Construction and Building Materials 187 (2018) 65–76

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Construction and Building Materials

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Design and characterisation of ternary cements containing rice husk ash

and fly ash
C. Medina a,⇑, I.F. Sáez del Bosque a,⇑, M. Frías b, M.I. Sánchez de Rojas b
a
Departamento de Construcción, Escuela Politécnica de Cáceres – Grado de Ingeniería Civil, Universidad de Extremadura, Unidad Asociada ‘‘SOSMAT” UEX-CSIC,
Instituto de Investigación de Desarrollo Territorial Sostenible (INTERRA), 10003 Cáceres, Spain
b
Departamento de Cementos y Reciclado de Materiales, Instituto de Ciencias de la Construcción Eduardo Torroja, Consejo Superior de Investigaciones Científicas (CSIC),
28033 Madrid, Spain

h i g h l i g h t s

The system RHA-FA has been used as SCMs in the design of the new blended cements.

The mortars designed compliant with the requirements laid down in European standard.

There is synergistic effect in the system RHA-FA.

The optimal RHA-FA replacement is 15%.

The addition of RHA-FA to the mortars lowers the total heat of hydration.

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

Article history: This study explored the interaction between rice husk ash (RHA) and fly ash (FA) as partial (0%, 15% or
Received 25 December 2017 30%) additions in new ternary cements designed to reduce cement industry energy consumption and
Received in revised form 5 June 2018 greenhouse gas (GHG) emissions by lowering their clinker content. To that end, the effect of the introduc-
Accepted 23 July 2018
tion of mixed RHA and FA on the pozzolanicity of the RHA-FA/lime system was assessed and its impact on
the chemical, physical, rheological, mechanical, calorimetric and microstructural properties of the new
ternary cements analysed. The joint use of these additions revealed mixture synergies, with an initial rise
Keywords:
in FA pozzolanicity in the presence of RHA, although this effect declined over time. The inclusion of the
Synergies
Supplementary cementitious Materials
RHA-FA mixture prompted changes in the pore structure of mortars that after 90 d translated into 2%
Calorimetry lower compressive strength than the control in mortars with 15% addition and a 19% decline in materials
Mechanical behaviour containing 30% waste. That notwithstanding, the new cements were European standard EN 197-1-
Microstructure compliant for cement types II/A-M, II/B-M and IV-A. Furthermore, the mortars prepared with 15%
RHA-FA released 5.67% less total of hydration than OPC and the materials containing 30% of the addition
13.54% less than the reference. In light of the foregoing, the new cements were found to be apt for use in
construction, particularly in structures where large volumes of concrete are needed, for the reduction of
the thermal gradient lowers the likelihood of surface cracking.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction defined four strategic measures geared to emission abatement in

the industry by 2050: i) improve thermal and electrical efficiency;
The reduction of greenhouse gases in general and CO2 in ii) seek alternative fuels; iii) reduce clinker content; and iv)
particular is one of the primary challenges facing the cement and develop CO2 storage and capture systems. Of the four, the third
concrete industry today. In 2009, it accounted for 5% of the total yields the most immediate results, with 25%–30% lower CO2
CO2 emitted worldwide [1]. That year, the International Energy emissions [2].
Agency and World Business Council for Sustainable Development Sights are being trained now more than ever on supplementary
cementitious materials (SCMs) to replace clinker in cement manu-
facture in an attempt to produce new, higher performing cements
⇑ Corresponding authors.
with less embedded energy and longer effective service lives [3].
E-mail addresses: cmedinam@unex.es, cemedmart@yahoo.es (C. Medina),
isaezdelu@unex.es, isa.f.saez@gmail.com (I.F. Sáez del Bosque).
European standard EN 197-1 [4] regulates the use of SCMs such

https://doi.org/10.1016/j.conbuildmat.2018.07.174
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
66 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76

