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    A Critical Review of Geopolymer Properties For Structural Fire-Resistance Applications

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    Construction and Building Materials ELSEVIER journal homepage: www.elsevier.com/locate/conbuildmat Review A critical review of geopolymer properties for structural fire-resistance (@) applications os Mukund Lahoti*, Kang Hai Tan”, En-Hua Yang” ‘beporment of Ci! ngnerin tris sae of Teno and Science. on Alo 33303. no "Schaaf i ond Enronnentl Engine Neryang Tele! Unie Singer 38788, Sgopore HIGHLIGHTS + Geopolymers ae chemically stable {thermal deformations oecuttng in geopolymers. 2 Scent of geopolymers is affected by microstructural and phase composition changes { Geopolvmes show inberenty superior ie resistance { Geopolvmersrequze careful mix design to achieve superior fire resistance ARTICLE INFO ABSTRACT rice Protection of structures fom fireisaf extreme importance, Geopolymer isa novel material tat has wide- ected 1 February 2018 ranging aplcations, and ths review ate focuses on assessing the potential of geopoymers towards Received in evied fot 29 May 2019 ‘Accepted 9 June 2018 ‘valable aline 18 June 2018, ‘enbancing the structural ire resistance by critically reviewing its properties subjected to elevated tem= perature exposure. The properties of geopolymers are categorized into three scales, namely, micro-scale, Tmeso-scale and macro-Scale, and are discussed at length tis noted that geopolymnes are chemically stable and do not undergo breakdown of chemical structure in contrary to OPC hyeration products ‘Thermal deformations occurring in_geopolymers, which cause macro-racking, are discussed, ‘Compressive strength of geopolymers i observed to be affected by microstructural changes (including ‘rack formation, pore structure changes, densification. sintering, and melting) and phase composition Keworas Fie. gopolymer evated temperature Thermal properties hase stay ‘changes (such 38 growth or destruction of crystals and transformations in-geopolymer’ pase) Meroe Geopolymer-based binders show inherently superior fire resistance a8 compared to Portland cement: ‘Thermal defamation based binders. However, it requires careful mix design, to achieve substantial chemical stbiity. low vel- sirens lume changes, strength endurance, and spalling resistance Factors such as choice of precursor, use of Spling aggregates, total alkali content in geopolymer, water content, et. are critical and should be controlled. Sacer appli ‘The influence ofthese factors is discussed at length inthis article, The current applications of geopoly- mers for heat and ie resistance have also been briefly presented. 1© 2019 Elsevier Le. All rights reserved. Contents 1. Introduction sis 2. Geopolymer science 516 24. Geopolymer: general introduction tothe novel material 516 22. _Geopolymerization: the process of eopalymer formation, S17 3. Geopolymer properties subject to elevated temperatures. 317 BL Microscale properties sis 34.1. Phase stability S18 5 Goresponding author a; NI-O1b-56, 50 Nanyang Avene, Singapore 625795, Singapore al adres chy ang us (EH. Yang tah oo fConsrction and lng Materia 2212018) S14-526 sis 51.2, Microstructure and pore structure changes sis 32, Meso-scae properties 520 321, Thermal deformation 520 33. Macro-scale properies 521 53.1. Compressive stength 521 332. _Fite-induced spalling and fie tests. 522 4. Fire performance of Portland cement concrete vs. copolymer concrete 523 5. Application of geopolyrers for heat ard fire resistance 523 6 Discussion, 523 7. Conclusions 524 Declaration of Competing interest 524 Acknowledgments 524 References 524 1. Introduction pressure rise, they have not been very effective in reducing the Fire damage can be critical in structures and in all cases, the protection of people and property is essential Despite all the tech nological advancements and measures for fire prevention, there always remains a threat of fire breakout, The fire arising fram ‘9/11 attack on World Trade Centre, the Windsor tower fire, the fire fn Mont Blane and Channel tunnels, have caused heavy losses of, life and human assets. Protection of structures from fire is vital since it would surely contribute to a reduction of losses in all respects, Therefore, research in a matter of fire safety is of utmost importance Concrete and steel are the most widely used construction mate- rials [1]. The reasons are that concrete has inherent fire resistance, is non-combustible, and has a relatively low thermal conductivity Cracking, spalling, and loss in mechanical strength of concrete after exposure to fire, however, are key concerns, especially with high strength concrete |2~10]. All concrete structures, especially struc: tures such as concrete liner of tunnels, must offer sufficient fire resistance. There has been an experience of severe dramatic tunnel fires in the past few decades. Table I [11] summarizes the life and property losses due to these fires. Incase of atunnel fire there is a rapid increase in air temperature within the first few minutes of fire. This results in considerable spalling of concrete and conse- quently, the tunnel lining suffers damage. It leads to safety issues Doth forthe tunnel users and the fire rescuers. As can be seen from the table, there are ditect econamic losses from repait activities and indirect losses related to tunnel closure, Fire resistance tests fn concrete elements are required, in most tunneling projects, to address the tunnel fire issues. Temperature-versus-time curves such as the ISO standard fire curve, RWS curve, hydrocarbon fire curve have been adopted in various tunnel fire testing regulations. All these highlight that fire safety of any concrete structure, not just tunnels, is a serious concern ‘The use of polypropylene (PP) fibers in concrete is generally undertaken to reduce the danger of spalling of concrete in the event of a fire [12-15]. Two chief causes for spalling are ~ a rise Jn pore pressure and development of thermal stresses. Although PP fibers have been shown to reduce the spalling caused by pore Damage caused by tunnel resin the past wo dcaes 1), thermal stresses. Ths is one of the drawbacks with using PP fibers ‘a8 a measure to prevent concrete from fire damage. Use of thermal barriers is another solution for concrete fire protection. However, this solution is available at a cost. Moreover, when OPC concrete is subject to high temperature, ordinary Portland cement (OPC) hydration products, namely, calcium silicate ydrate, calcium hydroxide and calcium carbonate degrade (Fig. 1). Iti challenging to avoid this deterioration of concrete micro-structure [15,17 Moreover, steel, both as reinforcement in concrete and for structural applications, is much more vulnerable to high tempera~ ‘ure as compared to concrete. Thus, steel structures need fire pro- tection. For steel members, in many applications, it is imperative to provide insulation to prevent softening of steel at high tempera- tures. Four common types of passive fire protection materials are listed below: 8) Traditional materials (concrete, plaster, bricks): These are readily availabe, and their implementation does not require special skills, These materials are weather resistant but are slow to apply on site. The thick casing takes up the floor space, and they are heavy. ) Board materials: These are pre-fabricated non-combustible boards made by gypsum and reinforced with inert fibers. The pre-fabricated insulation boards can be applied to exist- ing structures as a method for fie refurbishment. However, this is an expensive method and requires a long installation ©) Spray-applied fire-resistive material (SFRM): Ths is the most commonly used passive fire protection material for steel structures, It is also used in reinforced concrete structures to prevent explosive spalling. SFRM usually consists of cement matrix or gypsum plaster containing vermiculite, shredded polystyrene or mineral fibers. They can be sprayed either in the form of dry-mix (sprayed mineral ber SFRM) for wet-mix (sprayed cementitious SFRM). They have