Processing

Rev. and properties

Adv. Mater. of geopolymers
Sci. 44 (2016) 273-285 as thermal insulating materials: a review 273

PROCESSING AND PROPERTIES OF GEOPOLYMERS

AS THERMAL INSULATING MATERIALS: A REVIEW

Emy Aizat Azimi1, Mohd Mustafa Al Bakri Abdullah1,2, Liew Yun Ming1,
Heah Cheng Yong1, Kamarudin Hussin1,2 and Ikmal Hakem Aziz1
1
Center of Excellence Geopolymer and Green Technology, School of Materials Engineering,
Universiti Malaysia Perlis (UniMAP), P.O. Box 77, D/A Pejabat Pos Besar, 01000, Kangar, Perlis, Malaysia
2
Faculty of Engineering Technology, Universiti Malaysia Perlis (UniMAP), P.O. Box 77, D/A Pejabat Pos Besar,
Kangar, Perlis 01000, Malaysia
Received: August 06, 2015

Abstract. Geopolymers are inorganic polymers with 3D framework structures that exhibit supe-
rior mechanical and physical properties including high early strength, low shrinkage, good ther-
mal resistance and good chemical resistance. The global warming scenario increased de-
mands for the heat insulator material especially in the construction sector. Traditionally, ordinary
Portland cement (OPC) has been used as the binder for concrete. However, the OPC has less
resistance to thermal exposure. Therefore, development of other or alternative binders that can
withstand the thermal exposure is considered vital in order to produce better thermal insulation
material. Based on previous research, geopolymer offers good resistance to corrosion, abra-
sion and heat. Fly ash, metakaolin, kaolin, and slag are commonly used raw materials for the
preparation of geopolymer composites. This geopolymer material also offers an innovative and
sustainable solution for maintaining infrastructure. This paper summarizes review on the
geopolymer processing and along with the potential of geopolymer composites for thermal
insulating applications. This review includes geopolymer fundamentals and technology struc-
ture, geopolymerization mechanism, raw materials and preparation, and thermal performance
of geopolymers.

1. INTRODUCTION duce the exterior wall surface temperature effec-

tively. The insulation coatings painted onto the
Due to the global warming scenario, demands for
QdX[SX]Vvb฀TgcTaX a฀fP[[฀RP]฀TUUTRcXeT[h฀aTSdRT฀cWT
the material that can insulate heat are vital espe-
temperatures at the surface and within the building
cially in the construction sector. Traditionally, ordi-
and thus protect the building, which obviously can
nary Portland cement (OPC) has been used as the
aTSdRT฀cWT฀T]TaVh฀PQb a_cX ]฀ U฀P฀QdX[SX]Vvb฀TgcT
binder for concrete [1]. However, the OPC exhibits
rior wall, roof, and indoor area [6]. However, the cur-
high thermal transmission. The development of heat
rently available heat insulation coatings are organic
insulation coatings are new energy-saving materi-
binder coating so that they are easy aged under
als in recent years [2-4]. Cekon et al. [2] found that
ultraviolet [7]. Therefore, development of other or
coatings of hollow microspheres with geopolymer
alternative binders that resist heat transfer is con-
paste can contribute to the thermodynamic perfor-
sidered vital in order to produce better thermal insu-
mance up to 5% in daytime. Another study by Guo
lation material. Recently discovered geopolymers
et al. [5] found that the heat reflective insulation
are materials that are produced by alkali activation
coating made from geopolymer materials could re-
of aluminosilicate raw materials, which transformed
Corresponding author: M.M. Al Bakri Abdullah, email: [email protected]

o฀ ฀ SeP]RTS฀EcdSh฀ T]cTa฀ ฀ cS
274 E.A. Azimi, M.M. Al Bakri Abdullah, L.Y. Ming, H.C. Yong, K. Hussin and I.H. Aziz

