Construction and Building Materials 124 (2016) 961–966

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Technical note

Synthesizing one-part geopolymers from rice husk ash

P. Sturm a, G.J.G. Gluth a,⇑, H.J.H. Brouwers b, H.-C. Kühne a
a
Division 7.4 Technology of Construction Materials, Bundesanstalt für Materialforschung und -prüfung (BAM), Berlin, Germany
b
Department of the Built Environment, Eindhoven University of Technology, Eindhoven, The Netherlands

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

Article history: One-part geopolymers offer advantages over conventional geopolymers with regard to handling and stor-
Received 20 June 2016 age of feedstocks. However, they often suffer from a low degree of reaction, a high amount of crystalline
Received in revised form 5 August 2016 byproducts, and consequently low strength. In this study, one-part geopolymers were produced from rice
Accepted 7 August 2016
husk ash (RHA) and sodium aluminate, and investigated by XRD, ATR-FTIR, SEM and compressive
Available online 11 August 2016
strength testing. The compressive strength of the material was 30 MPa, i.e. significantly higher than
for comparable one-part geopolymers. This is attributed to an almost complete reaction of the RHA
Keywords:
and the absence of crystalline byproducts (zeolites) in the hardened geopolymer.
Alkali-activation
Geopolymers
Ó 2016 Elsevier Ltd. All rights reserved.
One-part formulation
Bio-based materials
Rice husk ash

1. Introduction the husks leaves about 25 wt.% of the initial mass as ash, the so-
called RHA [22]. Highly reactive, amorphous RHAs can be produced
Because of their versatile potential, conventional ‘‘two-part” at calcination temperatures up to 800 °C [23–26], which is signifi-
geopolymers, synthesized by activation of solid aluminosilicate cantly below the temperatures for the production of conventional
feedstocks (e.g., metakaolin, fly ash and blast-furnace slag) with OPC clinkers. Heating at higher temperatures is not beneficial
highly alkaline liquids (e.g., sodium hydroxide and sodium silicate because it leads to the formation of crystalline cristobalite and try-
solutions), have been subject of a large number of studies in the dimite in the ash [24], which decreases its reactivity. RHA has been
last decades (e.g. [1–10]). More recent approaches have focused investigated for its use in various industrial applications including
on so called ‘‘one-part” formulations. For this route the alkaline the use as supplementary cementitious material for conventional
activator is provided in solid form and just water has to be added cement based binder systems (e.g. [27–29]). Recent studies inves-
to initiate the geopolymerization reactions and hardening tigated the production of sodium silicate solutions from RHA for
(‘‘just add water geopolymers”) [11,12]. In these formulations the use as activating solution for conventional ‘‘two part” geopolymers
activator solution forms directly in the reaction system, thus the [30–33].
synthesis procedure is comparable to that for the hydration of ordi- In this communication we report on the use of RHA as solid pre-
nary Portland cement (OPC)-based binder systems. With this cursor in the production of one-part geopolymers. The results
approach handling of highly alkaline solutions and problems with show that the RHA is highly reactive and is able to form a typical
aging of these solutions are avoided, which can provide a better geopolymer gel with higher compressive strength than is generally
social and economic acceptance [12,13]. However, the investigated observed for one-part geopolymers.
one-part systems are often dominated by crystalline tectosilicates
(zeolites) and the reported compressive strengths are usually
lower than for conventional two-part geopolymers [11,12,14–19].
Rice husk ash (RHA) is a silica-rich agriculture waste material, 2. Materials and methods
typically consisting of 90–95 wt.% amorphous SiO2 [20]. In 2010
over 700 million tons of rice were produced worldwide [21] in a 2.1. Materials
context of a steadily increasing demand. This translates to a pro-
duction of about 140 million tons of husk in 2010. Calcination of The starting materials were characterized by inductively
coupled plasma optical emission spectroscopy (ICP-OES), X-ray
⇑ Corresponding author. diffraction (XRD), attenuated total reflection Fourier transform
E-mail address: [email protected] (G.J.G. Gluth). infrared spectroscopy (ATR FT-IR) and scanning electron