rela- tively low cost and can be applied to existing structures as well. However, the application of SERM makes the appear- nce of the structural element less aesthetically appealing, wats we) (oe) si6 Laos eo Consrion on Pung Motr 221 (2019) 514-526 200 300 400 S00 60 OPC Concrete subject to high temperature || Losstagabano | | itomissor) || 1 1 tr 1 1 ratign watet 1 1 1 1 io a) las mt EE | a | ere | issotiation’? | Congrete structurally not usatul | crt | Gesoparen OH) | Me || anal || Pooh | ‘Temperature(*C) 9 700 #00 900 1000 1100 1200 1300 ig. 1. Physcchemical processes occurring in ‘The adhesion or bonding to the surface of structural element is important, Missing fireproofing due to poor adhesion to steel and brittleness of SFRM has been observed, One pi: ‘mary reason of the collapse of the World Trade Center (WC) towers in 2001, for example, was the dislodging of SFRM from structural members due to aircraft impact, which resulted in rapid heating of unprotected structural steel. In reinforced concrete structures, heat-induced spalling can result in severe loss of integrity and collapse of structures. «d) Inturescent coating: Specially formulated paint-like coating can be applied onto steel surface, The coating swells upon hheating This approach is aesthetically pleasing and most tused in architecturally exposed structural steel, However, the material is much more expensive than SFRM, Intumes cent coating commonly provides a fire rating of 1-2 h. Gen- erally, the intumescent coating is applied on site Application of intumescent coating is fast, and it does not take up space or adds to the weight. The concern with itis the high cost (Overall, it has been reported that for many applications inelud~ ing fire protection of tunnels, underground structures, high rise Dulldings, strategic objects, metallic structures such as I-beams, ‘thermal insulation of furnace, chirmneys, boilers or as a composite ‘material for ships, automotives and aircrafts, itis necessity to develop new materials which have superior fire and mechanical performance to conventional concrete and other construction ‘materials (19) Geopolymer is a novel construction material which can be an alternative binder to OPC. It has also been referred to in the litera- ture as inorganic polymer glass ‘alkali-activated cement, mineral polymer, and ‘alkali-bonded ceramic’ [20], The term "Geopelymer ‘was coined by Joseph Davidovits in 1978 [21] It refers to a solid material formed by the reaction of aluminosilicate source with an alkaline solution [22], Aluminosilicate sources that are com- monly used are metakaolin fly ash and blast furnace slag. Geopoly: ‘mer is greener than OPC and can provide a route to reduce carbon footprint caused by excessive usage of OPC (23-28), Producing. geopolymer concrete based on coal combustion by-product, fly ash, isan useful technology to utilize fly ash, instead of amassing ‘or simply dumping this material to cause ecological concern [27.2830], The mechanism by which geopolymer hardens and sans strength is markedly different from OPC. Geopolymer pos- sesses excellent mechanical properties, and its compressive side Fordand cement concrete during heating (18). strength can be greater than 100 MPa [21]. It has excellent poten- ial for fire, alkali-silica reaction (ASR), and acid resistance. It has an inorganic framework and does not combust like organic poly: ‘mers. tis non-smoking and non-toxic and has low processing tem- perature as compared to ceramic composites [32], Geopolymer can serve as a green construction material with immense potential for sustainable development and fire resistance. Based on the above-presented descriptions it is realized that there is need of a green construction material for structural appli- cations with admirable fire and mechanical performance. Its also anticipated that geopolymer can fit the bill. AS a consequence, there is a need to conduct an in-depth literature review on the cur~ rent state of the art related to the performance of geopolymer sub- Jected to elevated temperature. The discussion to follow will be focused on assessing the potential of geopolymers towards enhancing the structural fie resistance by reviewing the phase sta- bility, microstructural changes, thermal deformations, strength endurance, and fire-induced spalling resistance of this material ‘on exposure to high temperature. I is an effort to critically review the latest developments on this matter and present it concisely The review of industrial applications and existing literature in an article such as this is by necessity less than exhaustive. However, the understandings provided by the current article will be valuable for researchers and engineers aspiring to develop high emperature-resistant or fire-resistant’ materials for structural applications. Fire-resistant geopolymer conerete/composites may be a potential solution for the construction of critical structures such as tunnels, underground caverns and high-rise buildings hich necessitate fire safety. 2. Geopolymer science 2.1. Geopolymer: general introduction to the novel material, Concrete is the most used human-made material in the world OPC is conventionally used as the precursor to produce concrete Portland cement production is one of the principal causes of green- house gas emission |23,24|, Thus there has been an ongoing search for alternate building and construction materials with reduced car- bon footprint (35,36) Davidovits [32) proposed in 1978 that novel binders could be synthesized by a polymeric reaction of silicon and aluminum- rich source materials of geological origin such as kaolin clay with alkaline liquids. These binders were termed as geopolymers which tah oo fConsrction and lng Materia 2212018) S14-526 sv Image showing 30 network structure in geopolymer SiO chain tom C20 sheet A. so chain a A 'i0 chain AX si0 chain Fig 2. Schematic molecular sructre of geapolyner in contrat 9 OPC base on 0) hardened just like OPC. An X-ray amorphous alkaline aluminosii- cate gel, characterized by short-range structural order, is the main reaction product in this process (37), In addition to the alkaline aluminosilicate gel, Na-Herschelite-type zeolites and hydroxyso- dalite are formed as secondary reaction products, when fly ash is used as the aluminosilicate source [38,29]. Besides these reaction products, the geopolymer binder comprises of un-reacted particles (from the solid precursor) and a pore network (containing water Used for mixing the precursor), Water is usually supplied through an alkaline activating solution (20). The geopolymer gel is a three- dimensional network of aluminate and silicate tetrahedra, Since AI” in the aluminate tetrahedra (AJO,)~' is in four-fold coordina tion, excess negative charge is balanced by the alkali metal cation provided by the alkaline activating solution. Usually, water in eopolymer binder does not form an integral part of the geopoly- mer chemical stricture. This is in contrast to calcium silicate hydrate gel in hydrated OPC paste, where water forms an integral part of C-S-H, Fig, 2 shows the schematic structure of geopolymer and OPC. However, it should be noted that in certain scenarios ‘when geopolymer is synthesized using a high calcium precursor such as class C fly ash and ground granulated blast furnace slag (GGBS), C-S-H or C-A-S-H is produced. In those cases the molecular structure of geopolymer will be different than as shown in Fig. 2 22. Geopolymerization: the process of geopolymer formation Geopolymers are a complex class of materials, The process of, zgeopolymer formation principally involves the reaction ofan alka- line solution with a reactive aluminosilicate precursor. Calcinated kaolin clay (metakaolin) or by-product from coal combustion (fiy ash), are commonly used precursors for geopolymers. Metakaolin has been relatively widely used for geopalymer synthesis. Its par- ticles have a plate-like morphology and thus it has a very high water demand for geopolymer cement and concrete applications Fly ash is a highly variable material and its properties depend on the coal ftom which it is produced and also