into reaction product by geopolymerization in a high that geopolymer compounds are the final and stable
pH environment and hydrothermal conditions at rela- phase [20]. This is in agreement with the investiga-
tively low temperatures (which up to 120 nC). Con- tions on ancient Roman cements that have indicated
sidering the fact that the organic thermal insulation the presence of amorphous compounds in it [21,22].
materials widely used today are flammable and the The outstanding performance and durability of
inorganic thermal insulation materials need com- ancient Roman cements and outcome of
plex processing conditions and high sintering tem- [dZW ebZhvb฀aTbTPaRW฀RaTPcTS฀X]cTaTbc฀X]฀cWT฀_
perature, which is high in manufacturing cost, the tential to produce a new cementitious material that
geopolymer material has good application potential is high in strength and more durable. Later, Rus-
as thermal insulation material in some situations bXP]฀aTbTPaRW฀SdaX]V฀cWT฀ vb฀฀aTbd[cTS฀X]฀P฀QTccTa
[8]. Due to the low energy requirements of produc- understanding of the setting reactions of alkali-acti-
tion from common raw materials and their inflam- vated slag cement and the hardening process which
mability at high temperatures, these compounds was found to be more complex than that proposed
(geopolymer) are attracting increasing interest as by Purdon [16]. The most comprehensive and suc-
ecologically friendly fireproof building materials, cessful research in this field was conducted by
sound and heat insulators and materials for encap- PeXS eXcb฀M N฀P]S฀P__[XTS฀cWT฀cTa ฀uVT _ [h Tav
sulating hazardous wastes for storage or disposal to these alkali activated aluminosilicates.
[9,10]. The need for environmentally friendly construc-
Geopolymers are class of binder materials that tion materials (especially in the structure of the build-
are formed by the activation of aluminosilicate ma- ing and wall that insulate heat) to sustain the devel-
terials with alkaline or alkaline-silicate solutions and opment is a critical environmental issue at this era
it was first named and introduced by Davidovits [11]. in the construction industry. The production of con-
Geopolymers which are also known as inorganic crete in industry is said to be one of the contribu-
polymers or alkali-activated binder have rapidly tors of the global warming. This fact is due to the
gained worldwide interests [12]. Geopolymer is con- widely use of Portland cement as the main compo-
sidered as the third generation cement after lime nent in the production that said to be responsible
P]S฀AB ฀FWT฀cTa ฀sVT _ [h Tat฀Xb฀VT]TaP[[h฀dbTS for about 6% of the CO2 emission worldwide [24].
to describe an amorphous alkali aluminosilicate. Using geopolymer materials as concrete are able
AcWTa฀cTa b฀c ฀STbRaXQT฀VT _ [h Tab฀X]R[dST฀sP[ to offer comparable performance to the traditional
ZP[X PRcXePcTS฀ RT T]cbt ฀ sVT RT T]cbt ฀ sP[ZP[X cementitious binders in a wide range of applications,
Q ]STS฀RTaP XRbt ฀P]S฀sWhSa RTaP XRbt ฀ [cW dVW but with the extra advantage of lower greenhouse
there is variety of nomenclature, all these terms emissions [25-27]. Geopolymer technology is also
describe materials synthesized utilizing the same attracting increasing attention because it provides
chemistry. It essentially consists of a repeating unit viable economical alternative to organic polymers
U฀ bXP[PcT฀ ] Ta฀ rEXrAr [rAr ฀ M N and inorganic cements in diverse applications, such
Geopolymers are amorphous to semi-crystalline as refractory adhesives and fire-proof [28]. The con-
three-dimensional silica-aluminate materials. They cern is also due to their excellent mechanical
are prepared by mixing and activating the alumino- strength, adhesive behavior, long-term durability and
silicate sources such as fly ash, metal slag, kaolin exceptionally high thermal and chemical stability
or metakaolin with alkaline liquid (sodium hydrox- [29]. Thus, due to these excellent properties,
ide and/or sodium silicate) and curing at a moder- geopolymers can be potentially thermal insulating
ate temperature [15]. Geopolymers are classified materials that help conservation of energy and re-
as one of the green materials that contain many duce the CO2 footprints. Previous investigations by
exceptional properties such as high compressive Davidovits [30], Barbosa and MacKenzie [31, 32]
strength, low shrinkage, and excellent fire and acid reported very good heat resistant properties of ma-
resistant [16]. terials prepared using geopolymer, having thermal
In the 1950s, it is believed that Victor Glukhovsky bcPQX[Xch฀d_฀c ฀ r ฀nC.
was the first researcher attempting the modeling of In contrast to organic exterior wall coatings,
the geological process of zeolite formation [17,18]. geopolymer-based coatings have anti-ultraviolet and
It was synthesized by alkali activation of alumino- anti-aging capability [33-35]. It makes the
silicates that normally present in industrial materi- geopolymer more suitable for fabricating inorganic
als or wastes and some of them occur from natural exterior wall building coatings. In addition, a heat
sources [19]. These novel binders were initially known insulative paint, including pigments and fillers, was
Pb฀ub X[฀bX[XRPcTbv฀M N ฀E T฀aTbTPaRWTa฀QT[XTeTb added to the film forming material and had an im-
Processing and properties of geopolymers as thermal insulating materials: a review 275

Table 1. Chemical composition of fly ash, data from [42].

