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    Engineering Properties of Geopolymer Concrete Incorporating Hybrid Nano-Materials - Elsevier Enhanced Reader

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    ‘Ain Shams Engineering Joural 12 (2021) 3641-3687, Contents lists availa at ScienceDirect Ain Shams Engineering Journal journal homepage: www.sciencedirect.com Civil Engineering Engineering properties of geopolymer concrete incorporating hybrid nano-materials oar Menatalah A. Kotop*, MS. El-Feky®, Yousef R. Alharbi', Aref A. Abadel", Abobaker S. Binyahya® 2 surucurl Engineering Departent, An Shas Unversity, Eypt ®epartren of Ci Engineering Netonal Research Cent Expt “Departmen oC Engineering Coleg of Eten King Sud Unversity, P.0. Box 90, Ryd PAZ, Sead Arabia a ARTICLE INFO ABSTRACT ‘rice ony Received 7 Ap 2021 eised 26 Ap 2021 ‘Accepted 26 april 2021 ‘enable okie ? May 2021 CGeopolymer concrete is considered to be a sustainable alternative to Portland cement in construction Industry. The incorporation of nano materials into geopolymer matrix contributes to enhance the ‘mechanical and durability properties of concrete, Carbon nanotubes (CNTs) ate characterized by high tensile strength and good durability properties. However, CNTs particles have significant lage specific surface area that lead to encounter adhesion and éisperson difficulties in geopolymer matrix. Nano clay (Nc) is utilized to increase pozzolanic activity and decrease the adhesion problems in geopolymer con- Rowen cate ree This researth ais investigate the hy eet of NC andl CNTs onthe esting performances Seopa ofr fy ashe geoolymerconerete nti stu, geoolymer mines were proce wn ly 2) i Slagasanaluminsttae sours The utlized allalneatvetor was composed of both, sda sicate sw {50 and sodium hydroxide (NOM) souls Mechanical properties ofthe mines were determined Fh based on compressive and xa srengths tet Also the impacts ofthe Inlsin of NC and CNTs on meee sens the a content chloride resistance and water penetration depth on hybrid fly shag geoolyne eon ton scenth Crete were demonstrated. twas observed that the superar compressive stent or gepolymer mix rie et ‘a found rem he mix ncororated hy (2 5) NC blend with (0013) CNTs The engineering prone tries were sgniant improved by using hybrid nanoparticles, The high pozolanc effec of NC led 0 Improve the compressive strength, slang asthe nanaes were ted oer the geopolyme on Crete and hence enhance the durability properties © 2021 THE AUTHORS. Published by Eset BV on bel of Faculty of Engineering Ain Shams Uni- vers, This isan open aces are under the €CBY-NC ND lense peetvecmvonoricnses] by.ne nl) 1. Introduction tural concrete members| |, Geopolymer concrete isa recent kind Nowadays global warming problems due to cement industry hhave become of great concern. It has been noticed that cement industty is accounted for nearly 7% of al greenhouse gases existed ‘worldwide (1). Additionally, production of cement is considered a high energy consumption industry. To conquer these bad impacts, researches have tured to invent novel building materials to replace the utilization of ordinary Portland cement (OPC) in struc- * Conesponding authors mal adress: asbadloksiedus (AA. Aba) eer review under responsibilty of Ain Shams Univers. = 2K | production and hosting by Elsevier ups: 10,1016fase2021.04.022 of sustainable and environmentally-fiendly material that can replace OPC in the construction industry|2). There is a great con- cern to enhance the durability of concrete structures|3.54), Recent studies had proven the excellent; mechanical, and durability prop- erties of geopolymer concrete when compared to conventional OPC ‘ones|4. Moreover, geopolymer concrete would not only conserve energy consumption and reduce greenhouse effect, but also it eliminates the byproduct wastes ofthe alumino-silicate materials [5]. Waste materials have become one of the most important and challenging aspects leading to environmental problems|6) Geopolymer conerete are built up from the alkali-activated solu- tion and the alumina-silicate based materials, The selection of both alkali-activated solution and the alumina-silicate based materials rely upon their availability and cost as well. The aluminosilicate source may be a by-product such as slag\?