the combustion and quenching process by which itis produced. The fly ash which is Tow in calcium content (Class F fly ash) is more often used as seopolymer precursor. Generally, the alkaline activating solutions are alkali hydroxides: or silicates under high-pH conditions [41]. The use of alkali hydroxide such as sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LIOH) alone, without any addition of si- Jcates, can be the simplest activating solution in geopolymer syn- thesis. The use of silicates generally involves sodium silicate, and potassium silicate, and their properties such as density and viscos- ity are a function of their composition In the conceptual model by Duxson et al. [23], the geopolymer- ization process is described in the following way. Dissolution of aluminosilicate source due to contact with alkaline activating solution leads to the formation of individual alumina and silicate species (probably as monomers). It isthe frst step in geopolymer- ization, These monomers interact to form dimers, and further tt: ‘mets, tetramers and so on. The aluminosilicate gel precipitates ‘when the solution reaches saturation. Since reactive aluminum dissolves faster than silicon (Al-O bonds are weaker than Si-O bonds), initially the precipitated get (Gel 1) is aluminum-rich. As the reaction progresses, more silicon is dissolved from the precu sor, and the concentration of silicon in the gel increases giving rise to Gel 2. All these stages involving dissolution, speciation, equilib- rium, gelation, reorganization, polymerization, and hardening go on simultaneously. I requires an alkaline solution for the dissolu- tion of aluminosilicate source, as well as for catalysis of the con- densation reaction (22) 3. Geopolymer properties subject to elevated temperatures Elevated temperature performance of any material is signifi- cant, especially when it is to be utilized as a fie-proof material for structures, a8 a thermal insulator, a material for the refractory application and so on. Geopolymeric materials have intrinsic fire resistance. They have an inorganic framework, and do not burn like organic polymers. They are non-smoking, non-toxic, and have a low processing temperature as compared to traditional ceramic composites [32|, Indeed, it should be noted that the properties and performance of geopolymer subject to elevated temperature depend on is composition or mix design and the synthesis proce dure as wel. ‘To apply geopolymer as a fire-resistant building and construc- tion material, geopolymer thermal performance should be exam: ined at miero-, meso- and macro-seales [42]. Fig 3 illustrates this idea, Micro-scale refers to observing the phase transformations ‘and nano-structural transformations occurring in the geopolymer Subject to high temperature. Thus, it relates to the chemical stabil- ity and the performance at this scale contributes tothe stability of ‘material at higher scale levels, namely, meso and macro. The abil- ity of material to resist volumetric deformations and thermally induced-cracks when subject to elevated temperatures is referred to here as the meso-seale thermal stability. Macro-scale stability is related to the ability of a material to possess strength endurance ‘and spalling resistance subject to elevated temperature. Under- Standing of the performance at these three scales brings a step closer towards the structural application of the material for Fe-resistance purposes. Important properties dealing with the sis © aot ea Consrcion ond ling Meters 21 (2018) 514-526 eeu one) fire resistance en ener cao) eed Coen > ees ig. 3. Methoélogy ensure good structural performance of gepolymers subject ‘micro-scale, meso-scale and macro-scale performance of geopoly- ‘mers have been reported in the literature, and an effort has been made herein to present the state of the art report summarizing the important properties of geopolymers subject to elevated temperature, 3.1. Miero-scale properties 3.1.1, Phase stability Knowledge about the phase change of geopolymers can be cr cial in understanding its macro-scale properties and thus the struc- tural performance on high-temperature exposure. Many researchers have reported phase change behavior of geopolymers subject to high temperature thermal treatment and iti significant to note that geopolymers exhibit remarkable chemically stability Barbosa et al. [| studied the thermal behavior of geopolymers synthesized using metakaolin and sodium silicate in a highly al line medium. This geopolymer, when adequately cured, exhibited remarkable thermal stability retaining its amorphous structure tll the onset of melting at 1300°C, They also synthesized K-PS Poly (Sialate) and K-PSDS Poly (Sialate-disiloxo) geopolymers starting from metakaolin, K-silicate, and KOH pellets based on specific ‘molar ratios (44), K-PS geopolymer melting point was around 1400°C and was stable till this temperature. X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) analysis suggested that the stability was due to its complete re-crystallization to fed spats leucite and Kalsilite at 1000°C. K-PSDS geopolymer, though thermally stable, and had a high melting point, became friable and porous when heated to temperatures above 1200°C. It did hot undergo complete re-crystallization and retained a certain degree of amorphous character. ‘A directed synthesis can help to regulate the structure forma- tion process and features of the geopolymer. Krivenko et al. [45] varied the Si0,/Al,0, molar ratio in the initial “geocement (geopolymer) made from metakaolin and fly ash, The following ‘Table 2 from their study shows the existence of a correlation between the initial molar ratio and products of dehydration or Phase change at $00 °C ‘Kovalchuk et al, [46] also reported the role of initial alkalinity, ‘Theoretically, the lower the initial alkalinity, the higher is thermal resistance because the onset temperature of crystallization increases when alkalinity i lowered. However, the inital alkalinity also determines the rate of alkaline activation and regulates the rabte2 Coretaton beraeen SAI rato of precursor and gropolymer éehyetion product 3 ‘Amina SOWALO; molar seocements crresponding phase) Metalacin 2 (nepheline) 2 (nepelie) s (rstobate}, 2 (eephein) 2 erste) 2 (epee) 2 (nephtine) ‘(alte 2 (nepheline) b= (erstobaite 2 (nephelne) yas development of compressive strength, That is why an optimum quantity of initial alkalinity is required to have sufficient initial strength and target properties after high-temperature exposure. The total alkali content in the system and the degree to which it is taken up by the reaction products formed is significant in deter- ‘mining the high-temperature properties such as the onset temper- ature of re-crystallization and sintering and the amount of viscous sintering [47]. Hence, itis important to tailor the initial alkali con- tent to realize a tight geopolymer mix for structural fire applications. _Duxson etal. [48] observed the formation of crystalline phases. for metakzolin geopolymers subject to elevated temperature expo- sure. The effect of changing alkali cation was also noted. It was ‘observed that regardless of the alkali type (Na, K or Na-K), the amounts of crystalline phases formed decreased with an increase in the Si/AI ratio of the geopolymer. The heating rate of geopoly- mers was also noted to alter phase composition and thermal shrinkage of geopolymers, which can be crucial in case of a fire incident. Temuujin etal, [29] found that geopolymers calcined at 1000 °C for 1-h duration showed an X-ray amorphous structure, that is, no phase change after heating. Rickard et al. (50) reported that all sgeopolymer samples, using fly ash as the precursor, exhibited strength improving microstructure changes such as enhanced inter-particle binding, due to sintering after firing, Some samples were unstable due to non-geopolymeric phases. After firing, the geopolymer remained largely amorphous, experiencing no phase transformation, Interestingly, Rickard eta [51] found that meta- kaolin geopolymers had crystalline (nepheline) structure afer ele vated temperature