http://dx.doi.org/10.1016/j.conbuildmat.2016.08.017
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
962 P. Sturm et al. / Construction and Building Materials 124 (2016) 961–966

microscopy (SEM). The experimental conditions are described in

Section 2.3.
The employed rice husks from Tanzania were calcined at 650 °C
for 90 min to yield the rice husk ash (RHA) and the ash then
allowed to cool down naturally to room temperature. After cooling,
the RHA was ground in a disc mill for 18 s. Particles that did not
pass a sieve with 63 lm mesh size were ground for further 18 s;
after the second milling all particles passed the applied sieve.
The particle size distribution (PSD) of the RHA was investigated
using laser granulometry (Fig. 1). The median of the PSD was deter-
mined to be d50 = 11.1 lm (and d90 = 39.8 lm), which is in line
with SEM micrographs of the RHA (Fig. 2). The BET specific surface
area of the RHA was determined to be 49.6 m2/g (average pore
diameter 12.9 nm), using N2 sorption at 77 K. An apparent parti-
cle density of 2.259 ± 0.003 g/cm3 was determined by He
pycnometry.
The RHA contained 88.49 wt.% SiO2 (Table 1). XRD showed a Fig. 2. SEM micrograph of the rice husk ash.
major amorphous hump, centered at 22° 2h, and minor amounts
of the following crystalline impurities: quartz (PDF # 00-046-
Table 1
1045), potassium magnesium phosphate (PDF # 00-050-0146), Chemical composition of the starting materials.
cristobalite (PDF # 00-039-1425), and calcite (PDF # 01-086-
0174) (Fig. 3). Component RHA NaAlO2

The employed sodium aluminate (NaAlO2) had an almost stoi- (wt.%) (wt.%)
chiometric Na/Al ratio of nearly unity (1.001 mol/mol; cf. Table 1). SiO2 88.49 <0.01
Besides anhydrous sodium aluminate (PDF # 00-033-1220), XRD Al2O3 0.58 59.74
also indicated minor amounts of hydrated sodium aluminate Fe2O3 0.31 0.02
TiO2 0.03 <0.01
(PDF # 01-083-0315) and natrite (PDF # 01-072-0628). This is in
CaO 1.00 0.39
agreement with the low loss on ignition of 2.63 wt.% (Table 1) MgO 0.88 0.01
and the tendency of alkaline compounds to carbonate. Na2O 0.24 36.35
K2O 2.91 0.01
SO3 0.54 0.04
2.2. Geopolymer synthesis
P2 O5 1.83 n.d.
LOI 2.48 2.63
One-part geopolymers were synthesized by mixing RHA and
solid sodium aluminate, and subsequently adding water at a nom- n.d.: not determined; LOI: loss on ignition at 1000 °C.

inal water/binder ratio (w/b) of 0.5 by mass to yield molar Na2O:

Al2O3:SiO2:H2O ratios as presented in Table 2. The alkaline activa-
tor was provided as the sodium aluminate, which dissolves readily
in water, thus water only had to be added to initiate the reactions.
The mix-design was chosen to facilitate comparison with previ-
ously investigated formulations with the same molar ratios
[16,18,19].
Pastes were mixed for 4 min using a contact free planetary cen-
trifugal mixer at a rotation speed of 1200 min 1. After mixing the
pastes were immediately cast into 20 mm  20 mm  20 mm cube
moulds. The samples were cured in the open moulds at 80 °C and

100

90
Volume passing size (%)

80

70

60

50

40
Fig. 3. XRD patterns of the RHA feedstock and the one-part geopolymers after 1 d,
30 3 d and 7 d of curing. (q = quartz, c = cristobalite, P = potassium magnesium
phosphate; C = calcite, T = thermonatrite.).
20

