Construction and Building Materials 227 (2019) 116621

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Studying different silica sources for preparation of alternative waterglass

used in preparation of binary geopolymer binders from metakaolin/
boiler slag
Mónica A. Villaquirán-Caicedo
Composite Materials Research Group, (Centro de Excelencia de Nuevos Materiales), School of Materials Engineering, Universidad del Valle, Calle 13 # 100-00, Cali, Colombia

h i g h l i g h t s

 Rice husk ash (RHA) and silica fume (SF) were used to prepare potassium waterglass.
 Geopolymer binder with RHA/boiler-slag show a homogeneous and more compact material.
 MK-based geopolymer binder from RHA has higher compressive at long ages than SF binders.
 FTIR indicates that RHA-based binders has greater dissolution of MK than SF-based at 360 days.
 RHA100 geopolymer at 360 curing days and SF100 show 42.5 and 34.7 MPa respectively.

a r t i c l e i n f o a b s t r a c t

Article history: The production of geopolymeric binders based on metakaolin (MK), coal boiler slag (BS) and alternative
Received 1 February 2019 silica sources (rice husk ash (RHA) and silica fume (SF)) to produce potassium waterglass was successfully
Received in revised form 22 July 2019 carried out. The binders were characterized microstructurally and mechanically at different ages.
Accepted 1 August 2019
Monitoring of the reactions of the cements was carried out by techniques such as scanning electron
microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermo-
gravimetric analysis (TGA/DTG). The results show that byproducts such as BS and RHA can be used with
Keywords:
MK as starting materials for the preparation of geopolymer binders. The using of by-product rich on silica
Geopolymer
Silica source
produces materials with microstructures similar to those traditionally obtained with commercial potas-
Microstructure sium silicate (PS). Regarding SF-based binders, the strength declines over time, with late-age instability.
Compressive strength The most stable or homogeneous binders over time are those based on RHA. The MK/BS30 binder exhibits
good mechanical performance 42.1, 51.04 and 48.3 MPa at 7, 180 and 360 days respectively. The MK/
BS30 binder shows a high degree of geopolymerization, a more homogeneous and enhanced connectivity
between the grains and geopolymer gel and likewise, a lower content of MK unreacted. In general, the
results indicate that geopolymers manufactured with RHA could replace materials produced with com-
mercial silicates.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction impact of mining, and waste generation. Due to the high environ-
mental impacts previously mentioned, the construction sector
Portland cement-based concrete is the most widely used con- and specially the cement industry are continuously working to do
struction material from XIX century because of its economy, of this sector more environmental sustainable, through incorpora-
strength, facility production, durability to aggressive agents and tion of (i) innovative chemical admixtures, (ii) supplementary
availability of raw materials for clinker production. However, major cementing materials and (iii) novel binders. The amount of CO2
environmental impacts associated with Portland cement include emitted from the world production of ordinary Portland cement
the energy required for production (at temperatures above (OPC) is estimated to approximately 7% of the total emissions into
1250 °C) and transportation of clinker, the emission of greenhouse atmosphere [1]. In addition, the cement industry in developing
gases either directly or indirectly during manufacture, and the countries consumes about 10% of the total energy used [2]. These
percentages are gradually increasing because the use of OPC is
steady in advanced countries and rapidly increasing in developing
E-mail address: monica.villaquiran@correounivalle.edu.co

https://doi.org/10.1016/j.conbuildmat.2019.08.002
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621