exposure. Perera etal. [52| prepared geopolymer using metakaolin, potas sium silicate and potassium hydroxide and cured at 80 °C for 24h and progressively heated it from ambient to 140°C in the air to observe the phase changes. Till 800°C, they found amorphous phase and kalslite as the major phase at 1000°C and 1250- 1400 °C, leuciteas the major phase at 1200 °C and till 1400 °C there was no sign of significant melting. They found an open porosity of 38% at 1000 °C. The material was found to be suitable for refractory applications due to the presence of two refractory phases (Kalsilite and Jeucite) and high porosity leading to excellent thermal insula- tion properties. Thus, the phase changes observed in the previous literature can be summarized in Table 3, Remarkably, researchers have reported different phase changes for geopolymers subject to thermal treatment, Noteworthy is that geopolymers are chemically stable and do not undergo breakdown ‘when subject to high-temperature exposure. On the contrary, OPC hhydration produets such as calcium silicate hydrate (C-5-H), cal cium hydroxide (CH), and calcium carbonate (CaCO,) undergo sev- cre deterioration on thermal exposure [16,17 Fig, | shows the physic-chemical processes occurring inside Portland cement con- crete during heating based on the ‘thermometer’ analogy | 15] IM toh eo /Consructon and Bung Materia 221 (2019) 514-526 sie ‘able? ‘Observation on phase changes by vrous researches. Researchers ‘ceepalymer pe (Dbseved phase a high emperatues besa (2005) tS (MK based) “Aorphou ll the onset of meng 1300 bikes Complete re-crstalization to espe stable up to 400°C) e505 Incomplete re-stalization Feable and pores > 1200°C era (2008) Mx base ‘Aayorpheus tl 800°C. crystaline(Kallite) a5 2 major phase a 1000°C ané 1230~1400°C (Leet) a the major pase a 1200°C Dexson (2007) Mk based Keven (2007) MK based: FA based {cystine ater 800°C ‘emuyin (2017) MK based ‘ovorphous (Calened at 1000°C for ckare (2012) abused Largely amorphous afer Firing at 1000" Strength improving structural changes Rckaré (2013) Mik pase Cystine (Mephatine ater fring st 1000°C Sables (2013) Fen sla based Wel Crystalline said afer 1000" 3.1.2, Microstructure and pore structure changes Exposure of geopolymers to high temperature affects the microstructure in many ways. Following discussion elucidates how the geopolymer paste morphology changes due to sintering, and crystallization happening at high temperature. It is also explained how the removal of physically or chemically bound water (dehydration) at high temperature would affect the pore size distribution in geopolymers. These microstructure and pore struc- ture changes affect the macto-scale performance of geopolymers subject to elevated temperatures ‘The first microstructure change in geopolymer happens due to dehydration of free water (from room temperature to above 200 °C) The vapor pressure generated due to the heating of water ide the material would try to escape by forming pathways. This process would damage the material due to the formation of micro- cracks. The pore structure will also change. The degree of ‘microstructure change would depend on several factors. Kong et al. [53] found that metakaolin-based geopolymers experienced ‘more significant damage to microstructure compared to their Oy ash-based counterparts twas attributed to a much higher amount ‘of water required to mix metakaolin-based geopolymers and also to their lower interconnectivity of the pore structure. {At temperatures around 550°C and above, sintering and densi- fication of the geopolymer matrix would cause changes in micro- structure [54-50]. Geopolymer paste after high-temperature expo- ‘sure has fewer voids and exhibits smoother texture. The viscous sintering of the paste at high temperature also leads to crack heal- ing (Fig: 4) and has been reported in the literature [57]. Geopoly- mer concrete will have additional micro-structure changes due 0 the difference in coefficient of thermal expansion of geopolymer paste and aggregates. Bakharev [54] found that the average pore size and cumulative pore volume in fly ash geopolymers increased after exposure to ‘800°C and 100°C. It was suggested that the increase in porosity ‘was related to the crystallization happening in the material at a high temperature, Gourley et al, [58] mentioned that since -geopolymer cement is effectively a glass unlike OPC, which is a hydrate, resistance to heat and specifically to fire is much improved, The absolute volume of water contained in the pore structure is low, and the pore structure is continuous, Thus the ig 4. SEMBSE micrographs showing fonmaion and healing of mico-cracks in geoplymes on high-emperatue exposure (Solid artows showing micro-cracks) (57 50 [Mtn eto Construton ond Bung Mater 221 (2019) 514-526 High strength geopolymer Low strength geopolymer As-cured After fire As-cured Afterfire Sle] Um ower ee I 4 8 O77. Se [iceopolymerge! Wh Unreacted fly ash particle Crystalline material Voids and pores Fig. 5. Schematic depiction othe proposed mic structural changes in gepolymer paste upon fring ‘mode of decomposition is to melt at temperatures over 1000°C, rather than explosively release water or dehydrate to a powder. Geopolymer has water in pores which absorbs heating for some time, thus reducing the temperature of the sample, and when it vaporizes and exits, it does not damage the structure much due to the permeable pore structure Rickard e€ al, [59] studied the microstructure of two geopoly- ‘mer mixes, one was highly reacted high-strength geopolymer with ‘a compact microstructure, and the other mix had a higher degree fof un-reacted fly ash resulting in low strength and low-density -geopolymer, It was reported that the initial high-strength geopoly- ‘mer was more vulnerable because of compact microstructure and showed more reduced thermal performance, more strength loss, and higher dimensional instability due to dehydration damage ‘and macro-cracking. The initial low-strength geopolymer was found to be little damaged by dehydration, better able to accom- ‘modate volumetric changes and exhibited strength gains after thermal exposure due to the sintering process. The model shown in Fig. 5 was proposed to describe the results. 3.2, Meso-scale properties 3.2.1. Thermal deformation ‘Materials tend to expand or contract subject to elevated tem- peratures. Coefficient of thermal expansion is indicative of the degree to which material undergoes thermal deformation. It is defined as a change in length per unit length of material per unit inerease in temperature. It can be measured in-situ using tech- rnigues such as dilatometry and thermo-mechanical_analys (TMA) or ex-situ through dimensional measurements. Since thes- ‘mal deformations during heating can cause stresses and poten- tially damage the material, these measurements are of specific interest while evaluating the thermal performance of geopolymers {or high-temperature applications. Dilatometry (ASTM Committee E37 2011) is a traditional method used to precisely measure dimension changes in the material as a function of temperature ‘The use of a differential dilatometer makes the measurement even ‘more precise since the sample holder expansion is eliminated. Fig. 6 shows an example of thermal deformation characteristics of geopolymers measured using a differential dilatometer (55), It has been proposed that fist significant shrinkage even in sgeopolymers is due to dehydration of free water (100-300 °C) [60,61], Henee, the water content in geopolymeric material is nificant for high-temperature applications, and tailoring of water content is thus very important. In temperature range, 300-600 °C, thermal deformation can be attributed to two phenomena, One is slight shrinkage due to Sample temperature °C) 0 20 400 6a st 1000 o os et = sas 2 2s 3 ig. 6. thermal éeformation characerstis of geopolymers observed using datometer 5). physical contraction of geopolymer caused by condensation reac- tions of the hydroxyl groups present in geopolymers to form shorter T-O-T linkages (where Tis aluminum or silicon atom) [55.60.62], Another is due to the