as fly ash, blast furnace slag and silica fume in the design of strength and corrosion resistance [21,22]. All show pozzolan per-
cements CEM II, III, IV and V to ensure good performance. Nonethe- centages of over 20% to induce a slight decline in end performance,
less, the accessibility of such additions is geographically limited directly dependent upon on the intrinsic characteristics of the
compared to the yearly demand of cement and concrete for new additions, rice husk ash in particular.
builds and rehabilitation works. Consequently, the viability of The relevance of this study stems from the present gap in scien-
using any available glassy or amorphous material as an SCM should tific and technical knowledge of cement-fly ash-rice husk ash tern-
be researched with a view to lowering the clinker content in ary cementitious systems. Its innovation lies in the scientific
cement and concrete [5]. verification, based on the mechanical, rheological and calorimetric
One waste material whose valorisation in construction has properties of RHA-FA, of the aptness of this waste for manufactur-
recently roused a good deal of interest is the husk generated during ing eco-efficient ternary cements.
rice processing. According to Food and Agriculture Organisation The aims were to assess the pozzolanic properties of the fly ash /
(FAO) data, rice production amounted to 712.5 million tonnes in rice husk ash mixture, analyse the synergies of the two wastes in
2014, approximately 20 wt% of which consists in husk. Incineration (15%–30%) pozzolan/(85%–70%) cement systems and determine
reduces that mass by 80% to around 28.5 million tonnes of rice the chemical, rheological, mechanical, calorimetric and microstruc-
husk ash (RHA) [6,7], a by-product that has been the object of con- tural properties of new, low clinker content ternary cements.
siderable research and used as a mineral addition in the cement
[6,8] and concrete [9–11] industry. Its effect on the physical and
mechanical properties and durability of the fresh and hardened 2. Materials and methods
product has been associated primarily with its origin, combustion
2.1. Materials
process and particle size.
In today’s socio-economic context the development of ternary One of the additions used, fly ash (FA), is standardised and the other, rice husk
cements containing several additions such as fly ash or rice husk ash (RHA), non-standardised. The latter was obtained by incinerating rice husk at
ash with other industrial by-products or waste (silica fume [12], 600 °C for 3.5 h (DT = +10 °C/min for 40 min; T = 400 °C for 25 min; DT = +10 °C/
cement kiln dust [13], sugar cane bagasse ash [14], nano-TiO2 min for 25 min; and T = 600 °C for 2 h), the optimal regime, according to the liter-
ature [6,23]. It was subsequently ground and sieved through a 63 lm sieve. Rice
[15], oxygen furnace slag [16], ground granulated blast furnace slag husk morphology is depicted in Fig. 1. Fig. 1a.1 shows the husk as received at the
[17] and paper sludge [18]) is attracting ever greater interest. The laboratory, with its elongated, fibrous particles. The SEM micrographs of the husk
joint introduction of several SCMs has consistently been shown to surface at different magnifications in Fig. 1a.2–a.3 show its papillae and branches
be beneficial, providing a satisfactory balance can be struck of different sizes, all arranged in a profile characterised by neatly aligned linear
ridges and furrows. Overall, it exhibited a honeycombed structure. The changes
between replacement ratio (which depends on the specific surface,
attributable to calcination and sieving are visible in Fig. 1b.1–b.3, particularly the
chemical composition and other characteristics of the additions) changes in colour (from yellowish to white) and morphology. These micrographs
and performance. revealed a general breakdown of the rice husk structure into small, irregularly
Research on the joint valorisation of fly ash (FA) and rice husk shaped fragments, along with a certain degree of porosity.
ash (RHA) as cement constituents is incipient, with very scant lit- A 50 wt% mix of these additions (RHA:FA ratio = 1:1), labelled RHA-FA, was
mixed in a blender for 15 min to ensure uniformity.
erature on the subject to date. The studies published primarily The commercial OPC used in this study, defined in European standard EN 197-1
address the effect of these additions on conventional [19] and [4] as CEM I 42.5R, was supplied by Lafarge, a manufacturer in the Spanish province
high-strength [20] concrete and mortar durability, mechanical of Toledo. The XRF chemical composition of the cement is given in Table 1.

Fig. 1. Rice husk morphology (to the naked eye and under the SEM): a.1) pre-incineration rice husk; a.2) SEM micrograph of pre-incineration rice husk at 30; a.3) SEM
micrograph of pre-incineration rice husk at 1200; b.1) post-incineration (600 °C) husk; b.2) post-incineration husk < 63 lm; b.3) SEM micrograph of post-incineration husk
at 1200.
 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76 67

Table 1
Chemical composition of the starting materials.

Majority oxide (wt%)

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O SO3 P2 O5 Other LoI
FA 44.41 26.42 16.80 1.45 5.63 0.23 1.52 1.05 0.23 0.95 1.17
RHA 89.75 0.14 0.19 0.85 1.76 0.04 3.65 0.35 1.40 0.18 1.64
OPC 20.27 4.61 2.44 3.35 59.40 0.84 1.41 4.14 0.22 0.17 3.04
RHA-FA 73.06 8.29 8.18 1.07 3.12 0.12 2.46 0.56 0.92 0.52 1.63
Trace element (ppm)
Sr Cu Ni Ba Cr V Zn Pb Cl
FA 387 6 150 396 166 208 140 19 31
RHA 32 – 11 – 46 1 17 – 167
OPC 506 – 62 – 104 37 53 3 284
RHA-FA 219 – 76 – 95 93 56 – 105