Composition SiO2 Al2O3 Fe2O3 CaO MgO SO3

Wt.% 55.3 25.8 5.5 2.9 0.8 0.3

Table 2.Chemical composition of rice husk ash, data from [43].

Composition Al2O3 SiO2 P2O5 SO3 K2O CaO Fe2O3 MgO

Wt.% 0.45 89.34 2.58 0.90 4.98 0.76 0.40 0.49

portant effect on the heat insulation coating perfor- attributed to the low thermal conductivity character-
mance [36,37]. istics of the lightweight aggregate which inhibits the
In this paper, the geopolymer processing, ther- heat diffusion through the structure.
mal properties and the suitability of geopolymers
as thermal insulator are reviewed. 2.1.2. Rice husk ash
Rice husk ash (RHA) is originated from waste pro-
2. RAW MATERIALS FOR duced by burning rice husk primarily for the genera-
GEOPOLYMER FORMATION tion of electricity, a type of sustainable biomass
2.1. Waste material energy. It is another pozzolanic material obtained
from the combustion process of rice husk [43]. Rice
2.1.1. Fly ash husk which is the hard protective shell of rice grains
Fly ash which is also known as flue-ash, is one of is an agricultural by-product of rice mills [44]. The
the residues generated in combustion, and com- growing environmental concerns and need for en-
prises fine particles that rise with the flue gases ergy from renewable biomass have led to a useful
[38]. Fly ash is normally captured by electrostatic and economical solution which burning rice husk
precipitators or other particle filtration equipment for electricity generation with zero net carbon out-
before the flue gases reach the chimneys of coal- put to the atmosphere. After burn process, the re-
fired power plants. Fly ash, together with bottom sidual ash is known as rice husk ash (RHA).
ash removed from the bottom of the furnace is in The main component of the ash is silica (which
this case jointly known as coal ash [39]. Depend- R ]bXbcb฀ U฀ r ฀fc ฀ c฀TgXbc฀_aTS X]P]c[h฀X]
ing upon the source and makeup of the coal being amorphous and partly in crystalline phases (although
burned, the components of fly ash vary consider- the duration and temperature of burning affect the
ably, but all fly ashes contain substantial amounts ratio of amorphous to crystalline phases of silica),
of silicon dioxide (SiO2) (both amorphous and crys- with remaining carbon as the major impurity and
talline), aluminum oxide (Al2O3) and calcium oxide other trace elements such as K and Ca [45]. In gen-
(CaO) [40]. Table 1 shows the chemical composi- eral, after organic constituents of the rice husk are
tion of fly ash. It is observed that fly ash consists being burnt off, RHA consists of highly porous par-
mainly of silica (SiO2) and alumina (Al2O3) (more ticles, leading to a low bulk unit weight and a very
than 80%), which make it suitable to be the raw high external surface area [46]. The amorphous silica
materials for geopolymer formation. is found reactive and suitable to be used as a poz-
Omar et al. [41] in their studied on effects of zolana. RHA has been successfully used in con-
elevated temperatures on the thermal behavior and crete for reduced permeability and enhanced sul-
mechanical performance of fly ash geopolymer fate resistance [44,47]. In addition, it has also been
stated that the use of fly ash geopolymeric struc- used to partially replace fly ash to regulate the Si/
ture along with the incorporation of lightweight ag- Al ratio in geopolymers [48]. Table 2 shows the
gregates enhances the mechanical and microstruc- chemical composition of rice husk ash. He et al.
tural properties of the geopolymers at elevated tem- [49] studied the synthesis and characterization of
peratures. This study also found that fly ash red mud and rice husk ash based geopolymer com-
geopolymer exhibits low thermal conductivity which posites. The study found that rice husk ash based
leads to better thermal insulation. This was also geopolymer obtained good strength and have po-
276 E.A. Azimi, M.M. Al Bakri Abdullah, L.Y. Ming, H.C. Yong, K. Hussin and I.H. Aziz

Table 3. Chemical composition of kaolin, data from [54].

Chemicalcomposition SiO2 Al2O3 Fe2O3 TiO2 ZrO2 K2O MnO2 LOI

wt. (%) 54.0 31.7 4.89 1.41 0.10 6.05 0.11 1.74

Table 4. Composition of metakaolin geopolymer mixtures, data from [33].