phase transformations occurring in secondary phases such as quartz especially in case of fly ash szeopolymers and not so much for metakaolin-based geopolymers. thas been reported that quartz, a commonly found crystalline phase in fly ash, transforms from low to high quartz at 573°C [63] causing thermal expansion Between 550 and 900°C, the second major shrinkage event ‘occurs due to the densification of geopolymer; the geopolymer gel sinters and viscous flow fils the pores [48,61 Since erystal growth causes expansion, the degree of crystal growth in this region can also affect the magnitude of thermal deformation [95]. Mix composition and the type of impurities may also affect the deformations. Researchers have reported inconsistency in tend in this temperature range. Rahier et al. (54) and Rickard tal. [51] found some thermal expansion events along with shrink- age caused by viscous sintering in this temperature range. On the ‘ther hand, Duxson et al. 48] and Dombrowski et al. [55] mea- sured only shrinkage events while Barbosa etal. [4 found dimen- sional stability of geopolymers in this region. Duxson et al. [55] reported for metakaolin-based geopolymers, that the thermal shrinkage is influenced by the composition of alkali activating solution (Si/Al ratio) as well as the type of alkali cation. Using potassium as alkali cation, thermal shrinkage was reduced when compared to using sodium as alkali cation, Duxson et al. [60] also observed that although alkali cation type does not tah oo fConsrction and lng Materia 2212018) S14-526 sa significantly affect the onset temperature of crystallization and {quantity of crystalline phases developed in geopolymers, it affects the onset temperature of densification in the order K> Nak > Na The amount of erystalline phase and gel viscosity of geopolymers ‘were thought to be critical in determining the extent of shrinkage uring densification Bakharev [5 studied the effect of alkali cation (sodium and potassium) on thermal deformation of fly ash geopolymers. How: ever, the result was studied only briefly without significant tailor- ing of the mix design. The thermal deformation measurements were exsitu hence less precise than the in-situ measurements Recent research reported the influence of alkali cation (sodium, potassium or a mixture of two) on thermal deformation (volume stability) of fly ash geopolymers when subject to high- temperature exposure (57), It was noted that K-geopolymer experienced minimum thermal deformation, followed by Nak: and Na-geopolymers, respectively. High-temperature exposure causes thermal shrinkage/expan- sion in geopolymers, which in tum causes/macro-cracking [42,66]. Kong et al, [53] found that metakaolin-based geopolymers required a much higher amount of water as compared to fly ash- based geopolymers due to metakaolin being finer than fly ash and also due to plate-like morphology of metakaolin as compared to spherical shape particles of fly ash. Macro-cracks in the order of 0.1-0.2 mm were noticed on the surface of metakaolin geopolymer samples whereas fly ash geopolymer samples had no such cracks. Bernal et al. (57) reported macro-cracking in metakaolin-based sgeopolymer pastes (when subject to elevated temperatures) could be recuiced by the addition of refractory aluminosilicate particles and fibers. 33, Macro-scale properties 33.1, Compressive strength Changes in the compressive strength are significant in evaluat~ ing the high-temperature performance of geopolymers, which can be affected due to microstructural and phase composition changes. Microstructural changes can include cracking. pore structure changes, densification, sintering, and melting. Phase composition changes can be growth or destruction of crystals and transforma- ‘dons in geopolymer paste. The expansion of secondary phases such asin fly ash based geopolymers and the deformation of aggregates also affect strength, Some of these changes may even enhance ‘mechanical properties. Densification of geopolymer causes a reduction in the voids and inereases mechanical strength [57,55] Sintering reactions cause stronger bonding. between particles thereby enhance mechanical strength. Geopolymer mix composi- tion and presence of secondary phases would affect the tempera- ture of densification and sintering, ‘Annumber of factors affect the compressive strength of geopoly- ‘mers on exposure to elevated temperatures, These factors may Include the choice of precursor (whether metakaolin or fly ash or GGBS or a combination of these), use of aggregates (whether use of no aggregates at all or use of only fine aggregates, ot use of dif- ferent kinds of coarse aggregates such as quartz aggregates, light- weight aggregates, or use of different grading of aggregates, or use of fibers and fillers), roal alkali content in geopolymer, ec Following is a literature review on the effect of these factors on compressive strength of geopolymers. 3.3.1.1 Choice of precursor. Kong etal. [56] studied the behavior of ‘metakaolin-based geopolymer matrix exposed to 800 °C and Si/Al ratio was found to be a critical parameter. The deterioration of compressive strength reduced with increasing Si/Al ratio. This effect was very prominent at high Si/Al ratios (>1.5) where the strength reductions were minimal of the order of 5X, This latter observation was partly attributed to sintering of un-reacted Si-tich particles in the mixtures. The effect of variation in Si/Al molar ratio on residual compressive strength of metakaolin polymers, as been comprehensively investigated by Lahoti ec al, (42), A high degree of cracking damage and low residual strength retention was observed for metakaolin geopolymers, sig nifying the need to improve the macro-scale stability of metakzolin ‘Beopolymers for structural fire applications. Fly ash-based geopolymers are found to be better candidates for high-temperature resistance applications as compared to their metakaolin-based counterparts. Kong et al. [53] compared the residual compressive strength after exposure to elevated tempera- tures for fly ash and metakaolin based geopolymer matrices. Fly ash geopolymers gained strength (6%) while metakaolin geopoly. mers lost strength (34%) after exposure to 800°C in a furnace for one hour. A large number of small pores facilitating the escape of, ‘moisture on heating and sintering of un-reacted fly ash particles ‘were suggested to be the reasons for the strength increase in fly ash-based geopolymers. Since metakaolin geopolymers have higher moisture content than fly ash geopolymers, they are prone to greater damage on exposure to high temperatures, Water-to- solids ratio is an important factor tobe considered while designing ‘geopolymers for fire-resistance, Guerrier etal. [59] studied the high-temperature performance up to 800 °C of combined fly ash and slag geopolymers at the ratios ‘of 100/0, 65/35, 50/50, 35/65 and 0/100 by weight. t was found that as the initial strength increased, residual strength exponen- tially decreased. The ability of the materials with high ductility (Ge, less brittleness) to accommodate thermal incompatibilites due to uneven temperatures caused during heating was reported to be the main factor leading to reduced strength losses. ‘The importance of reactive SiJAl ratio and iron content ofthe fly ash on compressive strength after high-temperature exposure was highlighted by Rickard etal. (50,70). Rickard et al. (59) also com- pared the thermally-induced micro-structural changes of two fly ‘ash mixes, one highly reacted, and one lowly reacted. In these ‘works, fly ashes from different sources were assessed for their suit= ability for producing geopolymers for high-temperature applica: tions. Although the assessment of different fly ash sources is important, nonetheless, the know-how of tailoring the geopolymer mix using a single fly ash is also essential and needs exploration. Not all geopolymer formulations possess good thermal resistance, and thermal performance greatly depends on mix design factors such as SI/AI ratio, Al/Na ratio, and water/solids ratio, other than factors such as curing condition, precursor type and