countries. The concrete industry has introduced regulations to solutions prepared containing high level of KOH will suffer an even
reduce CO2 emissions during concrete production such: (i) utiliza- larger temperature rise than is observed in the NaOH case [20].
tion of industrial or agro-industrial byproducts that can be used Additionally, sodium aluminosilicate solutions will depolymerize
as alternative materials. The most common materials are fly ash, faster than solutions containing potassium, resulting in a higher
4
ground granulated blast furnace slag, calcined-clay such metakao- concentration of Al(OH)(aq) [21] and K+ can lead to a higher degree
lin, silica fume, rice husk ash and natural pozzolans, which can be of condensation compared with Na+ under the same conditions,
used such addition or as partial cement replacement. The alterna- obtaining higher compressive strength than NaOH-based geopoly-
tive cementing materials are aluminosilicates and often are used mer [22,23], it is because KOH-based geopolymer has lower porosity
in concrete mixes to reduce OPC cement contents, improve proper- in its structure [24].
ties in fresh state: stability, segregation, and bleeding are controlled In clay-based alkali-activated cements such as metakaolin, the
with utilization of fly ash [3]. In hardened state the OPC concrete roles of different alkaline activators, the use of commercial sodium
with silica fume shows a lowered expansion [4] and in general there or potassium silicates, and the influence of the curing temperature
is an enhance durability due to pozzolanic activity and formation of have been studied [25–27]. The last decade alternative silica
gels such calcium-silicate-hydrated [5,6]. (ii) Incorporation of new sources such wastes glass, rice husk ash, silica fume, and diatoma-
technologies such binders alternative to Portland cement, the alkali ceous earth has been evaluated. M. Torres-Carrasco [28], evaluated
activation materials and geopolymers, which have been develop- the formation of sodium silicate solutions from dissolution of glass
ment world around from aluminosilicates supplementary materials wastes in NaOH/Na2CO3, and the result most important is that sil-
such fly ash [7–9], binder reaching compressive strength up to icon dissolved has important potential for activation of materials.
49.2 MPa using NaOH and sodium silicate [10] and to concrete The development of ecofriendly activators with reduced CO2 foot-
based on fly ash/blast furnace slag the residual strength after expo- print when are used for geopolymers mixing is therefore much
sure at 700 °C was 23.71 MPa; spent catalyst residue has been used desired and can lead to significant reduction in the global warming
[11,12] and mortars were prepared yielding compressive strength potential (GWP) of alkali activated binders. For activation of meta-
about 68 MPa; natural volcanic pozzolan mixed with blast furnace kaolin: geopolymers binders with high capacity of water retention,
slag was used to producing geopolymer pastes and compressive low thermal conductivity and low GWP emission (47.45% lower
strength around 30 MPa was achieved [13] producing a material than using traditional commercial silicate) has been obtained using
with 44.7% lower carbon footprint, and the characteristics of an alternative silicate from rice husk ash with potassium for activa-
environmentally sustainable material (green) that can be used in tion of metakaolin [29,30]; using sodium and rice husk ash, the
the construction sector [14]; these materials are examples of mate- compressive strength for geopolymer cements were between 33
rials that can also be used as raw materials in the technology of and 40 MPa at 28 days [31,32], metakaolin blended with GBFS
alkaline activation. In general, depending on the used raw materials using waterglass from rice husk ash and silica fume [27], geopoly-
and synthesis conditions (temperature, curing time, humidity, mers mortars based on fly ash/GBFS were development in Vietnam
molarity of alkali used), the geopolymers show different properties, achieves compressive strength 60 MPa at 28-day curing [33].
such high compressive strength (above at 40 MPa) [3], fast or slow Mejia et al evaluated the synthesis of geopolymer from fly ash:
setting time, acid resistance [7], fire resistance as capacity of main- GBFS using waterglass from rice husk ash, and the compressive
taining residual strength of 15 MPa after exposure to 1100 °C [9] strength was 30–40 MPa at 7-day curing [34], in a recent study
and a lower carbon footprint than Portland Cement [14]. It is Mejia et al investigated using spent diatomaceous earth for synthe-
believed that the production of geopolymer binders has environ- sis of geopolymers based on fly ash:metakaolin and compressive
mental benefits because of reduction in CO2 emission, in compar- strength was between 35 and 40 MPa after at 360-day curing
ison to manufacture of Portland cement due to utilization of [35]. Reactive silica and quartz have been used by Autef [36] such
industrial wastes, and low temperature of synthesis, generally alternative alkali activators for preparation of geopolymer based
lower than 100 °C [15,16]. on metakaolin, the results show the compressive strengths reach
The alkali activation process involves a series of solution- 43.6 MPa for the composition amorphous silica90:quartz10 at 28
condensation reactions of the –Si and –Al phases of the starting –day curing. Zivica [37], produced GBFS:OPC mix which were acti-
materials due to the alkaline hydrolysis solution generated by vated using of silica fume and NaOH solution; the compressive
alkali hydroxides, including the most commonly used NaOH, which strength of the mortars were between 10 and 45 MPa at 90 days.
generates active species of aluminosilicates. During the polymer- Nevertheless, RHA has been used in many studies as a starting
ization, new structures are formed from active species of silicates, material mixed with metakaolin or fly ash, and using commercial
aluminates and aluminosilicates through polymeric condensation sodium silicate and NaOH solutions [38–40]. When RHA or SF are
mechanisms, whose proportions and stoichiometric equilibrium used for alternative waterglass preparation, the great majority of
determine the kinetics of the activation reactions and the final studies are tested to short ages [27,33,35,41–44] and there is few
properties of the solid material formed [17–19]. The gelation and information available to stability of binders and behavior for long
setting process of the polymerized aluminosilicates vary depend- ages [45–47]. RHA, is a potential silica source for been introduced
ing on the reactivity of the starting materials and the activation in geopolymer technology, considering that the rice worldwide
conditions (alkaline solution molarity), such as the type and con- production was estimated at 20 Mt by 2013 [48] and globally the
centration of the activating solution generally based on Na+ or K+ leading producers of rice are Chinese (7.2 Mt), India (5.5 Mt),
alkaline hydroxide. During hardening, three-dimensional alumi- Indonesia (2.2 Mt) and Bangladesh (1.7 Mt). According to the
nosilicate networks are formed with a high degree of amorphous- USA Rice Federation the rice production it is estimated to exceed
ness if the starting materials are typically reactive clays, on case of 20 billion Ton annually, that gives an approximately 0.35 Mt of
fly ash there are some traces of crystalline impurities such quartz, RHA [49]. Locally, in Colombia for the year of 2018 the production
hematite generated during coal combustion process. Finally, to of Paddy rice was 2.925.557 Ton [50] of which it is estimated that
adequate conditions of waterglass concentration, temperature the amount of rice husk ash was 131.650 Ton, amount consider-
and time, a three-dimensional network are transformed to a solid able for final disposal.
state, generating the geopolymer. Certain authors mention that In this research, geopolymer binders were manufactured by
there is a significant increase of viscosity for Na+ solutions at activating metakaolin (MK) and coal boiler slag (BS) with an alter-
molarity between 5 and 11 M compared with K+, it is associated native silicate obtained by mixing potassium hydroxide with alter-
with the heat of dissolution, which increase with cation size, so native silica sources (rice husk ash (RHA) and silica fume (SF)). The
 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621 3