After blending the dry materials in a turbula blender for approximately 1 h to Mortar pore size distribution was quantified as per ASTM standard D 4404 [29]
ensure homogeneity, seven mixes were prepared to characterise the mortars: on a Micromeritics Autopore IV 9500 mercury porosimeter (scale, 0.006–175 mm,
OPC, OPC + 7.5FA, OPC + 15FA, OPC + 7.5RHA, OPC + 15RHA, OPC + 15(RHA-FA), pressure, 33,000 psi (227.5 MPa)).
OPC + 30(RHA-FA). Heat of hydration was found with the Langavant semi-adiabatic method
described in European standard EN 196-9 [30], except that the w/c ratio used
was 0.4. Further to this method, mortars were prepared with the three cements
2.2. Characterisation of materials studied and placed in sealed bottles in a Dewar flask. Mortar temperature during
hydration was compared to the temperature of a thermally inert mortar (mixed
Fly ash and rice husk ash mineralogies were characterised by X-ray diffraction at least 12 months prior to the test, further to the standard) placed in a second flask
(XRD) and their chemical compositions were determined with X-ray fluorescence as a control.
(XRF). For scanning electron microscopic (SEM/EDX) analysis, the samples were
XRF scans were performed on a Bruker S8 TIGER wavelength dispersive X-ray secured to a metallic holder with a two-sided graphic adhesive after carbon coating
fluorescence spectrometer with standardless Spectraplus Quant Express software. the surface to ensure conductivity and detection of all the signals sought.
Mineralogy readings were taken at 2h diffraction angles ranging from 5° to 60°
on a Bruker D8 Advance X-ray diffractometer fitted with a Lynxeye detector and
a Ni K-beta filter. The X-ray source was a Cu anode X-ray tube (radiation, 1.54 Å 3. Results and discussion
CuKa) running at 40 kV and 30 mA.
Material fineness, expressed as Blaine specific surface, was measured on an 3.1. Characterisation of the starting materials
Ibertest Autoblaine Plus analyser to the procedure described in European standard
EN 196-6 [24].
Table 1 gives the chemical compositions of each ash individu-
ally and the 50 wt% mixture of the two. The data show that the
2.3. Pozzolanic behaviour sum of the main acid oxides (SiO2 + Al2O3 + Fe2O3) accounted for
over the 70% minimum specified in U.S. standard ASTM C618-15
Pozzolanicity was analysed using both an accelerated chemical method [25]
and the Frattini test described in European standard EN 196-5 [26].
for fly ash [31], which also contained Sr, Ba and V as trace elements
The former consisted in soaking 1 g of RHA-FA in 75 mL of a 17.68 mM/L cal- (<200 ppm–400 ppm). Further to the CaO-SiO2-Al2O3 ternary dia-
cium hydroxide (portlandite)-saturated solution for 6 h, 1 d, 2 d, 7 d, 28 d and 90 gram in Fig. 2, the chemical composition of both RHA and RHA-
d at 40 °C. At the aforementioned ages, the filtrate was analysed for the concentra- FA resembled that of silica fume (addition standardised in EN
tion of CaO ions and the amount of lime fixed was found as the difference between
197-1 [4]).
the initial concentration (17.68 mM/L) and the amount of CaO in the solution in
contact with the sample. The solid residue was rinsed with acetone and vacuum The X-ray diffractograms in Fig. 3 show that the FA was much
dried for 24 h to detain hydration, after which it was studied with XRD and Fourier more crystalline than the RHA. The wide amorphous hump peaking
transform infrared spectroscopy (FTIR). at 2h = 22° in the RHA was attributed to its high amorphous silica
In the Frattini method, 20 g of the cement to be tested (85 wt% OPC + 15 wt% content, and its sole reflection line at 2h = 26.62° to quartz. The
RHA-FA or 70 wt% OPC + 30 wt% RHA-FA) were mixed with 100 mL of distilled
pattern for FA contained reflections identified as quartz (SiO2),
decarbonated water and stored in an air-tight polyethylene container in an electric
oven at 40 °C. After 8 d and 15 d, 20 mL of the solution were titrated with 0.1 N mullite, hematite (Fe2O3), lime (CaO) and magnetite (Fe3O4). It also
hydrochloric acid (HCl) and the [OH] was found with methyl orange. Calcium
ion concentration was determined from the titrated samples in which the pH was
adjusted to 12.5 ± 0.2 with a 4 N NaOH solution. The sample was then titrated
against a 0.02 mol/L solution of EDTA. Using calcein as the indicator, the endpoint
was the change in colour from pinkish to violet. The presence of Ca(OH)2 in ordinary
Portland cement was determined from the solubility curve resulting from plotting
the [OH] values in mmol/L vs [Ca2+], expressed as the CaO equivalent in mmol/L.