alkali cation ‘ype, 3.3.1.2, Use of aggregates. Kong etal. 7) also studied the behavior of geopolymer and geopolymerjaggregate composites when exposed to elevated temperatures. The strength of the fly ash- based geopolymer declined with the inclusion of aggregates ic, ‘geopolymeraggregate composites caused by differential thermal expansion between the geopolymer and the aggregates. Separate dilatometry tests showed that while aggregates underwent expan- sion at elevated temperatures, the geopolymer matrix experienced contraction. The effect of sample shape was also noted, Cube sam- ple (25 mm) of fly ash geopolymer paste exhibited strength gain When exposed to high temperature (800°C) while cylinder speci- ‘mens (35 x 70mm and 100 > 200 mm) made of the same material showed a decrease in strength. Fly ash geopolymer mortar and ‘geopolymer concrete made using aggregates of size less than 10mm, showed almost no strength retention after elevated tem- perature exposure. Geopolymer concrete using graded basalt per- formed better than that using graded slag aggregates and also performed better than those using either 10-14mm or 14-201m sized aggregates. sa © aot ea Consrcion ond ling Meters 21 (2018) 514-526 Pan et al. [72] compared the performance of geopolymer and ‘OPC concretes in 100 x 200 mm cylinder. Residual strengths were found to degrade to approximately 60% of their original strength after exposure to $50 °C. Thermal strain differentials due to tem- perature gradient were a major reason for the strength loss of ‘geopolymer and OPC coneretes, In comparison with OPC concrete, 2 higher strength loss occurred in geopolymer concrete during heating, This was attributed, on the one hand, to the geopolymer concrete experiencing substantial thermal incompatibility between aggregate and matrix in the range of 200-450°C and, ‘on the other hand, to the absence of transient thermal creep in geopolymer to accommodate non-uniform deformation dutit ‘thermal exposure. This also indicates that since not all eopolymer ormulations perform better than OPC when exposed to elevated temperature, it is vital to tailor the geopolymer concrete mix design. Both the performance of geopolymer paste and selection ‘of compatible aggregates are important factors for high- ‘temperature applications. Rickard etal 73] observed that the use of quartz aggregates in, fly ash geopolymer concrete led to greater strength losses (at ele- vated temperatures) when compared to using expanded clay aggregates. It was due to the large thermal expansion of quartz ‘aggregates. t was also observed that the quartz aggregate geopoly- ‘met experienced more severe dehydration-induced cracking and strength losses at temperatures below 300 °C, due to its lower per- ‘meability. At temperatures above 500°C, sintering was found to Promote strength increase It was also suggested in this study that performance improvements could be realized by optimizing the paste formulation so that itis less prone to dehydration damage andjor by altering the alkali cation type ‘Abdulkareem etal [74] found thatthe introduction of commer- cially available lightweight expanded clay aggregates to the Beopolymer paste considerably enhanced the mechanical and ‘microstructural properties subjected to elevated temperatures. The compressive strengths of geopolymer concrete in this study before and after exposure to elevated temperature were not very high due to the use of lightweight aggregates. Vickers etal, (75] found that the use of low Si/Al ratios in their fly ash geopolymers resulted in superior thermal properties after ‘exposure to 100°C. It was also noted that shrinkage during, high-temperature exposure could be reduced by the addition of inorganic fillers such as alumina and wollastonite, Masi et al [75) studied the thermal and fie resistance properties of foamed ‘geopolymers containing PVA and basalt fiber reinforcement. PVA fibers were found ta increase the flexural strength and toughness ‘of the geopolymer composite. Basalt fibers helped to improve the flexural behavior of the composite after elevated temperature ‘exposure. Aslani [77] has proposed constitutive relationships for ‘the normal and high strength geopolymer concretes when exposed to re, 3.2.12 Tota alkali content in geopolymer. The total alkali content in ‘geopolymer system is significant in determining the room temper- ature mechanical properties as well as the high-temperature prop- erties. Hence, optimum alkali content is desirable to atain a good -gcopolymer mix with sufficient initial strength and least damage after heating, Shaikh et al [78] found that the fly ash geopolymer concretes produced using higher molarity NaOH solution (13 M and 16M) exhibited much loss of compressive strength when ‘exposed to 800°C, contrary to geopolymer concrete produced using 10M NaOH solution which showed an increase in strength at 600 and 800 C, Bakharev (54) studied the effect of alkali cation type (sodium and potassium) on the thermal performance of fly ash geopolymers. It was reported that potassium based geopoly- mers performed better than sodium-based since they underwent an increase in compressive strengths after thermal exposure, whereas sodium-based geopolymers experienced strength redue- tion, However, it was reported that due to large changes in com- pressive strength and deformation of geopolymer samples on ‘thermal exposure, they were unsuitable for refractory applications. Lahoti etal. [57] showed that geopolymers with stable (or even enhanced) strengths upon thermal exposure for structural applica- tions could be realized by proper mix design tailoring. Results showed that K-geopolymer exhibited marked strength enhance. ‘ment (30-40%) while Na-geopolymer showed reduced strength (10%), but the strength of mixed sodium and potassium (Na-K) geopolymer remained unchanged after exposure to elevated {temperature 3.32, Fire-induced spalling and fie tests Following discussion helps to understand that geopolymer has excellent fire resistance capabilities and that geopolymer-based binders show inherently superior fre resistance as compared to Portland cement-based binders (52) Joseph Davidovits |79) observed that geopolymer cements pro- vide excellent fre resistant properties up to 1200 °C. Two comple- mentary properties inherent in geopolymer binder make it an attractive fire barrier. i. Nano-porosity in 3-D structure allows physically- and ‘chemically-bonded water hydroxyl groups ~OH) to migrate ‘and evaporate without damaging the geopolymer cement. Residual compressive strength of geopolymer cement was ‘observed to be 20MPa after 3h at 100°C (9OMPa at 20°C). in comparison, high-performance Portland blended ‘cement (100 MPa at 20°C) exploded between 300°C and 400°C, because hardened Portland paste does not allow any release of vapor pressure. ‘The same bonded water (OH groups) provides high ‘endothermic properties to the substrate. Endothermic regu- lation is a function of SifAI ratio. For a 10mm thick panel ‘exposed to a 1000°C flame, the measured rear face temper- ature after 30 min of exposure reached 180°C, 270°C and 300°, respectively for 3 different geopolymers, namely, Na-Poly (sialate), K-Poly (sialate-siloxo) and K-Poly (sialate-disiloxo), Zhao etal. [80] concluded that, when compared at the same strength level, the geopolymer concrete possessed higher spalling resistance ina fire than Portland cement concrete due to its increased porosity (measured using surface exposure test and standard gas furnace fire test). Geopolymer concrete was found to have more connected pores (measured by the sorptivity test). Hence, it was suggested that water vapor could escape from the -geopolymer matrix more quickly than in Portland cement concrete, resulting in a buildup of lower internal pore pressure Provis etal (51| conducted fire testing on geopolymer concrete derived from coal fly ash and metallurgical slag reacted with sodium silicate solution and using quartz sand and crushed granite as aggregates, Geopolymer concrete panels (4’ x4’ x 6") were tested following the standard time-temperature curve (ISO 834- JEN 1363-1/ASTM E119). The rate