10
80% r.H. in an oven with climate (r.H.) conditioning. The curing
0 temperature of 80 °C was chosen to accelerate geopolymerization
0.1 1.0 10.0 100.0 1000.0 reactions and hardening, as is standard in geopolymer technology
Particle size (µm) (e.g. [4,5,12,18,30]), though geopolymers from highly reactive
feedstocks in an optimized mix can also be cured at room
Fig. 1. Particle size distribution of the rice husk ash.
 P. Sturm et al. / Construction and Building Materials 124 (2016) 961–966 963

Table 2 to the composite-like character of zeolite-containing one-part sys-

Mix-design and molar ratios of the one-part geopolymers. tems mentioned above [16,18,19].
m(Na2O) m(Al2O3) m(SiO2) m(H2O) Na2O/Al2O3 SiO2/Al2O3 H2O/Al2O3 Minor amounts of thermonatrite (Na2CO3
H2O; PDF # 00-008-
(wt.%) (wt.%) (wt.%) (wt.%) (mol/mol) (mol/mol) (mol/mol) 0448) could be identified in the geopolymers, due to minor carbon-
10.17 16.76 34.46 35.03 1.00 3.48 11.81 ation of the highly alkaline reaction system. The phosphate and the
calcite, present in the starting RHA, disappeared after curing, indi-
cating their dissolution during curing; cristobalite and quartz
remained in the system after curing (Fig. 3).
temperature in a reasonable time [6,9,10,15]. After the desired cur- Curing for longer periods than 1 d did not lead to significant
ing times (24 h, 3 d or 7 d) the specimens were removed from the changes in the phase content, as observed by XRD. This leads to
oven and the moulds, allowed to cool down to room temperature, the conclusion that after one day of curing the geopolymerization
and tested according to the procedures described in Section 2.3. reactions were almost complete. This behavior has also been
Curing times longer than 24 h are unusual in geopolymer technol- observed with one-part geopolymers based on other silica feed-
ogy and would require higher energy consumption; nevertheless, stocks cured at 80 °C [16,18].
longer curing times were investigated to clarify whether these The infrared (ATR FT-IR) spectra of the unreacted RHA and the
can improve the mechanical properties of the material. cured geopolymers are shown in Fig. 4. All spectra, particularly
the spectra of the cured geopolymers, exhibited broad and overlap-
ping absorption bands, which demonstrates the amorphous char-
2.3. Structural and mechanical investigations acter of the compounds.
Bands around 3350 cm 1 (vibration 1; numbers refer to desig-
XRD investigations were conducted on powdered samples on a nations in Fig. 4) correspond to overlapping asymmetric and sym-
Rigaku Ultima IV device using the following measurement condi- metric stretching vibrations of the incorporated water and are only
tions: Bragg-Brentano geometry; CuKa radiation (k = 1.5419 Å); present in the geopolymer samples. Their intensity decreased with
scanning range: 5–65° 2h; step size: 0.02° 2h; scanning speed: increasing curing time, indicating a slight water loss during curing,
0.5° 2h min 1; sample rotation speed: 15 rpm. despite the fact that relative humidity was 80%. The same behavior
ATR FT-IR experiments were performed on powdered samples – a decrease in intensity with increasing curing time – was
on a Bruker Tensor 27 device with a diamond ATR module. Spectra observed for the bending vibration of water (vibration 2). No water
were recorded in the range 4000–400 cm 1 with a resolution of bands were observed in the RHA spectrum, consistent with the fact
4 cm 1 and 16 scans per spectrum (detector: RT-DLaTGS). that the material was produced by calcination at 650 °C.
SEM observations were carried out on a Carl Zeiss EVO MA10 Bands around 1440–1400 cm 1 (vibration 3) in the geopoly-
device at an accelerating voltage of 7–10 kV using a secondary mers are attributed to carbonate [35], i.e. the signals are caused
electron (SE) detector. The investigations were conducted on frac- by the incorporated thermonatrite, which has been observed by
ture surfaces of the specimens after compressive strength testing. XRD (Fig. 3). These carbonate absorptions bands were only found
Samples were sputtered with gold before the SEM measurements. in the geopolymer samples, i.e. the marginal amount of calcite in
The compressive strength tests were performed on a ToniPRAX the anhydrous RHA was not observed in its infrared spectrum.
device at a loading rate of 240 N/s, which is equivalent to 0.6 MPa/s Peaks at 1059 cm 1 (vibration 4) and between 985 and
for the investigated specimens (cubes, 20 mm  20 mm  20 mm). 975 cm 1 (vibration 5) correspond to asymmetric stretching vibra-
Testing was always conducted within the first 30 min after remov- tions of Si-O-Si in the RHA and Si-O-T (T = Si or Al) in the geopoly-
ing the samples from the curing regime. Compressive strength was mers, respectively. The absorption bands of asymmetric Si-O-T
tested after 1 d, 3 d and 7 d of curing.