2.4. Characterisation of mortars

New eco-efficient cement rheology (normal consistency, start and end setting
times) was determined with a Vicat needle, proceeding as described in European
standard EN 196-3 [27].
Cement soundness was studied with a Le Chatelier analyser, using normal con-
sistency cement paste as specified in European standard EN 196-3 [27].
The effect of the inclusion of the mixture of rice husk and fly ash at 15% and 30%
replacement ratios on the compressive and three-point bending strengths of the
new eco-efficient cements was assessed pursuant to European standard EN 196-1
[28]. The 4x4x16 cm mortar specimens tested were prepared with a sand/cement
ratio of 3/1 and a water/cement ratio of 1/2. Twenty-four hours after preparation
they were removed from the moulds and cured at a temperature of 20 ± 1 °C and
a relative humidity of 100% until tested. Fig. 2. CaO-SiO2-Al2O3 ternary diagram for starting materials.
68 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76

Fig. 3. XRD patterns: a) fly ash (FA); b) rice husk ash (RHA).

exhibited an amorphous hump at 2h = 20°–35°, denoting the pres- mixture in less than 24 h. These findings attested to synergies
ence of amorphous or glassy components. The existence of these between RHA and FA, with the RHA-induced activation of early
humps in the RHA and FA diffractograms, along with the high age FA pozzolanicity contributing to the high percentage of lime
SiO2 content detected by XRF, heralded high pozzolanicity in the fixed by the RHA-FA mixture from the outset. As the intensity of
RHA-FA mixture. these synergies declined over time, however, the empirical
The Blaine specific surface in RHA was 7100 cm2/g, in FA, pozzolanicity for the mixture at the end of the test was essentially
2395 cm2/g and in RHA-FA, 3947 cm2/g. The smaller particle size the same as the theoretical value.
in RHA than in FA and the RHA-FA mixture and its optimality Other non-standardised silica-high agroindustrial additions
(7000 cm2/g, as per Antiohos et al. [10]) were subsequently such as elephant grass ash have been reported to fix 85%–96% of
shown to have a direct impact on pozzolanicity. the total lime after 7 d [33], a value very similar to the percentages
found for RHA-FA (88%), despite the low (12%) pozzolanicity in
3.2. Pozzolanicity FA when studied separately. At 93.3%–97%, the 28 d pozzolanicity
for elephant grass ash was slightly higher than the 89% observed
3.2.1. Saturated lime solution method for the RHA-FA mixture. RHA-FA pozzolanic activity was also sim-
Pozzolanicity over time for the RHA-FA mixture and each addi- ilar to that exhibited by bamboo leaf, studied by Frías et al. [34],
tion individually is shown in Fig. 4. The mixture exhibited high who observed 28 d lime fixation values of 91%. In a study of the
early age pozzolanicity, fixing around 49% of the total lime in the valorisation of sugar cane straw and bagasse ash as cement addi-
first 6 h and 83% after 1 d, the same percentage as observed for tions after incineration at 800 °C, Villar-Cocina et al. [35] reported
silica fume [32]. This contrasted sharply with fly ash, for which high 1 d lime fixation values (51% and 38%, respectively), which
scantly any pozzolanicity was detected. Pozzolanicity in the RHA- rose after 90 d to 92%–93%.
FA mixture was only slightly lower than in RHA, however, the
amount of lime fixed by the RHA-FA mixture was much higher 3.2.2. Frattini method
than calculated theoretically on the grounds of the pozzolanicity The Frattini pozzolanicity test results for the cements contain-
of each component (see Fig. 4a). Furthermore, as Fig. 4b shows, ing 15% and 30% RHA-FA are shown in Fig. 5. The 8 d ternary
FA pozzolanic activity grew significantly between 7 d and 28 d, cements lay below the CaO solubility curve, an indication of the
whereas similar rises in pozzolanicity were observed in the huge uptake of the calcium hydroxide released during cement

Fig. 4. Lime fixation vs time (pozzolanicity test) a) RHA-FA; b) FA and RHA.