Samples Sodium silicate, wt.% Metakaolin, wt.% Sodium hydroxide pallet, wt.% Water, wt.%

MK1 70.24 28.43 0.89 0.42

MK2 67.64 27.38 0.86 4.09
MK3 64.56 26.13 0.82 8.47

tential to use as construction material. It also stated geopolymer material can withstand temperature and
that the rice husk ash show acceptable resistance able to insulate the thermal transmission.
towards thermal exposure [49, 50]. Metakaolin (MK) is prepared from kaolin clay.
According to Temuujin et al. [33], metakaolin is
2.2. Natural resource obtained by calcining kaolin at temperature 750 nC
for 24 hours. The main reason metakaolin is suit-
2.2.1. Clay able to be used as raw material for forming
Kaolin is a clay mineral that conventionally has been geopolymers is because it contains alumina and
used in the manufacture of porcelain. Kaolinite is silica composition in it [56]. It is also common in-
the mineralogical term that applies and refers to dustrial mineral which can be obtained in a large
kaolin clays [51]. Kaolin is a naturally occurring quantity with homogeneous properties. Metakaolin
material composed primarily from fine-grained min- is also environmentally friendly compared to OPC
erals and also the most abundant mineral found in because its production requires much lower calcin-
the earth [52]. Kaolin basically is composed of alu- X]V฀cT _TaPcdaT฀P]S฀T Xcb฀ r ฀[Tbb฀ A2 than
mina, silica, and water in variable combinations. It OPC [57]. Temuujin et al. [36] reported that Si:Al
has the huge potential to replace the conventional ratio of 2.5 and Na:Al of 1.0 are the optimum com-
OPC materials due to its unique properties and position to produce metakaolin-based geopolymers.
chemistry for producing environmentally friendly Table 4 shows one of the design compositions to
composites. Kaolinite is formed by rock weathering form metakaolin geopolymer mixtures [33].
process and the process of kaolin formation is called Temuujin [58], used metakaolin in his study on
kaolinization. It is white, greyish-white, or has the preparation and thermal properties of fire resis-
slightly colored. The main constituent, kaolinite, is tant metakaolin based geopolymer type for coat-
a hydrous aluminum silicate of the approximate ings. This study found that the metakaolin
composition 2H2O-Al2O3-2SiO2 [53]. Table 3 shows geopolymer coating samples showed up to 3% ther-
the chemical composition of kaolin. As refer to Table mal expansion after heating to 800 nC. However,
3, kaolin composed mainly of silica (SiO2) and alu- the geopolymer coatings also maintained high struc-
mina (Al2O3) (more than 85%), which make kaolin tural integrity with steel substrates when subjected
suitable to be the raw materials for geopolymer for- to a heat treatment by a gas torch and formulations
mation [54]. calcined at 1000 nC for 1 hour.
Jaarsveld et al. [55] study the effect of composi-
tion and temperature on the properties of fly ash 3. ALKALINE SOLUTION
and kaolinite based geopolymers. This study found
Alkaline solution is one of important parts in pro-
that kaolin based geopolymer can withstand the
ducing geopolymer. The main criteria for developing
temperature from 50 nC to 90 nC for long time with-
stable geopolymer are that the source materials
out significantly affect the crystalline part of the
must be highly amorphous and possess sufficient
geopolymer sample. It shows that the exposure of
reactive glassy content, low water demand and be
the geopolymer certain high temperature does not
able to release aluminum easily. The alkaline acti-
affects the structure of geopolymer. These prove that
vators such as sodium hydroxide (NaOH), potas-
Processing and properties of geopolymers as thermal insulating materials: a review 277