binders developed were manufactured at room temperature and 1.85, 2.99, 3.62 and 5.53 mm for MK, BS, SF and RHA, respec-
evaluated for up to 360 days. For monitoring of the behavior, tively. The PSD d90 size were 13.57, 42.81, 42.30, 48.34 mm for
microstructural characterization of the products was carried out MK, BS, SF and RHA, respectively.
using instrumental techniques such as X-ray diffraction (XRD),  The density of starting materials was measured using pycnom-
Fourier transform infrared spectroscopy (FTIR), thermogravimetric etry based on ASTM C329 [52].
analysis (TGA/DTG), scanning electron microscopy (SEM) and  X-ray diffraction (XRD) patterns were taken on a wide-angle
mechanical characterization via determination of the compressive goniometer RINT2000, using CuKa signal at 45 kV and 40 mA,
strength. with step size of 0.02° y over the range 5 60° 2h at a scan speed
of 5°/min. According XRD test (Fig. 1), the MK contained small
2. Materials and methodology traces of quartz (SiO2, ICSD 027834) and anatase (TiO2, Inorganic
Crystal Structure Database ICSD 154604). The X-ray patterns of
2.1. Starting materials and characterization RHA and SF show a typical broad hump diffraction peak in the
range between 15 and 30° 2h with a maximum around 22°
The aluminosilicates raw materials used for synthesis of (Fig. 2). This implies the presence of high amount of amorphous
geopolymer binders are metakaolin clay (MK) and coal boiler slag phases of silica in RHA and SF [41] and trace crystalline quartz
(BS). MK was purchased from BASF corporation under the commer- in RHA are observed. This is in agreement with the general lit-
cial name of MetamaxÒ. Rice husk ash (RHA) and microsilica Silica- erature [31,33,34,37,41]. The BS contained quartz (SiO2, Pattern
fumeÒ (SF) were used as silica sources mixed with potassium Diffraction File, PDF 46-1045), mullite (Al6Si2O13, PDF 15-0776)
hydroxide solution to generate the alternative waterglass. BS was and hematite (Fe2O3, PDF 02-0919) and in addition, it was pos-
collected from a boiler of a local paper industry in Cali (Colombia), sible to identify a slight increase in the base line for the 20°- 30°
the BS was initially crushed in a hammer mill and then milled in a 2h which suggests the presence of amorphous-state material.
ballmill for 1 h, and it was introduced in the mixture to replace cer-  The solubility of solid silica sources was determined by dissolu-
tain portions of MK content as the source material. It was purposed tion of 1 gr of material in a KOH solution at 10 M during 24 h at
to alter the SiO2/Al2O3 molar ratio in the source material and room temperature. The difference in mass before and after was
improvement the strength properties of geopolymer binder RHA- estimated as solubility.
based waterglass.

 The chemical composition of starting materials were deter- 2.2. Geopolymer binder preparation
mined by X-ray fluorescence (XRF) using MagixPro PW-2440
X-ray fluorescence spectrometer (PANalytical, USA), equipped Geopolymer binders with 100% MK were designed with molar
with a Rhodium tube with a maximum output of 4.0 kW and ratios of SiO2/Al2O3 = 2.5, K2O/SiO2 = 0.28. The ratio water/solid is
0.02% sensitivity. RHA with 92 wt% amorphous silica was the mass ratio of water (including free water plus water in activat-
obtained by means of the controlled calcination of rice husks ing solutions) over the mass of binder and added solid chemical
in an electric oven at 600 °C for 2 h according to process activator (Na2O and SiO2) and were determined in previous studies
patented by Mejia de Gutiérrez [51], subsequently it was sub- [29,53]. This ratio was kept constant at 0.4 for all the samples
jected to a grinding process by a ball milling for 30 min. EnsureÒ based on MK exclusively. The control geopolymer binder was
Potassium hydroxide (KOH) pellets from MerckÒ were used denoted PS100 and it was produced with 100 wt% commercial
(64271 Darmstadt, Germany, 2017) for preparation alkaline potassium silicate. For producing alternative geopolymers, the
solution. A commercial available potassium silicate solution commercial silicate was replaced by the alternative waterglass
from Productos quimicos panamericanoÒ (with a composition of based on silica from RHA or SF at 50 wt% and 100 wt%.
K2O = 13.06 wt%, SiO2 = 26.38 wt% and H2O = 60.56 wt%) was The alternative waterglass was obtained by adding of RHA or SF
used as a control activator solution. The chemical and physical with potassium hydroxide pellets with tap water to achieve a con-
properties of the solid raw materials used as MK, RHA, SF and centration of 9.3 M and a pH = 13, this solution is allowed to stand
BS are listed in Table 1. for 20 h at room temperature, for later mixing with the MK.
 The particle size distribution (PSD) curve for each starting mate- The potassium waterglass from exclusively RHA was used to
rial (Fig. 1) was determined with laser particle size analyzer producing a binary geopolymer binder with BS in 20 and 30 wt%
(MASTERSIZER 2000, Malvern, UK). MK, BS, SF and RHA had MK replacement, the molar ratios had to be adjusted (SiO2/
an average particle sizes of 6.57 mm, 19.1 mm, 21.5 mm and Al2O3 = 3.0; K2O/SiO2 = 0.25), and L/S = 0.35 to obtaining a slurry
22.84 mm respectively. Additionally, the PSD d10 size were with paste consistency.
For producing geopolymer binder specimens, aluminosilicate
sources (MK and BS) were initially blended manually to ensure
the homogeneity of the binder; potassium waterglass solution
were added to the dry constituents and mixed for a further 7 min
in a Hobart mixer until adequate fluidity was achieved. Then, the
Table 1
wet geopolymer binder was rapidly cast in
Chemical compositions of starting materials.
20 mm  20 mm  20 mm silicone moulds, and subsequently
Component (% weight) MK BS RHA SF these were covered by a plastic film to avoid evaporation of the
SiO2 51.52 49.24 92.33 87.60 mixing water, followed by curing at conditions 70 °C for 20 h. After,
Al2O3 44.53 25.39 0.18 0.38 the samples produced were demolded and placed in a chamber
TiO2 1.71 – – 0.01
with a relative humidity of 90% at 25 °C (fixed by the chamber
Fe2O3 0.48 7.65 0.17 0.66
Na2O 0.29 – 0.07 1.26
conditions) until the desired testing age was reached.
K2O 0.16 – 0.15 2.36 The geopolymer binders were mechanically tested at ages of 7,
MgO 0.19 0.53 0.49 3.67 28, 180 and 360 days, and to ensure reproducibility, four speci-
CaO 0.02 0.77 0.63 0.57 mens were prepared for each geopolymer composition. The frag-
Loss on ignition (1000 °C) 1.09 16.36 2.57 3.29
ments resulting from the compressive strength tests were ground
Density (kg/m3) 2500 2310 2140 2200
until powder and the microstructure was analyzed.
4 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621