 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76 69

A calcium silicate hydrate (C-S-H) gel was also detected at 2h =

16.16°, 28.97°, 29.96°, 31.70°, 42.07°, 49.44° and 54.83°.
The 0 d, 2 d and 90 d FTIR spectra for the RHA-FA/Ca(OH)2 sys-
tem (Fig. 6b) contained a series of intense, overlapping adsorption
bands between 1200 cm1 and 1000 cm1 characteristic of TAO
and SiAOAT (T = Si or Al) bonds in silicate (quartz, amorphous
SiO2, glassy phases) and aluminosilicate (mullite, glassy phases)
tetrahedra (TO4) [37,38]. In the spectrum for the anhydrous (0 d)
RHA-FA mixture, the signal in this region was fairly narrow and
centred at around 1102 cm1 with a shoulder at 1200 cm1, both
characteristic of the asymmetric stretching vibrations generated
by TAO bonds. In contrast, in the 2 d and 90 d spectra, the afore-
mentioned band was much wider, perhaps denoting greater phase
overlapping, and shifted to around 1090 cm1. A shoulder at
approximately 967 cm1 was associated with C-S-H gel and,
according to Yu et al. [39], more specifically to the Q2 units in
the gel. That shoulder corroborated the pozzolanicity observed in
the saturated lime test (Fig. 4) and the formation of C-S-H gel
Fig. 5. Cement pozzolanicity (Frattini test results). during the pozzolanic reaction in the RHA-FA/portlandite systems
as a result of the high silica content in the addition. The medium
intensity band at around 800 cm1 and the intense band at around
465 cm1 present in the 0 d, 2 d and 90 d spectra were due to sym-
hydration. Pursuant to European standard EN 197-1 [4] specifica-
metric stretching vibrations in the TAO bonds, as well as OATAO
tions, therefore, both OPC + 15% RHA-FA and OPC + 30% RHA-FA
bond bending vibrations in the starting silicates and aluminosili-
constituted pozzolanic cements (CEM IV/A). The data point for
cates present in FA and RHA and the OASiAO bonds in the C-S-H
the ordinary Portland cement used (CEM I 42.5 R), which exhibited
gel.
no pozzolanic activity, lay above the CaO solubility curve.
All the spectra contained a wide band centred at around 3431
Further to the literature, the cement containing 30% RHA was
cm1, attributed to the stretching vibrations generated by the
Frattini pozzolanicity test-compliant, with 8 d values below the
OAH bonds in adsorbed water, although according to Yu et al.
CaO solubility curve [10]. In contrast, while the 7 d cement con-
[39], C-S-H gel exhibits a band at around 3300 cm1 induced by
taining 20% FA was not always compliant, the respective 28 d
the interlayer water in the gel, which would overlap with the
materials consistently passed the Frattini test [36]. As Fig. 5 shows,
adsorption water band. A bending band on all the spectra at
both 8 d cements bearing RHA-FA studied here met the pozzolanic-
ity requirement, further supporting the presence of synergies
between the two additions. Table 2
Chemical requirements for low clinker cements.

3.3. XRD and FTIR identification of the hydration products in the RHA- Requisite/cement type Chemical Pozzolanicity
FA/portlandite system constituent (wt%) (Frattini test)
SO3 Cl
Fig. 6a shows the mineralogical phases forming in the 2 d and Standard requirement for cement 4.00 0.10 –
90 d pozzolanic reaction, including the reflection lines characteris- type II/A-M y II/B-M
tic of mullite, hematite, magnetite and quartz present in the start- Standard requirement for cement Positive result
type IV/A
ing FA, as well as the calcite (2h = 29.04°, 39.34°, 43.19°, 47.37°,
OPC + 15% RHA-FA 3.60 0.03 Compliant
57.45°, 64.74° and 60.70°) resulting from the slight carbonation OPC + 30% RHA-FA 3.06 0.02 Compliant
induced by atmospheric CO2 during handling, testing and curing.

Fig. 6. Pozzolanicity over time: a) XRD; b) FTIR.

70 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76

1630 cm1 was attributed to the HAOAH bonds in water. Lastly, The cements nonetheless met the EN 197-1 initial setting time
the 2 d and 90 d spectra exhibited a weak absorption band at requirement for strength class 42.5 MPa.
around 1422 cm1 due to the carbonates formed during sample The presence of the mixture was observed to increase the water
handling [40]. demand for a normal consistency of 34 ± 2 mm as measured with
the Vicat device (Table 3). That higher demand, which rose with
the replacement ratio, was attributed primarily to the larger speci-
3.4. New cement compliance with chemical requisites
fic surface in the RHA-FA mixture than in OPC. That same pattern
was reported by other authors analysing systems with two addi-
Table 2 compares the SO3 and Cl ceilings laid down in European
tions, one more and the other less reactive, such as oxygen furnace
legislation (EN 197-1 [4]) for cements II/A-M, II/B-M and IV/A to
slag – rice husk [16] or fly ash – silica fume [12].
the values found for the additioned cements, which proved to be
Further to the tests conducted at a water/cement ratio of 0.50
standard-compliant. As noted in item 3.2.2, the cements also
(Table 3), inclusion of the addition reduced consistency relative
passed the pozzolanicity test, although this requirement applies
to OPC by 26% in OPC + 15% RHA-FA and by 34% in OPC + 30%
to type IV cements only. Consequently, OPC + 15% RHA-FA could
RHA-FA. These findings were directly related to the higher water
be used as II/A-M cement, OPC + 30% RHA-FA as II/B-M cement
demand in the new cements, attributed primarily to the inclusion
and both as type IV/A cement.
of rice husk ash [16,42].