3. Results and discussion

3.1. Structural investigations

The XRD results for the untreated RHA as well as for the cured
geopolymers are shown in Fig. 3. The hump from the RHA, maxi-
mum located at 21.82° 2h, disappeared after curing and a new
hump with its maximum at 27.68° 2h, representing the geopoly-
meric gel [34], occurred after curing. The disappearance of the
hump from the RHA indicates its virtually complete reaction, i.e.
a degree of reaction of the RHA close to 100%. This contrasts previ-
ously investigated one-part geopolymer systems, in which the
silica feedstocks reacted only partly, depending on the initial SiO2/
Al2O3 ratio [16,18]. In particular, at a starting SiO2/Al2O3 (i.e. total
SiO2/Al2O3 ratio of the mix including silica and sodium aluminate)
of 3.5 mol/mol the degree of reaction of the silica feedstocks
(microsilica or silica-rich residue from chlorosilane production)
in these previous investigations was only 55%, while the degree
of reaction of the RHA at the same starting SiO2/Al2O3 (Table 2)
is near 100%.
The diffractograms of the 1 d, 3 d and 7 d cured specimens indi-
Fig. 4. ATR FT-IR spectra of the RHA feedstock and the one-part geopolymers after
cated almost completely amorphous reaction products. No crys- 1 d, 3 d and 7 d of curing. (1 = mas,s H2O; 2 = d H2O; 3 = carbonate; 4 = mas Si-O-Si;
talline aluminosilicates, such as zeolites, were observed; thus the 5 = mas Si-O-T (T = Si or Al); 6 = ms Si-O-Si; 7 = ms Si-O-T (T = Si or Al); 8 = CB (complex
cured mixes can be considered to be pure geopolymers, different band); 9 = d O-Si-O in RHA; 10 = d O-Si-O in geopolymers.)
964 P. Sturm et al. / Construction and Building Materials 124 (2016) 961–966