Fig. 1. Particle size distribution for starting materials.

time for geopolymer binders. The setting time measurement

started after 5 min of samples preparation at room temperature
up to the final setting time. Initial setting time is the time at which
the penetration of needle is 25 mm while the final setting time is
the time at which the penetration of needle is less than 0.5 mm.
The surfaces of the pieces obtained after the mechanical tests
were observed using a JEOL JSM-6490LV SEM at an accelerating
voltage of 20 kV. The pieces were coated with gold, and the obser-
vations were made in vacuum mode.
FTIR was carried out in a PerkinElmer Spectrum 100 spectrom-
eter in transmittance mode in the wavelength range from
450 cm 1 to 4000 cm 1. The samples were prepared through the
compressed KBr method.
Thermogravimetric analysis (TGA/DTG) of the samples was per-
formed in a TA Instruments STD Q-600 using alumina crucibles
(TAInstruments, Newcastle, UK). The test was performed at
between 40 and 1250 °C at a heating rate of 10 °C/min with a nitro-
gen purge rate of 100 mL/min.
Fig. 2. XRD pattern for starting materials.

2.3. Geopolymer binder characterization techniques 3. Results and analysis

The compressive strength was measured using 20 mm cubic 3.1. Mechanical performance
specimens, the tests were performed on an InstronÒ 3369 universal
tester at a displacement speed of 1 mm/min. The compressive strength of geopolymer binders were evalu-
The Vicat Needle ASTM C187/C191, BS 4550 model NL ated at different days (7, 28, 180, and 360 curing days), this is an
3012X/002 was used for determining the initial and final setting indicator to the performance of alternative starting materials, since

Fig. 3. (a) Compressive strength of MK-based geopolymer binders at different curing ages, and (b) performance indexes with respect to PS100 reference binder.
 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621 5

it provides a description on the quality of geopolymerization pro- the quality of geopolymeric gel is the parameter that governs the
cess. In Fig. 3a, the compressive strength results obtained for each strength. The strength of geopolymers binders is increased with
of the developed binders are shown. In general, most of the mate- the availability of reactive silica, because the density of the
rials exceed the strength of the PS100 reference sample at different SiAOASi bonds increases with the Si/Al ratio [41], suggesting that
ages, however, it is important to note that when using the RHA and at short ages there is major availability of silica from SF than RHA-
SF-based waterglass a higher variability in compressive strength is particles, similar results were found by Bernal [27]. Another reason
observed (displayed in Fig. 3a as an increased standard deviation). is that RHA solid particles are larger size than SF-particles, causing
Bernal et al [27], considering that the increased variability in the a slow reaction rate and delay the geopolimerization reaction [41],
binders activated with the modified SF or RHA may potentially which makes the results to SF-based specimens stronger than
be attributed to an increased brittleness exhibited by the binders RHA-based.
activated with modified SF or RHA, although any possible reasons Over time (360-day curing), the geopolymeric gel possibly sta-
for such behavior are unclear. The values reached by the age of bilizes, indicating that the polycondensation process improves and
28 days in samples based on commercial potassium silicate and this suggest that the dissolution of metakaolin particles increases
RHA-based waterglass are similar to those reported by Tchakouté with increasing the curing time, thus, the strength for RHA50
[31] for geopolymers based on RHA + NaOH. At early ages, the and RHA100 are increased and the SEM images for RHA100 con-
strength increases due to the influence of the curing temperature firm a microstructure more homogeneous and connected and
used (72 °C for 20 h). Rovnaník [26], explaining that for high curing low quantities of unreacted MK is identified (Fig. 4, this is dis-
temperatures, the degree of geopolymerization is higher than at cussed in Section 3.2). For the RHA100 binder at 180 days, the
room temperature, and the quantities of formed reaction product strength has decreased; however, this behavior is atypical since,
are greater at short curing times, on the other hand, at long curing at a curing time of 360-day curing, the RHA100 binder strength
times, when the degree of geopolymerization remains the same, is almost the same that obtained at 28-day curing; thus, it is

Fig. 4. SEM of the geopolymer binders at different ages.