of thermal transport was found to be low and very minor degree of structural damage was observed during the 4h fie tet. Gluth et al, [82] studied the performance of two fly ash geopoly- ‘mer concretes (using quartz aggregates or using expanded clay lightweight aggregates) when exposed to ISO 834 standard fire curve, Both concretes were found to be unsusceptible to spalling, which was attributed to their high permeability and presence of low amount of chemically-bound water. Acoustic emission mea- surements were employed to study the spalling events and crack propagation in the samples. Ali et al. (82) found that geopolymer tah oo fConsrction and lng Materia 2212018) S14-526 sa conerete had excellent heat resistance capabilities. On exposure to hydrocarbon fire, no spalling was observed, Fly ash geopolymer concrete panels retained 60% of strength, while cylinders retained 10-20% strengths after exposure to high temperature. Vickers etal {84 found that the use of alumina filler together with a fiber tr: blend aided the development of composites with good integrity ater fire testing for 3 h. However, thermal conductivity was found to increase due to the use of alumina, Cracking on hot and cold faces was observed to be minimal 4. Fire performance of Portland cement concrete vs geopolymer concrete Ie is very important and interesting to understand the differ ences between the performances of Portland cement concrete as compared to geopolymer concrete, Table 4 describes some of the differences, It can be observed in the table that both Portland cement concrete and geopolymer concrete are incombustible However, thermal conductivity for geopolymer concrete could be Tower than OPC concrete. Geopolymer concrete has shown better spalling resistance compared to OPC concrete. This has been attrib- tuted to the interconnected pore structure in geopolymers, as well as to the finding that water does not form part of the chemical structure in geopolymers. In the case of OPC concrete, high- temperature heating seriously affects the chemical structure of hydration products such as calcium silicate hydrate (C-S-H) and calcium hydroxide (CH) while the chemical structure of geopoly- ‘mers is litle affected by the dehydration reactions. Furthermore, strength loss in geopolymers subject to high-temperature heating could be prevented in geopolymers by a careful selection of binder and aggregates. Recently, Nazati etal [85] showed that geopoly- ‘mer concrete performs better than OPC concrete in thermal shock situations, Geopolymer concrete can thus find applications in situ. ations with a greater risk of fire that requires instant quenching with water, 5. Application of geopolymers for heat and fire resistance ‘There have been several applications of geopolymers as cements and coneretes [58,71,80.93,94), heat and fire resistant material [2,4%,79,95-106], thermal insulator [11,49,51,107— 115}, thermal energy storage concretes [114 refractory material [52,115-117], intumescent coating for steel fire protection [118,119] and precursors to ceramic formation [120,121]. It also has applications in high tech composites (85,122-125] and medi cine [126]. Geopolymers have been used to make heat-resistant lightweight concrete and composites for making abrasive and heat-resistant industrial instruments, They can be used to make Fie performance of Porand cement concrete vs, gepolyer concrete composites filled with lightweight filler (vermiculite or perlite) for heat insulation of high-temperature equipment, They have been applied to make fireproof doors of elevators and as a heat resistant adhesive to install heat-resistant aerated concrete tiles to the hot surface ofa stove [19]. Buchler [95] illustrated the use of Geopolymer resins and GPMC composites in the field of air fl- tration at high temperatures. Liefke (95) demonstrated different industrial applications of foamed inorganic polymers, geopoly: mers, for ire protection, sound absorption, and thermal insulation (TROL foams), Varela and Privorotskaya [127] explained the use of geopolymer as a concrete coating for fire protection. These industrial applications of geopolymers show the potential of ‘geopolymers to be applied as a heat and fie resistant material 6. Discussion ‘There is a need of a green construction material for structural applications with admirable fire resistance and mechanical perfor ‘mance. It is anticipated that geopalymer has the capacity to fit the bill. However, to ensure the good structural performance of geopolymets subject to high-temperature heating, geopalymer ‘must perform well at micro-scale (ie, the stability of chemical structure), at meso-scale (ie, resistance to deformation) and rmacro-scale (ie, strength endurance and spalling resistance), Many researchers have reported the performance of geopoly- mers at micro-scale and itis noted that geopolymers are chemi- cally stable and do not undergo breakdown of chemical structure in contrary to OPC hydration products which undergo severe dete Hloration on thermal exposure. Its observed that the factors such 4s Si/Al ratio, alkali cation type and alkali content are important to determine the chemical structure of geopolymers before and after exposure to elevated temperatures. These factors should thus be tailored to realize a right geopolymer mix for structural fire applications. High-temperature exposure causes thermal shrinkage/expan- sion in geopolymers, which in tum causes macro-cracking. [tis importance to control the water content in geopalymer mix to reg ulate the meso-scale thermal deformations. For example: since rmetakaolin-based geopolymers require a significantly higher amount of water as compared to fly ash-based geapolymers for ‘workability purpose, metakaolin-based geopolymers might not be a good choice for structural fie-resistance applications (42 Thermal deformations are also influenced by the composition of alkali activating solution as well as the type of alkali cation. For example: Using potassium as alkali cation, thermal shrinkage is found to reduce when compared to using sodium as alkali cation [57]. These factors are important and should be considered while designing geopolymer mix for high temperature applications. (as Wink) 1s Tncombustible doesnot barn [2180871 103-04 Wink or geapelymer binge |S8) eter spalling resistance than OPC canctete [8981338 0-92) Strength oss water dase to 20°, alum nyeronde stats dssocatng dase to 5S00-100"C, and clcum site Bydrate undergoes a continuous Dyeakdowa subject elevated temperatures Dae toss in seagth cement pastas wellasagsegte, a empeatutes above 500"C Concrete is considered structurally het use! Loses suength wath use in temperature By care selection of aggreztes, sven ss canbe minimized up o 600°C. At further ger erperture, hee sgnican stengh ss 8) Compare to Portland cement concrete, eopeymecs ana ‘nfostuctrl stably The chemical ands geoplymes 6 net Breakdown eventhough a tansfosmaion rom the amerptous pase tthe cystine pase afte observed a temperatures ‘Wh appropriate agarqats geoplymer concrete provide excelent ‘re estan propertes up 1200°C 3) 524 [Mtn eto Construton ond Bung Mater 221 (2019) 514-526 Compressive strength of geopolymers can be affected by ‘microstructural changes (including crack formation, pore structure changes, densification, sintering, and melting) and phase composi- tion changes (such as growth or destruction of crystals and trans- formations in geopolymer paste). A number of factors affect the ‘compressive strength of geopolymers on exposure to elevated tem- peratures. These factors may include the choice of precursor, use of ‘aggregates, total alkali content in geopolymer, etc and have been dis- ‘cussed at length in this article. Geopolymers with stable (or even enhanced) strengths upon thermal expasure can be realized. It hhas also been observed that geopolymer-based binders show inherently superior fire-induced spalling resistance as compared 10 Portland cement-based binders. Further, since not all geopolymer formulations perform soundly at ambient as well as on high-temperature exposure, tailoring of ‘mix design to produce geopolymers with good thermal stability is essential. With careful mix design, remarkable chemical stabil- ity, low volume changes. strength endurance, and spaling resis- tance can be achieved for geopolymers. Mix design factors which need to be controlled include SifAl ratio, Al(Na ratio, and water/solids ratio other than the factors such as precursor type, allali cation type, and curing condition. The performance of ‘geopolymer paste as well as the selection of compatible aggre- gates, fibers and/or fillers, ate important considerations for high- ‘temperature applications. Fucure research is necessary to have a Detter understanding of interrelation between micro-, meso-, and ‘macro-scale properties, the mechanism related to the reaction of sgeopolymer when exposed to the elevated temperature, and the ‘optimum formulation of geopolymer related to the best perfor- ‘mance at high temperature exposure. 