stretching vibrations in tectosilicates shift to lower wavenumbers SEM micrographs of the 3 d cured one-part geopolymer are
with increasing aluminum content [36–38]. Therefore, this shift shown in Fig. 5. At lower magnification (Fig. 5, top), a microstruc-
proves the incorporation of aluminum in the geopolymer network. ture comprising homogeneously distributed, small pores, was
The Si-O-Si symmetric stretching vibration of the RHA at observed. At higher magnification (Fig. 5, bottom), the geopolymer
797 cm 1 (vibration 6) did not remain in the geopolymer samples. exhibits mainly the dense and homogeneous microstructure that is
Instead, Si-O-T (T = Si or Al) absorptions were observed at 684– observed for well-cured conventional geopolymers (e.g., based on
680 cm 1 (vibration 7). Again, there was a shift to lower wavenum- fly ash [40]) too. Besides, the micrograph also shows regions of par-
bers and the disappearance of the characteristic vibration 6 ticulate structure (e.g., bottom middle); these particles are how-
(ms Si-O-Si) was a further indication of a high degree of reaction ever not remnants of the RHA, as the latter has reacted almost
of the silica feedstock. completely.
Absorption bands in the range 575–573 cm 1 (vibration 8) in
the geopolymers are attributed to complex vibrations (CB =
3.2. Compressive strength
complex band) of stretching and bending vibrations (ms Si-O-Si; d
O-Si-O) [39]. Bands at 451 cm 1 (vibration 9) and at 421–419 cm 1
Fig. 6 shows the compressive strengths of the one-part geopoly-
(vibration 10) represent O-Si-O bending vibrations in the RHA
mer after 1, 3 and 7 days of curing. After 1 d the specimens reached
feedstock and the geopolymers, respectively.
compressive strengths of 29.8 MPa on average. After 3 d of curing
the average compressive strength reached the maximum value of
32.7 MPa. Curing for 7 d resulted in a slight strength decrease
(30.1 MPa). Since the compressive strengths at all investigated cur-
ing times were similar, it is concluded that curing times longer
than 24 h are of no use for the investigated material at the
employed curing conditions.
The obtained strengths are significantly higher than the
strengths of one-part geopolymers with similar compositions, but
different silica starting materials [16,18,19]. The principal reason
for the higher strength of the one-part geopolymers produced from
RHA is assumed to be the higher degree of reaction of the silica
and the absence of zeolites, as is discussed in more detail in
Section 3.3.

3.3. General discussion

Generally, one-part geopolymer mixes tend to form significant

amounts of crystalline zeolites as reaction products [11,12,14–
19]. In addition, it appears that these mixes often yield products
of comparatively low compressive strengths; in the published liter-
ature strengths are significantly below 30 MPa or strength data is
not reported [11,12,14,16–19]. However, Feng et al. [15] were able
to produce one-part geopolymers with a comparatively low
amount of incorporated crystallites, which reached compressive
strengths of >30 MPa after 7 days of curing at 25 °C. This suggests
that avoiding the formation of crystalline byproducts during
geopolymerization enhances the strengths of one-part geopolymers.

40

35
Compressive strength (MPa)

30

25

20

15

10

0
0 1 2 3 4 5 6 7 8
Curing time (d)

Fig. 6. Compressive strength of the one-part geopolymers after 1 d, 3 d and 7 d of

Fig. 5. SEM micrographs of the one-part geopolymers after 3 d of curing. curing. (Error bars represent one standard deviation in each direction.).
 P. Sturm et al. / Construction and Building Materials 124 (2016) 961–966 965