3.5. New cement compliance with physical requisites 3.6. New cement compliance with mechanical requisites

The rheological and expansive properties of the cements anal- Mortar compressive and bending or flexural strength is plotted
ysed are given in Table 3. Inasmuch as the introduction of the against time (0 d–90 d) in Fig. 7. With a 2-day compressive
RHA-FA mixture induced no expansion in the cement paste, these strength of 20 MPa and a 28 d strength of 42.5 MPa, the mortars
ternary cements (OPC + 15% RHA-FA and OPC + 30% RHA-FA) met complied with the mechanical requisites laid down in European
the soundness requirements set out in European standard EN standard EN 197-1 [4] for strength class 42.5 MPa cements. The
197-1 [4]. curves show that the inclusion of the RHA-FA mixture had no
The initial and end setting times were longer in the ternary impact on the relationship between compressive and flexural
cements bearing the RHA-FA mixture than in the reference and strength and the log of curing time, which exhibited a correlation
rose with the replacement ratio. That finding could be attributed coefficient (R2) of over 0.90, irrespective of mortar typology.
essentially to the higher amounts of Zn, Pb, Cr and Ni present in Fig. 7 shows that 2 d compressive strength was 9% lower in
RHA-FA ternary cements than in OPC [41]. OPC + 15% RHA-FA than in OPC and 24% lower in OPC + 30%

Table 3
New cement rheological properties and soundness.

Property OPC OPC + 15% RHA-FA OPC + 30% RHA-FA Standard requirement (EN 197-1)
Setting time (min) (±10 min) Initial time 147 207 315 60 min
End time 249 312 549 –
Water content (g) 149.0 180.0 216.0 –
Consistency (mm) 154.3 129.3 101.3 –
Soundness (mm) 1.0 1.0 1.0 10 mm

Fig. 7. Mortar compressive (CS) and flexural (FS) strength versus time.
 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76 71

RHA-FA 24%. That difference in performance narrowed with age the mechanical properties of new cements. The symbol q denotes
(90 d) to 2% in OPC + 15% RHA-FA and 19% in OPC + 30% RHA-FA, the percentage of conventional cement (OPC), Rb and Rr, the pro-
due to the effect of the RHA-FA mixture on material porosity and portion of strength accounted for by OPC and the system RHA-
pore size distribution (see Section 3.7). These findings revealed FA, respectively, and P the percentage contribution of RHA-FA to
that, as observed earlier by Paya et al. [43], due to high early age system compressive strength.
rice husk pozzolanicity and later age fly ash reactivity, the poz- The table shows that in cement containing 15% RHA-FA the per-
zolanic reaction was sustained across the entire curing time. The centage contribution of the addition to early age (2 d and 7 d)
optimal replacement ratio was found to be 15%, at which the syn- strength was greater than the percentage of rice husk in the blend.
ergies between the two additions practically offset the dilution In the material with 30% replacement, in contrast, the contribution
effect induced by the replacement ratio. was lower, lending further support to the premise that the optimal
The following factors determined the steeper decline in OPC + replacement rate is 15%. At later ages (>28 d), the percentage con-
30% CA-CV than OPC + 15% CA-CV mechanical performance: i) the tribution of the addition to strength rose steadily, reaching 12.95%
lower cement content prompted a decrease in the portlandite in the 15% blend and 13.15% in the 30% blend after 90 d. This find-
available for the pozzolanic reaction; ii) the pozzolanic reaction ing showed that with 15% replacement nearly all the addition
products from fly ash/ portlandite occupied a smaller volume than reacted, whereas a sizeable percentage of the ash in the 30% blend
the unreacted fly ash, leaving voids (see Fig. 10); and iii) the greater had not reacted after 90 d.
water demand in the former mortar lowered compressive strength,
as observed previously in earlier studies on ternary systems con-
taining rice husk: Sua-iam and Makul [44], Yang et al. [16] and Sha- 3.7. Total porosity and pore size distribution
tat [45], reported adverse effects of a high (>10 wt%) percentage of
this addition in ternary systems. Two day, 28 d and 90 d total porosity, mean pore diameter
This mechanical behaviour was similar to that reported earlier (MPD) and non-connected porosity data are given in Table 5. Total
for other ternary systems: porosity declined with age in all the mortars, while the effect of the
RHA-FA mixture depended on the replacement ratio. At 90 d and a
i) fly ash + blast furnace slag [17,46,47], where the difference replacement ratio of 15%, total porosity was 2% lower than in OPC,
in 28 d compressive strength relative to conventional whereas at a ratio of 30%, porosity was 10% higher than in OPC.
cement was greater than in the 90 d materials, which exhib- That pattern was consistent with reports by other authors who
ited only minor loss; recorded rises in total porosity with replacement ratios of over
ii) ferronickel slag (FS) + natural pozzolan (NP) [48] where a 20% [22] or 30% [21]. The increase in total porosity was due to
replacement ratio of 20% (FS:NP = 1:1) lowered 28 d com- the high specific surface in rice husk ash (RHA), which in turn
pressive strength by 14.0% and 90 d strength by 7.6%; and raised the water demand (see Table 3). Shatat [45] recorded similar
iii) fly ash (FA) + silica fume (SF) in different percentages (FA: findings when a mixture of metakaolin – rice husk was added to
10–30% and SF: 5–14%) where: cement at a ratio of over 10%. The anhydrous residue remaining
a) at a high fly ash replacement ratio (FA > 20%), compres- due to the failure of the addition to react fully contributed to that
sive strength declined irrespective of the content in silica result. Porosity may have also been intensified by the nature of the
fume [49,50] FA, normally consisting in hollow cenospheres which, once wholly
b) at percentages of FA equal to 20% and SF of 5%–10%, early or partially consumed in the pozzolanic reaction, leave voids that
age (<28 d) strength loss was recorded, whereas at later are not filled by the hydrated phases [54].
ages the material exhibited strength similar to the refer- Attendant upon the rise in total porosity, however, were a
ence cement [49–51] decline in the mean pore diameter and an increase in closed
c) at percentages of FA of 10% and SF of 5%–14%, perfor- porosity.
mance was higher than in the reference regardless of Irrespective of the replacement ratio, the pozzolanic activity of
mortar age [50,52]. the addition induced pore system refinement (Fig. 8) and a rise in
closed porosity, as observed by other authors [55]. The RHA-FA
The percentage contribution of the addition (RHA-FA) to com- mixture reacted, yielding: a) hydration products that occupy twice
pressive strength (P) at different ages is quantified in Table 4. This the anhydrous product volume [8]; b) accentuated sinuosity in the
parameter was determined using the methodology described by cementitious matrix; and c) a denser, less inter-connected matrix
other authors [53] to assess the contribution of granite sludge to [55]. Relative to OPC, MPD declined by 37% in OPC + 15% RHA-FA
and by 33% in OPC + 30% RHA-FA. Closed porosity was 16% greater
in OPC + 15% RHA-FA than in OPC and 7% greater in OPC + 30%
Table 4
RHA-FA.
Contribution of the RHA-FA mixture to compressive strength.