6 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621

believed that there was an error in the specimens tested in the the strength [61]. Kalaw [62] evaluated the utilization of coal fly
180-day curing. Possibly, the surfaces were not completely flat, ash and coal bottom ash using RHA-based sodium waterglass,
and therefore, stress concentrations were generated that caused and the compressive strength were 10.9–18.5 MPa. A spent fluid
the specimens to prematurely fail. In general, the instability in catalytic cracking catalyst has also been used as a partial replace-
samples based on MK was previously observed by De Silva [54], ment for MK, and it is reported that the ternary mixtures have
which, at 210 days, showed a decrease in compressive strength. stable mechanical strengths at long curing times [47].
Another possible explanation for this behavior is associated with Based on the results of the mechanical strength at different
the increase in porosity of this sample, as observed in the SEM times, this indicates that alternative potassium waterglass from
images (Fig. 4), and the formation of alkali-carbonated species RHA could be a more suitable alternative alkaline solution for
(K2CO3 and KHCO3), which has been previously reported by other geopolymer production compared to the SF source. Additionally,
authors [55,56] and observed in this investigation in the FTIR considering that RHA is a locally available material, the thermal
(Fig. 6 below). and microstructural characterization studies were conducted on
In general, the mixtures RHA-produced have compressive the binders based on 100% alternative alkaline activator and the
strengths comparable with those obtained with commercial PS geopolymer binder with 30 wt% BS.
(except for the sample tested at 180-day curing). It is possible that
there is a greater availability of silica from the SF-based waterglass
compared with the RHA-based waterglass due to incomplete disso- 3.2. Microstructural results
lution of RHA particles at early ages (similar behavior was found by
Bernal et al. [27]); under this effect, the highest compressive 3.2.1. Scanning electronic microscopy analysis
strength achieved is associated with the SF-based waterglass sam- SEM images of MK-based geopolymer binders from commercial
ples at 7-day of curing. The values of compressive strength of potassium silicate, potassium waterglass from RHA and potassium
geopolymer binders using SF or RHA, is likely to be determined waterglass from SF are shown in Fig. 4. The micrographs reveal
by the different rates of release of silicate in these systems in the considerable unreacted MK particles (distinguishable by their plate
late stages of geopolymerization [31,32]. This influences directly morphology that forms a laminar structure) embedded within
the structural characteristics of the binder, a more homogenous geopolymer gel and not connected to the networks are observed
geopolymer gel binder and consequently their compressive at 28-day curing age (Fig. 4A, D, G y J). When the curing time is
strength [31,32,57]. longer (180 days) there is a lower proportion of unreacted MK pre-
The Fig. 3a shows that the maximum compressive strength for sent. The gel is denser, although microporosity is present; this
SF-based waterglass at short age was 62.3 and 51.73 MPa at 7- morphology is considered typical of geopolymers based on MK
day curing to SF50 and SF100 respectively. Nevertheless, for long and has been previously observed by other authors [31,41]. Large
curing ages (360-day curing) the strengths drop to 44.9 MPa for amounts of unreacted MK are associated with high Si/Al ratios,
SF50 and 34.7 MPa for SF100. The rapidly reactivity of SF particles and geopolymers have less structural order [21] and low alkaline
at short ages, doing that SF100 hardens quickly (63 min), meaning solution (8 M) is used [63] (in this study the molarity was 9.3 M).
that part of the MK particles remain unreacted and the polycon- For RHA100 geopolymer binder at 180-day curing (Fig. 4E), there
densation process is slow, similar results were found by Nimiri is can be observed high quantities of micropores, attributed to air
[56]. Also, the effect of prolonged curing time at 70 °C, would be bubbles that remain entrapped into the pastes during the dissolu-
expected to slow down the availability of SiO2 for long ages tion and polycondensation process through initial mixing and the
[27,57]. Kather [58] noticed that the presence of small geopoly- space that was initially occupied by water and then left as a void
meric contents which fill the pores with low conjunction with each after water evaporation [31,41,64]. The cracks and voids have a sig-
other leading to low compaction of the formed geopolymer com- nificant detrimental influence on the compressive strength of the
posite. Zívica [37,59] found that silica fume activator contribute geopolymer specimens and this was evidenced in mechanical
to the decrease of the quality of the pore structure, and macropores strength of binder RHA100 at 180-day of curing (Fig. 3). The
are formed, consequently the compressive strength is decreased. replacement of MK with BS decreases the water requirements of
Additionally, this is related to the destruction of the polymeric sil- the mixture (L/S of 0.35, compared with RHA100 with an L/S of
icate chains [60], pores and microcracks are observed in SEM 0.4), producing at long ages a less porous material (Fig. 4H, I).
images (Fig. 4) for SF-based waterglass geopolymer binders. Although a greater amounts of water is necessary for proper work-
Fig. 3b shows the performance indexes of geopolymer binders ability and the mobilization of alkali ions during the mixing pro-
compared with the reference sample PS100. The performance cess and in the fresh state of 100% MK-based binders, more
indexes indicate in general a gain of strength against the reference water contributes to shrinkage and cracking and an increase in
sample. There is notable an improvement in the strength with the the porosity of the hardened gel microstructure, as confirmed by
substitution of MK by BS (MK/BS20 and MK/BS30), and this effect is other authors [65] and is evidenced in this study.
specially noted at 180 days. Rovnanik [26] evaluated the effect of The SF-based geopolymer binders (Fig. 4J–L) present relatively a
curing temperatures of 10–80 °C on the strength of MK-based heterogeneous microstructure for all curing ages compared to
geopolymers and reported a decrease in strength over time as RHA-based binders. At 360-day age, SF100 shows a less densified
the curing temperature increased, which is associated with a gel structure with less connectivity of geopolymer gel coinciding with
structure that is poorly compacted. Temperatures higher than lower compressive strength (Fig. 3). The micrographics of RHA-
60 °C increase the degree of geopolymerization, which contributes based geopolymer binder (Fig. 4F, I) show a homogeneous material,
to an increase in early-age strength; however, with rapid harden- more enhanced connectivity between grains and polysialates par-
ing, the formation of a highly porous structure occurs, which ticles with fewer unreacted MK and pores were overlapping in
affects the mechanical properties at later ages. For 180 days, while the samples. Tchakoute et al., using RHA-based waterglass found
the strength loss was about 21.6% for RHA100; the improvement in similar microstructure, although in his investigation a greater
strength with the addition of BS is 29.2% (MK/BS30), indicating that microcracking was evidenced [31]. These cracks may have two
the BS improved the strength due to its prolonged reaction activity possible origins (i) shrinkage cracks during geopolymer curing
over time. Other additions, such as fly ash have been used to when water evaporation takes place; (ii) load-induced cracks
replace MK; however, the mass percentage of replacement is lim- caused by the unconfined compression testing [41]. The results
ited to 10% because higher amounts of fly ash tend to decrease indicate that RHA-based potassium waterglass could be more
 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621 7