- 10.45.53), ly ash, and silica Fume|4,7.8,11,12), 2080-4475/0 2021 THE AUTHORS. Fished by Elsevier BV on behalf of Fact of Engineering Ain Shams University ‘hiss an open acces ate under the CC Y-NE-ND eens (itp zeatvacmamons rt icemny Bend.) (MA Koto, MS. ELely, VR Alri et ab [Nano materials have attracted an increasing attention in science and engineering fields| 13,4652). Generally, the inclusion of nano ‘materials to Portland cement mortars could potentially enhance their engineering properties| 4,15]. Nanomaterials can be catego- rized into twomain types; pozzolanicbased like(nanoalumina,nano clay and nano silica) and fiber shaped like (carbon nanotubes and, ‘carbon nano fiber). It was reported that pozzolanic nano materials possess high pozzolanic reactions forming extra C-S-H gel and hence improve mechanical sttength| 13.16). The fiber-like nano materials are found to have their needle action systems through their shapes [17-The needle shape assist in bridging the cracks and prevent their propagation and then improving the tensile properties of the matrix [18]. Nano clay showed high pozzolanie reactivity and exhibited a significant effect in mechanical performance| 18-20) Carbon nanotubes (CNT) are in the form of sheets of carbon, atoms presented in a hexagonal shape and rolled to form a eylin- dder{13}) IC has been observed that the inclusion of multi-walled ‘carbon nanotubes (CNTs) to concrete can lead to significant ‘enhancement in the tensile properties of the paste|21~23). The reinforcing effectiveness of CNTs relies on different parameters, like CNT type, and the efficiency of their dispersion, interaction ‘and bond strength with the paste[24),CNT particles intend to be ‘agglomerated due to the highly attractive van der Waals forces, ‘which is revealed to aspect ratio and the high specific surface area of its particles|21,25]. They have a significant large aspect ratio that ranges between 1000 and more than 2,500,000. It was reported that NaOH solution can get rid of the oxidation debris from CNT surface and hence improve its dispersion performance. ‘Therefore, the alkaline solution used for geopolymer development has the ability of acting as surfactant and boosting the deagglom- ceration|26-28). Also it was reported that the inclusion of very small amount of CNT leads to significant mechanical enhance- ‘ment{29). CNT posses both macro and micro effect which is repre- sented by bridging effect so the lead to stopping the crack propagation and succeed in load transfer|24). Combination of ‘CNT and nano materials is generally effective to enhance concrete properties and bond strength. Ics known that it is very important to achieve sufficient bond for good performance of reinforced con- ‘rete structures( 30-32. By consuming fly-ash and slag as a reliable replacement to ‘cement witere the activation process of this materials takes place in room temperature However, studies that have been dealing with the effect of the inclusion of nano materials on the mechanical properties of hybrid ‘geopolymer conerete are limited in the literature. Furthermore, ‘zeopolymer concretes are not involved in the structural design codes and structural applications. Therefore, due to the lack of knowledge in the material characterization of fly ash/slag.geopoly- ‘mer concretes with nano materials, extra study is needed to develop the insights considering their engineering properties. ‘Therefore, the aim of this study is to investigate the influence of the inclusion of NC and CNT on the mechanical performance (com- pressive and flexural strength) of the hybrid fly ashslag geopoly- ‘mer concrete. The influence of this hybrid mix, on the air content, chloride penetration and water permeability has been investigated 2. Experimental program 2.1. Material 2.1, Alumino-siicae source ‘The alumino-silicate sources used in this research are hybrid (fly ash Class F and slag). The slag was according to the Standard Specification for Slag Cement for Use in Concrete and Mortars ‘ASTM C989 / CO89M, The fly ash was according to the Standard ‘Ain Shams Exgoerng Journal 12 (2021) 364-3647 Specification for Coal Fly Ash ASTM C618. The specific gravity for fly ash and slag are 26 and 2.85g/cm3 respectively. The alumino- silicate sources were delivered from Sika Egypt Company. The chemical composition of used slag and fly ash are shown in Table 1 and Table 2 respectively. 