Age (days) Mortar q Rb Rr P

Table 5
2 OPC 100 0.418 0.000 0.000 Pore system in the 2 d, 28 d and 90 d mortars studied.
OPC + 15% RHA-FA 85 0.461 0.038 8.246
OPC + 30% RHA-FA 70 0.459 0.035 7.632 Mortar Age (days) Pt (%) MPD (mm) enon-connected (%)
7 OPC 100 0.544 0.000 0.000 OPC 2 14.40 0.08 57.49
OPC + 15% RHA-FA 85 0.606 0.066 10.885 28 12.95 0.06 59.62
OPC + 30% RHA-FA 70 0.607 0.063 10.386 90 12.61 0.06 60.93
28 OPC 100 0.657 0.000 0.000 OPC + 15% RHA-FA 2 14.36 0.06 62.52
OPC + 15% RHA-FA 85 0.746 0.086 11.532 28 12.62 0.05 67.41
OPC + 30% RHA-FA 70 0.747 0.089 11.907 90 12.35 0.04 70.74
90 OPC 100 0.691 0.000 0.000 OPC + 30% RHA-FA 2 17.75 0.05 61.72
OPC + 15% RHA-FA 85 0.795 0.103 12.949 28 14.47 0.05 64.02
OPC + 30% RHA-FA 70 0.798 0.105 13.150 90 13.92 0.04 65.24

Rb = fck/q; Rr = Rb-Rb(OPC); P = 100*(Rr/Rb). Pt: total porosity; MPD: mean pore diameter; enon-connected: non-connected porosity.
72 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76

Fig. 8. Pore size distribution versus time.

As shown in Fig. 8, the volume of macropores declined and the of medium-sized capillary pores was 36% higher in mortars with
proportion of small and medium-sized capillary pores rose over 15% RHA-FA than in OPC and 28% higher in materials with a 30%
time. In the 90 day mortars, the trend in macropore percentages addition. Small capillary pore volumes were 5-fold higher in
depended on the replacement ratio, declining by 18% in the mate- OPC + 15% RHA-FA than in OPC and seven-fold greater in
rials containing 15% RHA-FA and rising by 4% in those with 30% of OPC + 30% RHA-FA.
the addition, both relative to the OPC value. The failure of part of
the addition to react when RHA-FA accounted for over 15% of the 3.8. Mortar calorimetry
total (see Fig. 10) induced the aforementioned slight increase in
the volume of larger pores and total porosity, and consequently a The heat flow data for the mortars analysed plotted in Fig. 9
decline in mechanical performance [6,16]. show that heat peaked after 17 h or 20 h of hydration, depending
The volume of medium-sized and small capillary pores rose on the RHA-FA replacement ratio.
from the early ages due to the pozzolanic action of the RHA-FA In the first 3 h–4 h of hydration the mortars containing 15% or
mixture, which contributed to the formation of hydration products 30% RHA-FA exhibited greater heat of hydration than the reference
that filled the pores, refining the pore system [53,56]. The volume mortar (OPC), for pozzolanicity prevailed over the dilution effect.