7. Conclusions ‘This article reviewed the potential of geopolymers to enhance the fire resistance of structures by critically reviewing its proper- ties subjected to elevated temperature exposure. The properties ‘of geopolymers were classified into three scales, namely, micro- scale, meso-scale, and macto-scale and comprehensively dis- ‘cussed. It was noted that geopolymers are chemically stable and ddo not undergo breakdown of chemical structure in contrary to ‘OPC hydration products when exposed to high temperature. Ther- mal deformations and macra-cracks were found to depend on the ‘water content, composition of alkaline activator, and alkali cation type. Compressive strength of geopolymers was observed to be affected on the one hand by microstructural changes such as the evelopment of cracks, porosity changes, and densification, and ‘on the other hand, by phase composition changes. Geopolymer- ‘based binders showed innately superior spalling resistance as com~ pared to Portland cement-based binders. Nonetheless, it requires careful mix design and control of factors such as precursor type, aggregates, total alkali content, and water content, to realize desired chemical stability, volume stability, strength endurance, and spalling resistance, All this has been discussed at length in this article, The curtent applications of geopolymers for heat and fire resistance have been presented in a nutshell Declaration of Competing Interest None. ‘Acknowledgments ‘The authors would like to thank the funding support for this, ‘project from Birla Institute of Technology and Science, Pilani, India (Research Initiation Grant), and from Ministry of National Development, Singapore (Land and Livability National Innovation Challenge, 2NICCFP1-2013-4). References 1115 Mines, 1 Pans Youre. Daw, Concrete, Second ef. rece Hall Upper Sele ver NL 208 (a1 2k, aoe seg of ont th temper = 4 (81 fimo cou 2 aca Tehomme fre Cheops soning nop este ance) Exe Mech ASCE 105 (3) (190) 72-262, (a) Ya chan, lo, W Sun Compresve sengh an pore sre a eh Fevormss concer exper Io bigh teers upto BC Ces tes 502) (200) 27-25 (51 GX Ry, Ee of feo cnte and concrete sre, Pg. Sr. Ser en 2) 200 938-7 {61 Vtytea voc o apiiova Hosor, ect f empertreon prs const for nucaPafey sac, Com Cone Res 31) (209) (1 ane ¥ eta ltt eget othe re tate an Tectmal 38 (1) (2008) 23-34 (a) 1: Secson EA kee Wit Vaden. Youngs mals of cement paste ‘ltted empertces Com Cone Res 37) (2007) 29-262 (0 GA pany Pee pti of ct ates nC {0 | Zhan.) Zheng. GF. Peng. PS. Sun, Spllng ané cracking mogeling of hih- Desorance conte expose owe mperae Ma Cont Res 69 win See Bere 201) 8-308, {12} Dee Fyn ME. cee, A Noumowe, Thermal behav of nstested fn seed high sree cone tonlanng poypropsene bess Siete pert} Suc He ng 8 (42017) OE {331 Wo ihalg Wr Rod Eeaeness of payropyine ad tel es in ‘anc fre resiune of hate nett kms} Se Ee i) Gon, tna] CMa By. 6. Teas es toprol Re pe and dose on Sh pny shane coc ug ae ea OT) 118 Yer ya AL esau A Sion Noun nr of ‘Srpeatre Spee tanfer tn means proper, Cons Bui Nr 132 (2017) 26-250, tu Ema, ie Sy Oe {171 Fz Hamaty Thermal prpetis of cone a leat empertrs cer S118) {081 faa Fase ptectn of concee scree st ce fg Sect tue 6) 200) 15-10, {39 IF van Dever ceoples Sut, processing. popes tnd nanial appears, WoosesdPblahng 20 ta ftps] nen ict rier Fv Indu apicaton, Wocchecd Fulshing 20029. “ (21) Deo Dado, Copy = Ui igh Teper Taong Aaterat or ie Manatee sf Advanca Composter 20 Iteration SimpeSympontum an Exibon oak a '36 (1951) 198-ae, (231 HN TSE var Deventer, Te. ropsamersaon of akminorscate Migrant er rcs. 303) 200) 7-200 ta Bon Ferd ther LC ey. rao an ‘Steyn Baty 53 (2a Wet U fe. Dombromsi. A. Bohl Susinable sgn of Eeopaymers evcvon ofr mates by Ie interton of conore {saennonmenal aspects nh ay pases tel etl {SLT int) vane le pert or Sosa {jee Engneting Waseda Unveny. Tone, pan Jone Ith 1th 207, Springer non andon 2007, pp 218-285 (25] Non Wan, DG. have. Sk creemouse 35 emisions ip ohe Constuton lass an ansaid evalua fa cones pA) ‘tain Canes Pod 167 (207) 188 120 (25) CFs J Mss Mah SK Chava AA Muse Cooper tronae ar skal repair mater a comprehensive review Renew {27 Ferone Messina, Roviello Colangelo, Ciofh lll actvated waste fy ash as ‘aty-age pics mechan popes sh edo seg ater expose Seated temperate Comportes ar: eg 139 18) et 08, (281 A Sabo SauneM Melesa Rie cere, ote aa Sctnated cement buted on fel) bck tes sulle fore Siutactuig of bling ae) Ceaner ra 166 (2017) 22°95 and Concrete, Longman Scesite & IM toh eo /Consructon and Bung Materia 221 (2019) 514-526 325, [29] &. Messina, C Ferone F. Colangelo. Ciofh. Low temperature alialine dechation of weathered fi ash tnluence of mera admbeuzes on eal ae Delormance, Const Bud Sater 86 2015) 155-177 Iso) Andi Cott Calangel TCrieca F Montagna L Sato, Cal hy {sh ss raw materi forthe manlactre 6 geoplyner Dated. rogues ‘Waste Manage 28 (2) (2008) 416-423. Iau) €D Aue EB Gorur, ©. Kaban Bll, S,Ukenapa,£ Liga. Vey high Strength (120 MPa} css Fy ash geopotjer tray ached at dierent ul, Mater 86 (2015) 673-078 [32] | Davieows,Geopymes | Them, Al 37 (8) (1981) 1633-1656. 133] Pat kumar Reducing the enirnmental impset of concrete Conc nt. 22 {20) (200. [pa KE Scheer, 1, Kip asovaton in Use abd Resa ob Montes. Canada 2007 135) [LG Lin, SN. Raman. EC. ai, MEM. Zan, R Hamid, synthesis of nano femmenivous addves from agrcatural wases for the precuclion of Ssstanableconzete, Cleaner od 171 (2018) 1150-1160, [aay & Kajeate Me Hae, Cement Indust greene at emitons ~ Management options ang abatement om, Cleaner Pod. 112 (2016) fons). 1571 ML ranizo,s. Alonso, ML. Blanco Varela, A Falomo, Alkaline activation of tealao eet of alam hyaroice i the products of feacon, fA Ceram, Soc. 85 (1) (2002) 225-231 [D8] A femander Jmener, A Plame, Charactersation of fy ashes. Potential Teacorty a alalne cements uel 82 (18) (2003) 2259-2265, 1p91 APaloms, s. Alonso. A Fernandez mene | Sobragos, |. Sanz, Alkaline ection of ashes NMR study othe reaction product | Am Ceram Soe 57 (6) (2004) 1iat-1145 [ao] X chen. A Suso,L} tube, ect of calcium on setting mechanism of Ietatain base gepolynej A. Ceram, So. 101 2) (2018) 857-868 [a1] IL Pros, Acvating soliton chemistry for geopotymers. in J Prov 18 van Deventer (Eas). Geoplymers suuctre. Processing, Popemtes abd Industral Appcations, Wooehend Publishing, 200, 9. 56-71 [a2] Ke Labot KX Wong, El Yang. XI. Tas. ets of SAL moe etl 08 Strength endarance a volume sabity a metstaoinseopelyner subject to elevate temperature, Ceram int 44 (5) (2018) 3720-574, [a3] VER taboss, KID. Mackenzie, Synthesis and theal behaviour of otssum sate geopajmets, Mater Let 57 (9) (203) 1477-42 a FF Barbosa a) Macencie. Teal behaviour of tarzan geopolynes nd composites ested rom sodium potas, Mater Res. Bul 38 2) (2003) 318-331, 145] PV. Keven. G¥. Kove, Diected sythess of aliline aluminosicate Ininerls ina geocernent atx Mater Se. 2 (9) (200) 2944-2852 [as] Cx" Kovaudke Pa Kien, Prodicing. re and beaten fcopalymes. in: JL Provs. |S) vah Deventer (Eds), Ceoplyners ‘Sorte, Processing: Poperet ané Indu Applestions, Woodhese Pushing. 2008 pp 227-266, [a0] A Fernzncerjinanez. 1. Pastor, A Martin A. Palomo, High

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