2.1.2, Nano materials ‘The nano materials used in this study were nano clay (NC) and ‘multi walled carbon nanotubes (CNT). Nano clay was in the form of off-white powder. The multi walled carbon nanotubes (CNT) used in this research was prepared in the laboratory of National Research Centre (NCR). CNT consist of graphene sheets rolled in a cylindrical shape. The length is found to from 10 mm to about 100 mm with inner diameter ranges from 1.5 to 15 nm and outer diameter reaches 50 nm as shown in Fig. 1, The SEM and the XRD of CNT are represented in Fig. | and respectively. It can be seen in Fig. 2 that XRD pattems indicate the amorphous feature of CNT. The identified intensity peak is related as copper at 20 angles of 25. The chemical composition of nano clay (N.C) is clearly shown in Table 5. 21.3, Coarse and fine aggregate ‘The fine aggregate used was natural sand with particles size below 0.5 mm and with fineness modulus of 2.25. The specific gravity of natural sand is 2.65. Crushed dolomite with maximum size of 12 mm and specific gravity of 2.96 was used as coarse aggregate. The specific gravity of crushed dolomite is 2.96. A com bination of 65% and 35% dolomite and sand respectively were used by weight, 2.14, Alkaline activators ‘The alkaline activator used in this work was a blend of sodium hydroxide and sodium silicate solutions. The mass ratio of SiO, to 'Naj0 in the sodium silicate solution was 1.2[33]. Sodium hydrox ide was in the form of white solids flakes. The total percentage of, 'NaO in the solution equals 15%. The chemical composition of sodium hydroxide (NaOH) and sodium silicate (5.8) are shown in ‘Table 3 and Table 4 respectively. 2.2. Mix design proportions In this study, twelve concrete mixes were designed to investi- gate the influence of the prepared nano materials NC and CNT on the mechanical properties of the hybrid (ly ash ~slag) geopolymer conerete. The control mix is made of natural fine and coarse aggre- gates, aluminosilicate source (50% FA and 50% slag), alkaline acti- vator and no water. Mixes which were incorporated with NC are ‘made in the same manner but by replacement with NC at ratios (2.5%, 5%, and 72) by weight of total binder. Whereas CNT mixes are made by replacement with CNTs at ratios (0.01% and 0.02%) by weight of total binder. To enhance the particles dispersion of (CNTs, homogenizing process was applied. The basic homogenizer which has been used in this work have the properties shown in ‘Table 6. The other six mixes were designed by blending both NC and CNTs in geopolymer concrete with the suggested percentages Of each type of nano material. The mix proportions of designed sgeopolymer concrete mixes are shown in Table 7. 23. Preparation of the specimens and curing ‘The investigation of the effect of the inclusion of NC and CNT in the hybrid (fly ash -slag) geopolymer concrete was carried out in this study. All dry ingredients (slag, ly ash fine sand and coarse aggregate) were first added in a Hobart mixer. Nano clay was added as a powder to be dry mixed with the dry admixture in the mixes that contains NC as a binder replacement for 1.5 min. (MA Koto, MS. ELely, VR Alri etab ‘Ain Shams Enginerng ural 12 (2021) 364-367 Te cheers of sl Bene 3, Fa) mm os 0 3, sale2 The temic compotion oy ath (FA een 505 Fads i oo 0 , x 60 tor omen 3 99 ‘oH 192 a2 264 1635 aon a7 321 Fig. 1. SEM of CNTs pate, Posner (CU) Fig. 2, XRD OF CTS. ‘This was followed by the addition of the activator solutions to the dry materials and mixing for 2-5 mit ‘The alkaline solution was prepared in the laboratory by mixing sodium silicate and sodium hydroxide solutions at the required ratio, The admixture of the SS and the NaOH were added to the dry mixture and mixed for 1 min. In mixes which contains CNTs, the amount of CNTs were divide into four equal amounts (by weight). Each quarter of the CNTs was homogenized with a litre of the sodium silicate by using basic