sium hydroxide (KOH), sodium silicate (Na2SiO3) ties compared to those based on sodium silicate
and potassium silicate (K2SiO3) are used to acti- and NaOH or potassium silicate/NaOH mixtures.
vate aluminosilicate materials. Geopolymer is syn- Another research by Xie and Ozbakkaloglu [67]
thesized by mixing the aluminosilicate-reactive used the alkaline activators that consisted of dis-
material (raw material) with strong alkaline solutions tilled water, sodium hydroxide (NaOH) solution and
[13,59]. Alkaline activating solution is very impor- sodium silicate (Na2SiO3) solution. The proportions
tant for dissolving of Si and Al atoms to form of the three components of the alkaline activator
geopolymer precursors and finally alumino-silicate solution were 65.3% of water, 24.8% of Na2SiO3,
material. The selection of different activators for alu- and 9.9% of NaOH by weight. The sodium hydrox-
minosilicate dissolution and its solidification into ide (NaOH) solution with 14M concentration was
tetrahedral geopolymeric cementation structure is constantly used in all the mixes.
very important. In most cases, the alkaline reaction
of aluminosilicates leads to formation of zeolite which 4. GEOPOLYMER TERMINOLOGY
is not a part of the cementation phase. Thus combi- AND GEOPOLYMERIZATION
nation of different anionic group activator with alka- REACTION
line chemicals is quite important to build stable tet-
rahedral structure of alumino-silicate phases for Geopolymer involves the silicates and aluminates
development of strength [60]. of by products to undergo process of
The most commonly used alkaline activators are geopolymerization. It is environmentally friendly and
NaOH and Na2SiO3. Compared to NaOH, KOH pro- need moderate energy to produce.
duced a greater level of alkalinity. But in reality, it Geopolymerization is also known as a geosynthesis
has been found that NaOH possesses greater ca- (reaction that chemically integrates minerals) that
pacity to liberate silicate and aluminate monomers involves naturally occurring aluminosilicates [57,62].
[61]. The potassium based alkaline solutions are Davidovits [68] observed the amorphous to semi-
usually very costly and are not suitable for economic crystalline three dimensional silico-aluminate struc-
viability for the production of geopolymer materials. tures. Davidovits also further categorized the
The sodium based alkaline solutions are preferred geopolymers structure based on the ratio of Si/Al
and in such cases the formation of geopolymer as shown in Fig. 1. The chain structures of [SisO4]4-
matrix is also depended on its curing temperature. tetrahedra with cations and neutralizing anions build
The curing of the product above normal atmospheric the mineral polymer framework in order to achieve
temperature is not a flexible option to adopt in com- the strength. These silicate minerals with OH bear-
mercial practice. Therefore, selection of proper ing characteristics then possess excellent rock
chemicals with alkaline group for geopolymerization forming property [69].
reaction at atmospheric temperature has been the Other alkaline activators that can be used for
focus of research [62]. Usually this alkaline activa- geopolymer formation are strong alkalis of chemi-
tor is prepared by mixing water, sodium hydroxide cal salts of Na2CO3, Na2SO4, K2CO3, K2SO4, small
and sodium silicate but other alkali metal systems amount of cement clinker [62,70]. Other chemical
or mixtures of different alkalis also can also be used. salts such as KCl, K2C2O4.H2O, K2CO3, and K2HPO4
The solution strictly needs to be concentrated to are also used as activator for geopolymeric reac-
avoid the end product to be a crystalline zeolite rather tion and solidification [70].
than a geopolymer [63, 64]. The following empirical formula has been postu-
Joshi and Kadu [65] prepared the alkaline acti- lated by Davidovits [30] to describe geopolymers:
vator using commercially available sodium silicate
Mn[-(Si-O 2 )z -Al-O]n . wH2 O,
liquid and sodium hydroxide pallets which contains
Na2O = 14.61%, SiO2 = 25.18%, and water = where M is an alkali metal, z is 1, 2 or 3, and n is
59.99%. The alkaline solution was prepared with the degree of polymerization.
NaOH molar concentration varying from 8M to 16M By dissolving an aluminosilicate powder in al-
and the mass ratio of sodium silicate to sodium kali solution such as NaOH, first AlO24- and SiO24-
hydroxide varied from 1.75 to 3.0. A study by tetrahedra are formed and, according to the con-
Gharzouni et al. [66] stated the type of alkaline so- centration of silicon in the solution, a type of mono-
lution is important. The research found that the mers was naturally formed. The molecular arrange-
geopolymers based on a mixture of potassium sili- ments in some geopolymer frameworks are shown
cate and KOH display higher mechanical proper- in Fig. 2. A reaction mechanism for
278 E.A. Azimi, M.M. Al Bakri Abdullah, L.Y. Ming, H.C. Yong, K. Hussin and I.H. Aziz

Fig. 1. Types of oligomeric structures. Reprinted with permission from [S.D. Muduli, J.K. Sadangi, B.D.
Nayak and B.K. Mishra // Greener Journal of Physical Sciences 6฀ ฀ ฀o฀ ฀ aTT]Ta฀ da]P[b N