suitable alternative alkaline solutions for geopolymer binder pro- broad band toward the lower wavelength (1015, 995, 1011,
duction compared to the raw silica fume. 1007 cm 1 for SF100, RHA100, PS100 and MK/BS30 respectively),
indicating that the dissolution of MK and the occurrence of poly-
3.2.2. X-ray diffraction patterns condensation reaction leading to the formation of an aluminosili-
The X-ray diffraction pattern for the geopolymer binders at dif- cate network [31]. The shift to smaller wavelength from 7-day to
ferent curing ages are shown in Fig. 5. Regardless of the curing age 28-day curing and subsequently shifts to lower wavelength at
or the type of silica used, geopolymer binders show a broad hump 180-days and 360-days, are attributed to the development of
structure between 25 and 35° 2h with centered around 2h = 27°, amorphous structures where silicate species are partially substi-
which are attributed to the high structural disorder of the geopoly- tuted by aluminate species [27,33]. The shift to lower wavelength
meric gel and this observation also agrees well with the current of the principal band is due vibration mode of AlAO bond, which
state of art, where the geopolymers are amorphous to semicrys- vibrates at lower frequencies than the SiAO bond [67] because the-
talline aluminosilicates [17,31,34,37,41]. Peaks corresponding to oretically, the SiAOASi bonds are stronger than those of SiAOAAl
the anatase from MK are shown in Fig. 5 for all curing ages and and AlAOAAl [41]. For long curing times there is greater dissolu-
it has been identified previously by other authors using raw MK tion of the MK precursor, likewise, greater substitution of tetrahe-
[31], indicating that this is not dissolved under the activation con- drons of SiO4 for tetrahedrons of AlO4 in the geopolymeric gel [60]
ditions used. The resulting X-ray patterns show that the binder and at higher the Al inclusions, the lower the wavelength of the
could be the same using PS, RHA, or SF-waterglass. When BS is main bands, with a consequent decrease in the SiO2/Al2O3 ratio
used as a replacement of MK (30 wt%, MK/BS30), a greater number of the geopolymer due to the greater inclusion of Al in the system
of crystalline peaks attributed to the impurities previously present [31,68,67]. With the replacement of Si4+ by Al3+, the SiAOAAl angle
in the raw BS (Fig. 2) are still observed. After 28-days of curing became more acute, shifting the signal to lower frequencies due to
(Fig. 5a), phases such as mullite (Al6Si2O13) and quartz (SiO2) are the weaker bond and to the fact that the AlAO bond is longer than
still present, this indicates that these minerals remain unaffected SiAO bond [27,31]. The value of wavelength is higher on the FTIR
during the geopolymerization process. The formation of alkali spectra for SF100, indicating less Al inclusion in their structure
carbonates (CaCO3, ICSD 16,710 and K2Ca(CO3)2, reference code suggesting thus more unreacted MK particles as was observed in
003-0504) for sample MK/BS30 can be attributed improper sealing SEM images (Fig. 4).
of the samples, which alloys atmospheric CO2 to react with the The RHA100 geopolymer binder at 360-day curing, generates
K+ -rich pore solution, similar result was found by Hajimohammadi higher incorporation of Al atoms (at wavelength 995 cm 1) com-
using sodium silicates [57] and Kamseu et al. using RHA-based pared to SF100 geopolymer (at wavelength 1015 cm 1), which
waterglass [63]. confirmed a more enhanced connectivity between the grains and
polysialate particles due to greater depolymerization of MK
3.2.3. Fourier transformed infrared spectra (observed in SEM images, Fig. 4) this confirm thus higher strength
For geopolymer binders, a broad band of high intensity between achieved.
wavelength 1200 and 900 cm 1 is identified (Fig. 6) that corre- RHA-based waterglass generates a higher dissolution of meta-
sponds to the asymmetrical stretching of Si-O-T bonds (where T kaolin and subsequent gradual shift of the chemical system from
corresponds to tetrahedrons of Si or Al) [65,66]. In particular, the monosilicate chains and cyclic trimmers to species with larger
SiQ4 units show infrared absorption centered around 1200 cm 1, rings and complex structure and polymers [31], resulting in the
the SiQ3 around 1100 cm 1, the SiQ2 around 950 cm 1 and the 3D polymeric framework and increasing the compressive strength
SiQ1 around 900 cm 1 [31,32]. In general, for short curing times of geopolymer RHA-based. The signal of wavelengths 710 and
such as 7 and 28 days, the wavelength of the SiAOAT band is 712 cm 1 which belongs to SiAOAAl bending vibration, indicating
higher than those corresponding to 180 and 360 days. For short that main geopolymer structure generated after the reaction
curing times, the Si-O-T band is centered at wavelength 1054, between the silicon aluminates and the alkaline solution was
1047, 1040, 1034 cm 1 for geopolymer SF100, RHA100, PS100 SiAOAAl [31]. At 360-day of curing the Fig. 6 shows that this peak
and MK/BS30 respectively, and with increasing curing time, this is more pronounced on the FTIR spectra of RHA100 compared to

