in cement is to change strength properties where alumina controls the setting time of cement. Nano alumina is formed from alumina itself. There are limited studies reported on the use of nano alumina in concrete. The addition of nano alumina in concrete especially UHPC can hugely affect concrete properties as it controls the setting time of cement. The function of nano alumina in cement is to speed up the initial setting time for UHPC. This will reduce segregation and flocculation. Disruption in cement will create non homogene- ity in UHPC mixes, and hence the performance of UHPC will be affected. Nano alumina in UHPC acts as dispersion agent in cement particles [61–64]. Furthermore, since the size is in nano form, nano alumina also refines the voids in the hydration gel as nano filler. Since cement content in existing UHPC proportion is high, disper- sion of cement grains in UHPC must take place concurrently with silica action in the hydration process. Without nano alumina refin- ing of hydration product, the hydration process will be slower because the internal structure of hydration gel cannot be pene- trated by silica component. By adding nano alumina, the path will be created and silica or binding materials will be easily injected into the microstructure of hydration gel and the refining process will start [27,62,65]. 7. Carbon nano tube (CNT) Carbon nanotube (CNT) is allotropes of carbon with a cylindrical nanostructure. Nanotubes have been constructed with length-to- diameter ratio of up to 132,000,000:1, significantly larger than any other material. These cylindrical carbon molecules have unu- sual properties, which are valuable for nanotechnology, electron- ics, optics and other fields of materials science and technology [1,39,66]. In particular, owing to their extraordinary thermal con- ductivity and mechanical and electrical properties, carbon nan- otubes find applications as additives to various structural materials. Nanotubes are members of the fullerene structural family. Their name is derived from their long, hollow structure with the walls formed by one-atom-thick sheets of carbon, called graphene. These sheets are rolled at specific and discrete angles, and the combina- tion of the rolling angle and radius decides the nanotube properties [37]. Nanotubes are categorised as single-walled nanotube (SWNT) and multi-walled nanotube (MWNT). Individual nanotubes natu- rally align themselves into ‘‘ropes” held together by van der Waals forces or more specifically pi-stacking [67,68]. Those so called ropes in CNT structure are chemically bonded in CNT structure. The chemical bonding of nanotubes is composed similar to those 94 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 91–97 of graphite. These bonds, which are stronger than the bonds found in alkanes and diamond, provide nanotubes with their unique strength. The advantage of using CNT in UHPC is its flexibility. From this, the design of UHPC can be altered into either unique or rigid design. Flexibility provided by CNT also increases the strength of UHPC. As compared to other nano materials, CNT is the best nano material in terms of improving flexibility and enhancing strength of UHPC [37]. Most of all, volume and size of CNT are smaller as compared to other nano materials. The main reaction of CNT in UHPC is to improve the tension and compression abilities [69]. Steel reinforcement section can be replaced by CNT which permits extra loads to be handled. By replacing steel in UHPC, it was believed that more lightweight and less reinforcement sections can be created. In addition, time and the cost of construction can be reduced. However, lack of CNT sources reduces the interest of having CNT in UHPC. Being extremely pricy, having less expertise and limited guidelines in it preparation are some of the factors that makes CNT not unsuitable for UHPC mix. 8. Polycarboxylates Polycarboxylates is one of the nano materials that has been used in concrete [70]. In general, polycarboxylates (PCE) is a poly- mer based composed by methoxy-polyethylene glycol copolymer acts as secondary or side reaction that is reinforced with methacrylic acid copolymer which acts as the main component. The carboxylate group normally consists of water particle, provid- ing a negative charge along the PCE backbone. The polyethylene oxide group offers a non uniform distribution of electron cloud, which gives a chemical polarity to the secondary or side reaction. The number and the length of secondary or side reactions are flex- ible parameters that are easy to change. When the secondary or side reactions have a huge amount of electron units, they lower their high molar mass and change the density of the polymer, which results in poor performance on cement suspensions. In order for both chains to merge and paired at the same time, long side particles and high charge density must be connected from one to another reaction. Normally, polycarboxylate is applied in concrete as high range water reducer (HRWR). The addition of PCE will help to control the workability of concrete at low water to cement ratio. The prop- erties of PCE in concrete depend on the dosage of PCE. Too high dosage will result in false set or no hydration occurrence in con- crete [71]. Apart from that, inclusion of PCE at required dosage will produce Self Compacting Concrete (SCC). SCC increases the worka- bility of concrete and produces a flow concrete which gives great impact during the placing of concrete at low and high intensity area. Another advantage