homogenizer for 3 min with speed equal to 25°10° round/min, The achieved homogenizer mix- ture was then added gradually to the mixer to be mixed with the compounds for another 2 min, After mixing all the components for 3 min, the mix was poured in the desired moulds and com- acted manually in two and three layers respectively. Each layer was stroked for 25 times. After that, the specimens were de- ‘moulded after one day and cured in water at a room temperature to test days. 24 Testing method Compressive strength test was carried out on cubes of (100 * 100 * 100) mm after 28 and 60 days of water curing according to BS EN 12390-3)34]. Universal testing machine SHIMADZU 1000 KN, with rate of 0.5 N/mm*sec was used to test the samples. As the concrete mixing process was finished, air content test was performed on the fresh concrete according to ASTM C23135] Prisms (50 * 50 *200) mm? were prepared and cast for imple- ‘menting the flexural strength test after 28 days of water curing according to ASTM C293 [36]. For all tests, three samples were pre- pared foreach test and the result of the test was the average results for them. Cubes of (150°150*150) are prepared and casted for inquiring the chloride penetration test. Specimens ate examined after 28 day as per ASTM C 1202|37|. This test is performed on tuning electrical conductivity of concrete as an indicator for chloride ions penetration resistance. as Cubes of (150 x 150 x 150) mare prepared and casted for ee eee eee ae ed water permeability test. Specimens are examined alter 28 days Bement Nao) 10 __todetermine the water penetration test as per BS EN 12390-8338 3. Test results a ‘ompressive strer ‘The em compasiion of sad sae (85) seen steet dan Bement Nao 505 140 ‘The results of compressive strength for hybrid fly ashjslag ‘Content % 1s 310 570 __geopolymer concrete with replacement of nano materials with different percentages of NC (0, 2.5, 8 75) and CNT (0.01% and (0.028) at ages, 28 days and 60 days are represented in Fig. 3. Gen- The chemical eompasiion of ane cy (NC). Bement 50, Feo, os Go a0 0; Nao Lor 368. (MA Koto, MS. ELely, VR Alri etab Homesenizer properties. ‘The prover Value Speed range (cpm) “00-3000, Speed vanstion onload scale (8) rs Power consumption (Wat) wo Power ouput (Wat) 350 Frequency (2) 560 Dave Dimensions cum) Tr 66 « 221 Boom Dimensions (a) orsiise 16 weaht (Kg) erally, it was seen that compressive strength increases at 28 and ‘60 days as compared to the control mix. This increment in the strength can be related to the strong reactivity of the NC and ‘CNT which acts as a pozzolanic and filling material for the mixes. From Fig. 3, the highest values of the compressive strength among ‘the mixes incorporating NC individually were corresponding to the replacement of 2.5% by weight with NC. The enhancement values reached 90% and 70% as compared to the control mix at 28 and {60 days, respectively. While this improvement was reduced as INC % increases more than 2.5%by wrt. This obvious reduction can bbe referred to the agglomeration and poor dispersion of NC more than 2.5% resulting in porosity inerement| 15). Nano materials ‘enhances the reaction of geopolymerization through increasing the produced hydrated gel and density and hence improve com- pressive strength of hybrid fly ashjslag geopolymer concrete ‘matrix. It as informed that compressive strength of geopolymer affected by material type & theit fineness Fines create higher silica ‘and alumina leaching in alkali environment, lead to a higher com- pressive strength] 18]. It is more reasonable to correlate the com- pressive strength results to the ratio of gel/space percentage [3940], Therefore nano clay creates a denser mix with lower porosities and water absorption than the control mix. ‘The inclusion of 02% CNTs increased the compressive strength to the highest values among the mixes containing different per- ‘centages of CNTS individually. The enhancement values reached ‘81% and 57% as compared to the control mix at 28 and 60 days, respectively. The filling effect of CNT in the geopolymer matrix will improve the matrix uniformity and increasing the compressive strength values, According to literature, CNTS act as bridges for