Fig. 5. X-ray diffraction patterns for geopolymer binders at different ages: (A) 28 days, (B) 180 days, and (C) 360 days. The crystalline phases found are A: anatase, TiO2; M:
mullite, 3Al2O3.2SiO2; Q: quartz, SiO2; C: calcite, (K,Ca)CO3.
8 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621

Fig. 6. FTIR of the different geopolymer binders at different ages. (A) PS100, (B) SF100, (C) RHA100, and (D) MK/BS30.

the one of SF100, indicating the formation of highly cross linking gel formed [71]. The signal at 874 cm 1 is present only in MK/
geopolymer gel framework [31,69], suggesting thus higher BS30 and corresponds to the bending mode of carbonate ion in
strength, denser matrices with fewer unreacted metakaolin parti- CaCO3 [72], this calcium ions don not simply balance the charge,
cles. Signals that correspond to the bending vibrations of the but also act structural links to maintain the connectivity of the
SiAOASi bonds are detected at wavelength 460–470 cm 1. Gener- geopolymer network and induces a more condensed structure
ally, all the geopolymers generate signals between 570 and [31] as reported as SEM results. This signal is more intense in the
595 cm 1 attributed to vibrations from the symmetrical strain of sample based on BS. Fig. 6 shows a hump centered in the wave-
SiAOAAl [70]. The signal identified at 860 cm 1 in almost all the length at 3435 cm 1 which is attributed to the stretching mode
materials corresponds to the asymmetrical stretching vibration of of H-OH, whilst the band located at 1654 cm 1 is due to the
the tetrahedrally coordinated Al (AlIV) present in the geopolymer bending vibration of OAH of the hydrated reaction products
 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621 9

[31,33,73]. The bands located between wavelength 1370 and carbon present in the starting BS (unburned coal equals 19.36 wt
1430 cm 1 are more pronounced for long ages. For the geopoly- %) and (ii) carbonate species (K2CO3, CaCO3, and KHCO3) formed
mers RHA100 and MK/BS30, these bands are associated with the in these types of geopolymers that have been previously identified
ACO type bonds that correspond to the vibrations of CO3 2 com- by XRD, FTIR test (Figs. 5 and 6). Similar mass loss have been iden-
pounds. In particular, to RHA100 the alkaline carbonates type tified by Prud́homme [78]. At an age of 180 days, the MK/BS30
KHCO2 and K2CO3 [56] generated by the reaction of K+ -rich pore sample showed the greatest mass loss at 10.87%, followed by
solution with atmospheric CO2 (although in the XRD patterns of RHA100 (9.83%), PS100 (8.24%) and SF100 (7.14%). At 28-day of
RHA100 could not be appreciated). On the case of MK/BS30 curing, a higher degree of gel polymerization is identified for
geopolymer the carbonation is generated by the reaction of envi- RHA100 binder in comparison than SF100. At 360-days curing a
ronmental CO2 with the Ca+2 from the BS generating CaCO3 and more condensed geopolymers structure contains structural water
K2Ca(CO3)2 [74], which corroborates the result found in the XRD in the cavities, while in a less condensed structure, water is present
for MK/BS30 and could explaining the lower strength to 180-day mostly as free water and released during hardening [79]. The
of curing for RHA100 sample. Nonetheless, according to a recent results of mass loss show that approximately 8.07, 8.46, 8.47 and
study by Lee and van Deventer [75], the carbonate salts (K2CO3, 11.12 wt% for SF100, PS100, MK/BS30 and RHA100 were lost
CaCO3) can be beneficial to geopolymer binders by lowering the respectively (Fig. 7). This indicates that MK/BS30 and RHA100 are
dissolved water contents and preventing hydrolytic attacks on more condensed geopolymer structure suggesting thus the forma-
the geopolymer gels. Therefore, it is reasonable to intuit, carbona- tion of highly cross linking geopolymer framework, denser matrix
tion in geopolymer binder RHA100 and MK/BS30 may be beneficial and high compressive strength as reported as FTIR and compres-
to the durability of geopolymer binders. sive strength results. Results are consistent with Tchakoute results
[31], where the values of the wavelength of the main band on FTIR
3.2.4. Thermal analysis (TGA/DTG) test decrease with increasing the compressive strength and the
The results of mass loss from TGA results for geopolymer bin- mass loss of geopolymer binders and less unreacted MK, and this
ders at 28-day of curing indicates a mass loss of 6–7% (Fig. 7), this could be related to the higher degree of polycondensation reaction
is associated by a large endothermic band at temperatures below and therefore higher compressive strength.
300 °C in DTG (Fig. 8). This mass loss indicates the removal of
absorption water or free water in the larger pores [19,31]. The sec- 3.3. The setting time
ond degradation occurs between 300 and 400 °C and is associated
to the water bound in the K-A-S-H structure from the condensation The initial setting time curves for geopolymer binder are shown
of Si-OH and AlAOH groups [19,76,77]. According to Davidovits, in Fig. 9. The initial setting time was between 43 and 45 min for
this latter mass loss is due to dehydroxylation of OH groups, and geopolymer binders based exclusively on MK (PS100, RHA100
subsequent polycondensation into siloxo bond SiAOASi, linking and SF100). The final setting time was found to vary depending
neighboring geopolymeric micelles [17,76]. The results of mass of silica source used. The final setting time was 58, 63, 76 min
loss below 300 °C corresponds to approximately 90% of the total for PS100, SF100 and RHA100 respectively. This variability on set-
mass loss up show to 1100 °C (Fig. 7b). Comparing the different ting time is possibly associated with the particle size and solubility
geopolymer binders, while SF100 and MK/BS30 present a mass loss of solid silica sources, having the highest solubility for (79.5%) SF
similar to the PS100 reference binder, the RHA100 binder shows particles compared to the (74.6%) RHA particles. This indicate that
greater mass loss at larger curing time. This behavior presented the silicates in the SF-derived solution are more readily available
by the RHA100 geopolymer could be due to an increase in porosity, for the reaction than RHA-based waterglass. The binary MK/BS30
which is evidenced in the SEM results (Fig. 4E and F), an increase in geopolymer binder had an initial setting time of 158 min and a
porosity generates a greater water absorption capacity and there- final hardening time of 180 min. For MK/BS30 geopolymer binder
fore a greater water condensed from geopolymer structure is the setting times were greater than the binders based exclusively
released. on MK and the possible explanation for this behavior could be
For the MK/BS30 geopolymer, a remaining weight loss at due to (i) the introduction of 30 wt% BS particles of high
between 600 and 800 °C and this is associated to (i) unburned crystallinity and low solubility, which delays the dissolution and