Fig. 2. Reaction mechanism for geopolymerisation. Reprinted with permission from [J. Davidovits, In: Proc.
First international conference on alkaline cements and concretes฀ ฀_ ฀ ฀o฀ ฀ T _ [h Ta
Institute.]
Processing and properties of geopolymers as thermal insulating materials: a review 279

geopolymerization proposed by Davidovits [57] in- a 12M concentration of NaOH [76]. Mustafa et al.
volves the chemical reaction of precursors such as [77] in his research mixed the raw material with al-
alumino-silicate oxides (Al3+ in IV-fold coordination) kaline activator in the mixer. Further, the geopolymer
fXcW฀P[ZP[X฀_ [hbX[XRPcTb ฀aTbd[cX]V฀X]฀_ [h TaXR฀EXr was placed in the 50x50x50 mm mold and vibrated
Ar [฀Q ]Sb ฀F ฀T _WPbXiT฀cWT฀ H U [S฀R aSX]PcX ] for 20s on the vibrating table. The geopolymer
U฀ [฀X]฀cWTbT฀ [rEX฀ X]TaP[b ฀cWTbT฀R ]UXVdaPcX ]b samples were cured at different curing temperatures.
are usually written as (Si2O5wAl2O3) rather than Castel and Forster [14] in their research on manu-
(2SiO2wAl2O3). According to Davidovits the harden- facture the geopolymer used alkaline solution from
ing mechanism for geopolymerisation essentially a mixture of 12M concentration of sodium hydrox-
involves the polycondensation reaction of ide (NaOH) solution and sodium silicate solution.
geopolymeric precursors, usually aluminosilicate The mass ratio of alkaline solution to aluminosili-
oxides, with alkali polysilicates yielding polymeric cate material was 0.55. The specimens then were
Si-O-A1 bonds [72] that are also depicted in Fig. 2. cured for 24 hours. The ratio of the raw material with
In geopolymerization, aluminosilicate oxides the alkaline activator is important in forming the
firstly will dissolve in the alkali solution. Then the geopolymer [78]. The Si:Al composition for
dissolved Al and Si complexes diffuse from the par- geopolymer prepared from raw material were 2.5 and
ticle surfaces to the inter-particle spaces. Finally, a 3.5 respectively [79]. At the same time, Cheng and
gel phase is formed from the polymerization of added Chiu [80] used SiO2/Al2O3 ratio in the range of 3.16-
silicate solution and Al and Si complexes and fi- 3.46. Mustafa et al. [81], in his research used 2.5
nally hardened to form hard solid [18, 57]. as ratio of Na2SiO3/NaOH. Normally the ratio for solid
To produce geopolymer from kaolin, metakaolin to liquid (S/L) started from 0.6 and above.
or other clay materials, these three main steps are Liu et al. [82] in their research on thermal behav-
necessary [73]: ior of the geopolymer concrete used the ratios of
a) Thermal activation, the aim of which is to obtain the sodium silicate solution to sodium hydroxide
a clay material with high chemical activity. In this solution and the alkaline solution were 2.5 and 0.55
process dehydroxylation of clay mineral leads to by mass, respectively. They also used the sodium
an unstable amorphous solid. hydroxide with 14M molarity. The mixture of the
b) Alkali activation: activated alumino-silicate mate- solution was prepared at least 1 day prior to its use
rial is dissolved in highly alkaline solution to pro- to allow the exothermically heated liquid to cool to
duce silicate and aluminate monomers. ambient temperature. Wang et al. [83] studied the
c) Reactive setting or polycondensation, in which thermal conductivity of the geopolymer using raw
the silicate and aluminate monomers condense to materials with theoretical composition of SiO2/
a stable polymer network. Al2O3=4.0, the ratio of K2O/Al2O3=1.0 and H2O/
To obtain a well structured geopolymer with ac- K2O=11.0 (molar ratio).
ceptable mechanical properties, it is necessary to
T]WP]RT฀cWT฀PRcXeXch฀P]S฀b [dQX[Xch฀ U฀ [rEX฀b daRT 6. THERMAL INSULATION
materials in alkali solution. Thermal activation of the
source material is one way to meet this condition Thermal insulation is the reduction of heat transfer
and several investigations have examined the ther- (the transfer of thermal energy between objects of
mal activation process and its effects on final prop- differing temperature) between objects in thermal
erties [74]. contact or in range of radiative manipulated [84].
Thermal insulation is also known as a single mate-
rial or combination of materials that when properly
5. MANUFACTURING OF
applied, will retard the rate of heat flow by conduc-
GEOPOLYMER tion, convection, and radiation. It retards heat flow
Geopolymer is usually prepared by mixing material into or out of a object or building due to its high
(raw material) with the alkaline activator solution. thermal resistance [85]. Thermal insulation is the
The raw materials previously were ground by a cen- reduction of heat transfer (the transfer of thermal
trifugal ball mill until fine particles were obtained [75]. energy between objects of differing temperature)
The mixture of aluminosilicate and alkali activator between objects in thermal contact or in range of
solution then were turned into a slurry or paste and radiative influence. Thermal insulation can be
was cured at 70-80 nC for 24 hours. Normally, the achieved with specially engineered methods or pro-
dissolution of sodium hydroxide was modified in one cesses, as well as with suitable object shapes and
liter of distilled water in a volumetric flask to obtain materials. Thermal insulation provides a region of
280 E.A. Azimi, M.M. Al Bakri Abdullah, L.Y. Ming, H.C. Yong, K. Hussin and I.H. Aziz