limiting micro cracks propagation) Furthermore, the alkaline solution used to activate geopolymers affects CNTs dispersion by affecting CNTs interaction with geopolymer matrix. CNT was sur- factant by NaOH, allowing them Co form well-dispersed nano tubes and de-bundle within GEO-matrix|25-28), ‘The highest improvement in the compressive strength is ‘observed for the blending of the NCz=-CNTaos with an increase ‘Ain Shams Exgoerng Journal 12 (2021) 36-3647 il ig. 3. Compressive strength of groplymerconrete mies Besa of about 99% and 70% compared to the control specimens at 28 and 60 days respectively. This improvement was slightly decreased by increasing NC percentage in the used combination up to 5%, ‘The inclusion of different percentages of NC (5% and 7.5%) have generally affected the compressive strength negatively as com- pared to the mix contains 0,02%CNTs individually. This reduction can be revealed due to agglomeration aspects of NC particles the agglomeration of NC particles in which adding NC more than 2.5% affect negatively on the compressive strength. But blending INC with CNT increased the strength as compared to the control ‘mix. In case of NC; s-CNTo 2 mix, a reduction in the 28 &60 days strength as compared to the mix NCzs.This reduction can be due to agglomeration of CNT where the incorporation of only 2.5% NC wasn't enough to cause a proper dispersion for such percentage of CNTs (0.02%by wt). Furthermore it was observed that adding (0.02% CNTs to the mixes containing 5% NC and 7.5% NC individually increased the strength of these two mixes with enhancement 12% and 16% at 28 and 60 days respectively as compared to the mix NG, From the previous section, the highest was corresponding to the ‘mix NG; 5-CNTao; Which can represent the optimum percentage to enhance compressive strength on the hybrid fly ashislag geopoly- ‘mer concrete 32. Air content ‘The substitution of the binder with 2.5% of NC and 0.01% of CONT in mix NC, s-CNToo; has shown a reduction in air content percentage in the matrix by 25.93% relative to the control mix as shown in Table &. The significant decrease in air content with NC and homogenizer mixture of CNT can be atributed to the influence Of the homogenizer which breaks down the agglomerates of the Mares constituents of geoplymer concrete (gi). ‘Mie Binder) Ne oxr N08 3s ine 288, Coarse age yash Slag onto 250 250 = 5 wa 302 aa 03 Nes ais ma ns 2 tons 250 230 - 005 Mons 250 250 . a1 Neas-CNToor aoa 203 nas 005 NC-ENTosr a3 m3 25 005 NCj-ENToce ams as 25 ar Nejs-CNToot pia pia as 005 (MA Koto, MS. ELely, VR Alri etab needle shaped CNT particles into singly dispersed particles and also decrease the initial particles size. This would improve ability ‘of CNT in acting like filler to the nano pores of geopolymer matrix. ‘The air pores present in the matrix lead to a reduction in strength as their percent increase|41 | 3.3, Flexural strength ‘The flexural strength results ofthe control mix CNTo01. CNTooa ‘and NCz5-CNTop: conerete mixes were discussed and represented in Fig. 4. Generally, the mixes CNToo1, CNTao2 and NC25-CNToo} showed an enhancement in flexural strength in the late age (28 days) for all concrete mixes. The flexural strength enhance- ments reached 15.8%, 33.7%, and 26.3% in CNToo1 CNTooa and NCzs-CNToo; Fespectively relative to control mix. Generally, it was concluded thatthe use of CNT have led to significant improve- ‘ment of the mechanical properties of geopolymer concrete through ‘te bridging effect in the cracked zone. In addition, the homoge- nizer increased the ability of CNT particles to act as filling material to the tiny and nano pores in geopolymer matrix and also increas- ing the nucleation eect of CNT particles leading to reinforcing the matrix and improving the flexural strength) 22,4243 34, Chloride penetration test ‘The resistance of chloride penetration of concrete is one of the ‘main properties affecting the durability of concrete against corro- sive eavironment|3). The levels of chloride penetration are classi- fied based on the charge passed into specimens as specified in standard. The results revealed that, generally the binder substitu- tion by hybrid NC and CNTs enhanced the resistance