It is thus interpreted that the absence of crystalline side-products intraparticle porosity, which increases the water demand of the
(zeolites) in the RHA-based geopolymers (Fig. 3) contributed to pastes and leads to a poorer workability.
their higher strength when compared to one-part geopolymers Despite its coarser PSD, the RHA had a higher specific surface
produced from most other feedstocks. area (49.6 m2/g) than the microsilica and the residue from
The one-part mixes investigated in Refs. [16,18,19], synthesized chlorosilane production (20.1 m2/g and 32.3 m2/g, respectively).
in the same way as the formulations investigated in the present This can be explained by the fact that the particles of the RHA
contribution, but using microsilica and a residue from chlorosilane had a more angular shape, apparently a rougher surface (cf.
production as silica feedstocks, were found to have an silica/ Fig. 2) and a significant amount of mesopores (average pore diam-
alumina-ratio of the reactions products of SiO2/Al2O3  2 mol/mol, eter 12.9 nm; see Section 2.1) when compared to the particles of
independent of the starting mix-design of the pastes [16,18]. In all microsilica and similar materials. This higher specific surface area
cases, dissolution of the silica and formation of reaction products of the RHA is assumed to be a major reason for the higher degree of
ceased when this SiO2/Al2O3 ratio was reached. The silica not con- reaction of the RHA when compared to the other silica feedstocks.
sumed to reach this SiO2/Al2O3 ratio remained undissolved in the
hardened pastes. In contrast to these previous results, the one- 4. Conclusions
part geopolymers produced from RHA exhibited a virtually com-
plete reaction of the silica feedstock (RHA), as indicated by XRD One-part geopolymers were produced from rice husk ash (RHA)
and ATR FT-IR spectroscopy, and the pastes transformed into by mixing the RHA with solid sodium aluminate at a ratio to yield
amorphous sodium aluminosilicate (N-A-S(-H)) gel, i.e. no zeolites SiO2/Al2O3 = 3.5 and subsequently mixing the solid blend with
formed. It is known that it is this N-A-S(-H) gel that is mainly water and curing at 80 °C and 80% r.H. The compressive strength
responsible for the strength development of low-calcium alkali- of the geopolymer was 30 MPa after one day of curing. As shown
activated materials [2,34]. The strength of geopolymers is thus by XRD, the feedstocks almost completely reacted and transformed
dependent on the amount of N-A-S(-H) gel formed, its composition into amorphous geopolymer (N-A-S(-H) gel). Comparison of the
and its microstructure. As shown in Fig. 5 (bottom) the RHA-based infrared spectra of the RHA and the reaction products indicated a
one-part geopolymers exhibited a rather dense and homogeneous high degree of reaction of the RHA too. No crystalline reaction
microstructure. In contrast, the microstructure of the one-part products were observed, except for minor amounts of hydrated
geopolymers based on the other silica materials (i.e. microsilica sodium carbonate due to carbonation. Curing for longer times than
or silica residue from chlorosilane production) consists of ca. one day caused a slight decrease of the water content of the
100 nm-sized particles, possessing a large amount of interparticle geopolymer, but no other significant changes were observed in
pore space [16,19]. This difference can be attributed to the the XRD patterns and the infrared spectra.
SiO2/Al2O3 ratio of the geopolymeric gel: In their SEM study on The results of this study thus show that RHA can be applied
metakaolin- and fly ash-based geopolymers, Steveson and successfully for the synthesis of one-part geopolymers. The
Sagoe-Crentsil [41,42] found that there is a transition from a RHA-based geopolymers provide some improved properties when
particulate and porous microstructure at low SiO2/Al2O3 ratios compared to one-part geopolymers based on other silica materials,
(2.5–3 mol/mol) to a dense and homogeneous microstructure at in particular an almost complete reaction of the silica feedstock and
higher SiO2/Al2O3 ratios (3.5–3.9 mol/mol). Similar observations a comparatively high compressive strength. Optimization of the
have been made by Duxson et al. [43]. It can thus be concluded that RHA-based one-part geopolymers regarding chemical composition
the high degree of reaction of the RHA led to a comparatively high and water/binder ratio, as well as curing conditions and curing
SiO2/Al2O3 ratio of the reacted geopolymer (presumably in times will be subject of future studies.
the range of the starting SiO2/Al2O3 of 3.5 mol/mol; Table 2) and
consequently to a denser microstructure than in other one-part
Acknowledgements
geopolymers, which caused a higher compressive strength of the
RHA-based material.
The authors thank Christiane Weimann and Carsten Prinz for
Summarizing, we attribute the comparatively high compressive
help with the SEM investigations and the determination of specific
strengths of the RHA-based one-part geopolymers mainly to (1)
surface area and porosity of the RHA, respectively. The authors are
the absence of significant amounts of crystalline byproducts, and
also very grateful to Nsesheye Msinjili for providing the rice husk
(2) the almost complete reaction of the RHA, which resulted in a
ash sample. P.S. acknowledges financial support from BAM within
higher SiO2/Al2O3 ratio and a denser microstructure of the N-A-S
the MIS program (proposal Ideen_2012_36).
(-H) gel than in one-part geopolymers produced from other silica
sources.
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