Fig. 3. Thermal conductivity of foamy materials with different H2O2 contents in the geopolymeric paste.
Reprinted with permission from [V. Vaou and D. Panias // Minerals Engineering 23฀ ฀ ฀o฀
Elsevier Ltd.]

insulation in which thermal conduction is reduced a. Fibrous materials such as cellulose, cotton,
or thermal radiation is reflected rather than absorbed wood, pulp, cane, or synthetic fibers.
by the lower-temperature body [86]. The insulating b. Cellular materials such as cork, foamed rubber,
capability of a material is measured with thermal polystyrene, polyethylene, polyurethane,
conductivity (k). Low thermal conductivity is equiva- polyisocyanurate and other polymers.
lent to high insulating capability (R-value). In ther- There are several type of thermal insulation stan-
mal engineering, other important properties of insu- dard testing based on American Society for Testing
lating materials are product density (r), and specific P]S฀ PcTaXP[b฀ EF ฀ EF vb฀cWTa P[฀X]bd[PcX ]
heat capacity (c) [87]. standards are instrumental in specifying and evalu-
Heat flow resisted by thermal insulating materi- ating the materials and methods used to reduce
als as a result of the countless microscopic dead the rate of heat transfer. The flow of heat can be
air-cells, which suppress (by preventing air from delayed by understanding the conductive, convec-
moving) convective heat transfer. It is the air en- tive, and/or radiative behavior of the material in con-
trapped within the insulation which provides the ther- sideration. The ASTM that suitable for thermal insu-
mal resistance, not the insulation material. By mak- lation testing for geopolymer are ASTM C163 - 05,
ing small cells (closed cell structure) within thermal EF ฀ ฀ ฀ ฀ EF ฀ ฀r฀ ฀ EF ฀ ฀
insulation across which the temperature difference ฀ EF ฀ ฀r฀ ฀ EF ฀ ฀ ฀ ฀ EF ฀
is not large also reduces radiation effects. It causes - 07, ASTM C335 / C335M - 10e1, ASTM C1058 /
aPSXPcX ]฀u_PcWbv฀c ฀QT฀Qa ZT]฀X]c ฀b P[[฀SXbcP]RTb ฀r฀ ฀P]S฀ EF ฀ ฀M N ฀=WP[X ฀P]S฀= Sda
where the long-wave infrared radiation is absorbed [89] in their research used ASTM E 831-06 by us-
and/or scattered by the insulation material (low en- ing thermo-mechanical analysis (TMA) apparatus
ergy materials can also be used to minimize radia- to study the thermal conductivity and insulation of
tion effects). However, conduction usually increases geopolymer. Another study by Rickard et al. [90]
as the cell size decreases (the density increases) also used ASTM E831 to study the thermal insula-
[85]. tion of material from geopolymer. They used ther-
There are many types of material that suitable mal expansion testing to determine the insulation
for thermal insulation is available which fall under of material.
the following basic materials and composites [85]:
1. Inorganic Materials 7. THERMAL PROPERTIES OF
a. Fibrous materials such as glass, rock, and slag GEOPOLYMER
wool, fly ash.
b. Cellular materials such as calcium silicate, bonded Vaou and Panias [91] showed that the thermal con-
perlite, vermiculite, ceramic products and ductivity of foamy geopolymeric materials as shown
geopolymer. in Fig. 3. Thermal conductivity of the geopolymer
2. Organic Materials paste was decreased substantially from 0.053 W/
Processing and properties of geopolymers as thermal insulating materials: a review 281

Fig. 4. XRD patterns of the FA based geopolymer. Reprinted with permission from [N. Ranjbar, M. Mehrali,
U.J. Alengaram, H.S.C. Metselaar and M.Z. Jumaat // Construction and Building Materials 65฀ ฀ ฀o
2014 Elsevier Ltd.]