of chloride penetration for the concrete mix as compared to the control mix. ‘The charge (coulombs) passed was 620 for contro! mix (without ‘any Nano-materials) with chloride penetration level very low. While at mix NCz5-CNTao}, the passed charge (coulombs) were 480 (classified as very low) as shown in Table &. The chloride pen- tration resistance enhanced by 29.17% relative to control mix. This observation has 2 good agreement with literature that reported that the incorporation of CNT improve the chloride pen- ‘tration resistance of conerete|24). The nucleation effect of CNTS is responsible for high mechanical improvement. Additionally, the ‘well-dispetsed and good homogenized distribution of CNTS can _greatly enhance particle packing of geopolymer concrete and form= ing a highly compacted denser microstructure. These actions stop and bridge formation of cracks and prevent any crack propagation. ‘This in turn leads to the improvement of the chloride penetration resistance 3.5, Water permeability est Permeability of concrete affects the durability of concrete mas- sively. Whenever, the permeability increases, the resistance of con- crete to transfer aggressive agents decreases. Results show that, ‘water penetration depths were 150 mm and 60 mm for control ‘in Shams Enginerng Journal 12 (2021) 3661-67 ig. 4. Fenral strength of slated mits. Chord penetration est vals. Ma ‘Charge (oulombs) onde lon penetably™ ‘contol 20 Very low NeeCNTyo; 480 Very ow NGieCNTge 470 Very low NEEENToos 560 Ver low NE-ENToee 530 Very ow NGjeCNoo) 570 Very low NGieCNToy 580 ery ow ‘Recording ASTM C 120257) imix and the mix NCz=-CNToo: respectively as shown in Table 10. ‘With enhancements in the water penetration resistance equals 150% relative to the control mix. The good homogenized distribu- tion of CNTs increase particle packing of geopolymer concrete and forming a highly compacted denser microstructure which decreases the permeability of water through its matrix 44), 4. Conclusions ‘The following conclusions can be drawn from the test results: The gains in the compressive were ranged from 90.2%, to 8.4% when compared with control mix with 2.5% percentages of NC in hybrid fly ashslag geopolymer concrete. This improvement is due to high pozzolanic effect and filling effect of NC particles ‘Agglomeration aspects affect negatively on the compressive strength when adding NC more than 2.5%. ‘The gains in the flexural strengths reached 34% times of the agains with control mix with different percentages of CNT in, hybrid fly ashjslag geopolymer. The increase in the nucleation, effect of CNT particles leads to reinforcing the matrix and hence improving the flexural strength. This improvement is due tofill- ing effect and bridging effect of CNT particles. ‘The gains in mechanical properties were recorded to be high when utilizing hybrid nanoparticles. The pozzolanic reactivity ‘of NC significantly improve the strength, while the CNT has The water peetation depth values (em) ‘Sample Testvale aD ‘Water penetration pth (mam) onto 34 ‘conirot 150 NeveCNTan 27 NeeCNTao: # NCCNTon 2a NCCNToos 6 NC-ENTocs 27 NG-ENToer w NeeCNThon 26 NCNToo: n ses (MA Koto, MS. ELely, VR Alri etab reinforced the geopolymer concrete. Therefore, both the ‘mechanical and the durability properties were successfully, enhanced by using hybrid nanoparticles, 5. Future recommendations ‘The chloride penetration test needs ta be performed at late ages for the concrete age more than 28 days. More different mix proportions can be investigated with differ ent percentages of hybrid slag and fly ash. More different mix proportions can be investigated with differ ent percentages of hybrid nano materials. “Microstructure test like XRD and SEM could be provided to the test procedures. Declaration of Competing Interest ‘The authors declare that they have no known competing finan- cial interests or personal relationships that could have appeared to influence the work reported in this paper. ‘Acknowledgement The authors extend their appreciation to the Deanship of Scien- tific Research at King Saud University for funding this work through research group No (RG-1441-348).. 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