of having PCE in UHPC or concrete is its ability to be used in marine structure. Since PCE has the ability to remove air bubble in improving density of concrete, pores or voids in UHPC will be reduced to provide a compact structure. In addition, refining of UHPC microstructure will prevent or reduce the rate of permeability when dealing with marine condition. From that, the attacks of sea water such as sulphate and chloride content can be controlled or reduced. Besides, the use of polycarboxylate is considered as a greener technique compared to silica fume and any additives in refining microstructure of UHPC. Sobolev (2005)reported that utilisation of PCE in HSC enhances workability and performance compared to that of silica fume. Furthermore, almost 70% of depending material in UHPC such as silica fume, superplas- ticizers and fibers can be reduced [2,32]. Finally, the study showed that PCE in UHPC enhances the strength performance as compared to those of plain UHPC or HSC. Crainic (2002) reported that PCE inclusion at around 2.5% of cement weight rapidly increases strength of HSC at early age. It was reported that at day one, the strength of HSC can go from 40 to 80 MPa. At 28 days, strength can be achieved at around 70–100 MPa easily at lower dosage of PCE. This proves that PCE can be an alternative admixture to enhance the strength of concrete. Due to its easy handling charac- teristics with minimum guideline or technique required, makes PCE one of the most popular nano materials to be adopted in UHPC. 9. Titanium oxide Titanium oxide (TiO2) is also known as titania, is the naturally occurring oxide of titanium. The chemical formula for titania is TiO2. When used as a pigment, it is called titanium white. Gener- ally, it is sourced from ilmenite, rutile and anatase. It has a wide range of applications, from paint to sunscreen to food colouring. Titanium dioxide occurs in nature as well-known minerals rutile, anatase and brookite. Additionally, titanium is also formed from two (2) high pressures called monoclinic baddeleyite-like form and an orthorhombic form, both found recently at the Ries crater in Bavaria [67,72]. It is mainly sourced from ilmenite ore. This is the most widespread form of titanium dioxide-bearing ore around the world. Rutile is the next most abundant and contains around 98% titanium dioxide in the ore. The metastable anatase and broo- kite phases convert after heated above temperatures in the range 600�-800 �C [25,73]. Normally, the addition of TiO2 in UHPC and concrete has proven a great effect on self-cleaning ability and contribute to the applica- tion of green material in construction [74]. Self-cleaning effect of TiO2 has been utilised in buildings, paving material and the finish product can be seen on the construction of Jubilee Church in Rome Italy [25]. Another benefit of TiO2 is accelerating strength of con- crete at early age. Furthermore, performance of concrete also improves and abrasion resistance in concrete increases [75]. Basi- cally, those effects are provided by TiO2 in UHPC and concrete due to TiO2 is ability to act as glass layer or pigment outside the concrete particles and also in the microstructure of UHPC and con- crete. Those layers react to the hydration gel during mixing and act as protective layer that gives self-cleaning ability to the concrete surface. The self-cleaning effect provided by TiO2 surrounds the outer surface concrete and coats concrete surface which is hard and permeable. For enhancement in performance, TiO2 in concrete forms a fiber reinforced system which can be seen mimicking the glass fiber effect. Refining and tailoring the hydration gel by acting as fiber contribute to the strength enhancement and more durable concrete [76]. However, issues on safety and health were among the problems arised in TiO2. Although there is no report on the pollution but par- ticles of TiO2 which are dusty and small create the environmental effect to factory workers during packing and production. It was believed that titanium creates inflammatory effect and danger- ously causing cancer to factory workers [75]. Therefore, care during handling must be taken seriously which includes mixing process of TiO2. 10. Nano kaolin Nano kaolin is a by-product of kaolin. Kaolin or its chemical name, kaolinite is a clay mineral, part of the industrial minerals, with the chemical composition Al2Si2O5(OH)4. It is a layered sili- cate mineral, with one tetrahedral sheet linked through oxygen atoms to one octahedral sheet of alumina octahedral [77,78]. Rocks that are rich in kaolinite are known as kaolin or china clay [79]. Kaolinite contains white mineral that is also known as dioctahe- dral phyllosilicate clay. It is formed from clay which is produced by chemical weathering of aluminium silicate minerals such as feld- M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 91–97 95 spar [77,80]. The chemical formula for kaolinite as used in miner- alogy is Al2Si2O5(OH)4. However, in ceramic applications, the for- mula is typically written in terms of oxides, which after being treated by heat treatment change into Al2O3�2SiO2�2H2O. Further- more, kaolin after treatment or endothermic dehydration will change from crystal to amorphous stage [81]. The transformation will change it into new formation of clay called metakaolin. Meta- kaolin consists of amorphous silica and alumina, and the structure is in long order or hexagonal layers [79,82]. Metakaolin has been known as very reactive pozzolan and performs similar reaction to