Fig. 7. Mass loss determined via TGA curves for geopolymer binders at different ages, up to temperatures of (a) 300 °C and (b) 1100 °C.
10 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621

Fig. 8. Differential thermogravimetric (DTG) thermograms for the geopolymer binders at (A) 28, (B) 180 and (C) 360 days of curing.

hardening time [80,81]. Considering, aluminum components in

MK tend to dissolve more easily than Si components [82], and rel-
atively exists lower Si content in SiO2/Al2O3 = 2.5 ratio than in 3.0
ratio, it is possible that more Al(OH)4 4 species are available for con-
densation in the systems based 100% MK. In 100% MK systems, con-
densation reactions occur between aluminate and silicate species, to
produce polymeric polysialate structures. With the increase in sili-
con content, more silicate species are available for condensation
and the predominant reaction is between silicate species, resulting
in oligomeric silicates. The condensation between oligomeric silicate
species and aluminates results in a rigid 3D structure of poly
(sialate-siloxo) and 3D polymer structures of poly (sialate-
disiloxyl), the reaction rate of the silicate species is slower than
the reaction rate between silicate and aluminate species [82], and
finally the setting time is longer with the increase in silicon content
[33]. The final setting times of all geopolymer binders are in agree-
ment with the ASTM limit for the final setting time of OPC (less than
or equal to 375 min, according to ASTM C150) [83].

Fig. 9. Setting time curves for geopolymer binders.

3.4. Others considerations
subsequent geopolymerization reactions, (ii) the highest molar
ratio for MK/BS30 (SiO2/Al2O3 = 3.0) compared to geopolymer bin- In this work, the compressive strength of the studied geopoly-
der based on 100% MK (SiO2/Al2O3 = 2.5) makes the binder MK/ mer binders based exclusively on RHA (RHA100 and MK/BS30),
BS30 has lower aluminum content available to react delaying the were ranges from 40 to 50 MPa. Thus, the strength of RHA-based
 M.A. Villaquirán-Caicedo / Construction and Building Materials 227 (2019) 116621 11

potassium waterglass is very competitive and attractive, which is which contributed to the compressive strength being maintained
also comparable to that Portland cement with strengths of 9– at up to 51 MPa for 180 curing days.
21 MPa in the standard ASTM C-150 [83]. As such, developed In general, the results indicate that the geopolymer binders
geopolymer mixtures can be used can be used as a cementitious manufactured with RHA could be substitutes for materials pro-
material to replace Portland cement in certain engineering applica- duced with commercial silicates and would have less environmen-
tions, such as building materials. Geopolymer binders could be tal impact for reusing agro industrial wastes.
considered as matrix for the manufacture of composite materials,
which have also shown good performance at high temperature
and good thermal properties [53]. It should be expected that the Declaration of Competing Interest
utilization of the MK-RHA and MK/BS-RHA geopolymers can bring
both environmental and economic advantages. Considering that The authors declare that they have no known competing finan-
the utilization of RHA as silica source for waterglass synthesis cial interests or personal relationships that could have appeared
can save not only the expenses for waste disposal in landfills, but to influence the work reported in this paper.
also save the costs for utilization of commercial silicates. Advan-
tages of utilization of this geopolymer binders are (i) the recycling Acknowledgements
of the two wastes as boiler slag and RHA can minimize their poten-
tial damage to the environment and human health; (ii) the elimi- The author would like to thank the Universidad del Valle for
nation of Portland cement usage can save the energy associated their financing through the project titled ‘‘Valorización de residuos
with cement production and reduce the greenhouse gases emission para la elaboración de materiales de construcción CI 21025”. Addi-
caused by firing carbonates to Portland production [84]. Addition- tionally, to thank at Colciencias by support through ‘‘Convocatoria
ally, the using of alkaline activators based on commercial potas- 528 de 2011, Estudios de Doctorado en Colombia”.
sium silicate provide a higher carbon footprint, whereas activator
based on RHA are more ecofriendly reducing by 47.45% the GWP
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