฀=฀ c ฀ ฀ I% ฀=฀ P[ ]V฀ fXcW฀ cWT฀ X]RaTPbX]V฀ U tion and is a refractory. Mullite retains its room tem-
hydrogen peroxide (H2O2) content from 0.7% and perature strength at elevated temperatures and has
2.02%. Further increment of the H2O2 content in the high temperature stability with low thermal expan-
geopolymeric paste has considerably does not pro- sion and oxidation resistance [94]. After the expo-
duce an effect on the thermal conductivity value. sure to 300 nC, peaks of quartz are still stable while
The results showed that the thermal conductivity of peaks of mullite become progressively stronger. The
foamy geopolymers is correlated to their cellular phase transition from goethite to hematite occurs
structure. A substantial decrease of the thermal at about 300 nC. At this temperature, most of the
conductivity value also can be achieved by control- constitutional water molecules have been released.
ling appropriately cells type, size, shape and vol- The pattern of XRD analysis for FA based geopolymer
ume. The results from these studies are in good subjected to 800 nC shows hematite starting to dis-
agreement with the state-of-the-art on thermal insu- appear while crystalline nepheline AlNaSiO4 (sodium
lation foamed plastics where the thermal conductiv- aluminum silicate) was present in the specimen al-
ity is correlated firstly to the thermal conductivity of though quartz remains the major phase. The mul-
the filling gas followed by the apparent density of lite was still present [95]. These prove that the main
foams and then the morphology of the cellular struc- structure of geopolymer does not significantly af-
ture [92]. fect by the high temperature. It also prove that
Ranjbar [963] studied on compressive strength geopolymer material suitable to use and apply as
and microstructural analysis of fly ash/palm oil fuel thermal insulator [31,96].
ash based geopolymer mortar under elevated tem- Feng et al. [8] studied the thermal conductivity
peratures showed the XRD analysis of the samples. of porous fly ash based geopolymer. Fig. 5 showed
Fig. 4 shows the XRD patterns of fly ash (FA) based the thermal conductivity of the porous fly ash based
geopolymers. The patterns were taken after the geopolymer material. At the same curing tempera-
sample was exposure to room temperature, 300 nC ture and when same amount of sodium water glass
and 800 nC. These studies state that the strong (H2O2) were added, the increasing of the H2O2 leads
peaks in FA base geopolymer identify the presence to reduction in density and thermal conductivity
of quartz, mullite, and goethite at room tempera- along with increasing apparent porosity. The H2O2
ture. Mullite is the only stable crystalline phase of were added in 60 g, 80 g, and 100 g. In addition,
the Al2O3rEXA2 system under atmospheric condi- with the increase of H2O2 amount, numbers of voids
282 E.A. Azimi, M.M. Al Bakri Abdullah, L.Y. Ming, H.C. Yong, K. Hussin and I.H. Aziz

Fig. 5. Thermal conductivity of the porous fly ash based geopolymer material. Reprinted with permission
from [J. Feng, R. Zhang, L. Gong, Y. Li, W. Cao and X. Cheng // Materials & Design 65฀ ฀ ฀o฀
Elsevier Ltd.]

inside the material with air contained could be gen- ture and maintenance cost. Development of
erated, thus resulting in the reduction of density and geopolymer seems to present a greener alternative
thermal conductivity and increase in apparent po- to ordinary Portland cements. Although extensive
rosity. Density and apparent porosity are generally researches have already been carried out, the de-
correlated with thermal conductivity. This is because velopment of geopolymer as a thermal insulator are
higher porosity means more voids and the thermal less been explored. It is hoped that future research
conductivity of air within the voids is much lower in this field will drive a new era of greener materials
than that of solid substance, thus leading to a com- in the construction industry.
paratively lower thermal conductivity of the whole
material [97]. It clearly proved from Fig. 5, for sample ACKNOWLEDGEMENT
of 80 A, starting from 2 g, 4 g, and 6 g H2O2, the
thermal conductivity values are 0.0816, 0.0744, and We gratefully thank for funding by Fundamental
฀I% ฀= ฀aTb_TRcXeT[h฀P]S฀cWT฀aT[TeP]c฀ST] Research Grant Scheme (FRGS). Besides, we
sity and apparent porosity are 335, 260, and 239 would like to extend our appreciation to the Center
kg/m3 and 79.1%, 79.9%, and 81.2%, respectively. of Excellence Geopolymer and Green Technology
Comparing the thermal conductivity of this po- @ UniMAP and the School of Materials Engineer-
rous fly ash-based geopolymer material with other ing, Universiti Malaysia Perlis (UniMAP).
thermal insulation materials, it can be seen that the
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