silica fume. Strength enhancement and improved durability by refining microstructure, allowing reliable water penetration and making cost effective are the stronger points in metakaolin as com- pared to silica fume [19,20,83–85]. Nano kaolin is formed using either top to down or bottom to up approach. Those processes will influence the final formation of nano kaolin. Generally, the basic but major formation of nano kao- lin involves layering or stacking flakes. At a glance, the particle of kaolin is similar to nano kaolin. Morphological properties of kaolin after the transformation in size from micro to nano is its particles provide larger surface area. In concrete, nano kaolin must undergo treatment in order to form a more reactive or stable component; nano metakaolin. Nano metakaolin is still newly used as supple- mentary in concrete, but the enhancement in concrete properties is expected, due to the positive impact of metakaolin in UHPC and other types of concrete. In a report by Morsy et al. [86], nano metakaolin addition in concrete has improved the strength of mor- tar where almost 8%–10% increment of compressive strength can be achieved. The most interesting finding is, tensile and flexural enhancement of mortar containing nano metakaolin is around 10%–15% as compared to plain OPC [86,87]. Although the earlier discussion shows the advantages of nano metakaolin inclusion in improving performance of mortar, there are still limited resources on the application of nano metakaolin in UHPC. Lack of raw kaolin in certain countries makes nano meta- kaolin unpopular as compared to silica fume. Therefore, guidelines and commercial technique in producing nano kaolin and nano metakaolin need to be exposed and intensive research has to con- tinue in order to maximise its potential as nano material alterna- tive in concrete. 11. Nano clay Nano clay is nanoparticles of layered mineral silicates. Depend- ing on the chemical composition and nanoparticle morphology, nanoclays are organised into several classes such as montmoril- lonite, bentonite, kaolinite, hectorite, and halloysite. Nanoclay is one of the most affordable materials that have shown promising results in polymers. Nanoclay is made of montmorillonite mineral deposits known to have ‘‘platelet” structure with average dimen- sion of 1 nm thick and 70–150 nm wide. The unique structure of montmorillonite clay is it possesses several qualities that make it an excellent base for manipulation through nanotechnology. These qualities include stability, an interlayer space, high hydration and swelling capacity and a high chemical reactivity. Characterisation of clays and their modified organic derivatives can be characterised using simple as well as modern tools which include determination of chemical compositions by gravimetric analysis, inductively coupled plasma (ICP) or XRF, cation exchange capacity (CEC) using standard ammonium acetate method, surface area measurement, Fourier transform infrared spectroscopy (FT- IR), powdered X-ray diffraction (PXRD) and others [58,88–90]. The clays arealso characterised by their cation exchange capaci- ties, which can vary widely depending on the source and type of clay. The purity of the clay can affect the final nanocomposite prop- erties. Due to this, it is very important to have montmorillonite with minimum impurities of crystalline silica (quartz), amorphous silica, calcite and kaolin [77,88]. The technique mainly used for purification of clays includes hydrocyclone, centrifugation, sedi- mentation method and chemical treatment [78,82]. Clays can be considered as inexpensive materials. Having nano materials from clay based can be adaptable with adequate cost. Despite the occurrence of clay in most parts of the world, guideline and techniques to imply and form clay to nano materials is still unrevealed. Research on the advantages and disadvantages of nano clay as construction materials need to be explored. Nano clay has been widely used in polymeric system. However, the evidence on improvement and enhancement in material stiffness, thermal sta- bility, as barrier coating, solvents and other improvement espe- cially in electronic and new form of materials are needed. Normally in construction, nano clay is applied as an additive to enhance concrete properties. Morsy et al. [86] reported that, enhancement in compressive and tensile strength for mortar cement having nano clay as additive was recorded. Thermal beha- viour of concrete also improved after nano clay was added as cement additive in paste [91,92]. 12. Summary From the review of the existing literature, it is clear that the use of nano materials in concrete is beneficial in improving some tech- nical properties of cement based materials although it deficients in some properties for example on water demand. In this review also, utilisation of nano materials in concrete is reported. Nano silica, alumina and titanium oxide are among the nano materials used in the current research in developing the nano based concrete. The addition of nano materials in concrete has similar effect to the effect of micro based materials such as metakolin and silica fume. Pore refinement and increased strength and durability of concrete are expected. The only different is the size of the materials is deduced to nano scale. Since in micro based materials, enhance- ment of concrete in strength and durability is proven, when using nano particles, concrete properties are likely to be improved. 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