Fig. 9. Fluctuation in mortar heating during hydration.

 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76 73

Table 6
Heat of hydration in the mortars studied.

Mortar OPC OPC + 15% RHA-FA OPC + 30% RHA-FA

Total heat of hydration (J/g) 326.53 308.01 282.31
Linear regression for the relationship between replacement ratio and heat of hydration:
2
y = 1.47x + 327.73; R = 0.99

Note. y: heat of hydration (J/g); x: addition (wt% of binder).

Moreover, the higher the replacement ratio, the greater the heat of The pattern observed in the early hours of hydration was con-
hydration at these early ages, due primarily to high rice husk poz- sistent with research findings in which this semi-adiabatic method
zolanicity (Fig. 4). An explanation for that finding may lie in earlier was used to study the effect of including sanitary ware industry
studies [57]: the adsorption of Ca2+ ions onto the pozzolan surface waste (Medina et al. [58]) or paper sludge (Rodríguez et al. [59])
and concomitant smaller concentration of Ca2+ in the solution were additions in the design of new ternary cements.
observed to favour alite re-dissolution, raising the Ca2+ concentra- After these initial hours, dilution prevailed over pozzolanic
tion to saturation and inducing portlandite and C-S-H gel activity and the slope of the heat of hydration - time curve declined
precipitation. with rising replacement ratio. That translated into lower heat

Fig. 10. Micrographs of 90 d mortar morphology: a) OPC morphology; b) sand/paste ITZ in OPC); c) OPC + 15% RHA-FA morphology; d) sand/paste ITZ in OPC + 15% RHA-FA;
e) OPC + 30% RHA-FA morphology; f) sand/paste ITZ in OPC + 30% RHA-FA (key: C-S-H: C-S-H gel; uf: unreacted fly ash; rf: reacted fly ash; FA: fly ash; CH: portlandite; AFt:
ettringite; S: sand).
74 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76

release than in the OPC reference until the peak value was reached, recorded this effect when cement was simultaneously additioned
after which the value declined gradually. with fly ash and FCC catalyst [63].
Table 6 gives the total heat released and the linear correlation As observed in Fig. 10(b), (d) and (f), partial replacement of OPC
between heat of hydration and the RHA-FA replacement ratio after with RHA-FA had no adverse effect on the formation of cement
48 h for the three mortars. The former declined as the replacement hydration products. The sand/paste interfacial transition zone
ratio rose. After 48 h, the mortar containing 15% RHA-FA released (ITZ) comprised primarily C-S-H gel, elongated hexagonal crys-
5.67% less heat than the OPC, while the material bearing 30% talline portlandite plates (CH) and needle-like crystalline ettringite
RHA-FA released 13.54% less. (AFt) [56]. The unreacted fly ash observed in the OPC + 15% RHA-FA
The decline recorded was consistent with the pattern observed and OPC + 30% RHA-FA mortars resulted from its slower pozzolanic
in prior analyses of the early age behaviour of low (fly ash and san- reactivity than recorded for rick husk, which was consumed com-
itary ware industry waste) and high (FCC catalyst and paper pletely in the first few hours.
sludge) reactivity mineral waste [57–60].
Table 6 also reveals an intense linear correlation (R2 > 0.95)
between the total heat of hydration and the RHA-FA replacement 4. Verification of existence of synergistic effect in OPC/RHA-FA
ratio, a relationship likewise observed by Medina et al. [58] in a systems
study of construction and demolition and (fired clay) sanitary ware
industry waste. The 28 d compressive strength values for the reference cement
(OPC), the binary blends (OPC/RHA and OPC/FA) and the ternary
systems (OPC/RHA-FA), as well as the theoretical value for OPC +
3.9. Microstructure 15RHA-FA and OPC + 30RHA-FA, are shown in Fig. 11. The theoret-
ical value was calculated from Eq. (1), proposed by Radlinski and
The micrographs of the 90 d mortars reproduced in Fig. 10 Olek [51] for OPC/FA-SF ternary systems:
reveal the presence of calcium silicate hydrates (C-S-H gel), which
formed a dense, compact, continuous, strong matrix, along with
PTheor: XRHA=XFA ¼ POPC þ YDPXRHA þ ZDPXFA
other hydration products and the voids left by reacted fly ash. ¼ POPC þ Y  ðPXRHA  POPC Þ þ Z  ðPXFA  POPC Þ ð1Þ
The calcium-silicon (C/S) ratio in the C-S-H gel in the reference
OPC was 2.07, in the OPC + 15% RHA-FA, 1.92 and in the OPC + where POPC, PXRHA and PXFA are the OPC and binary blend OPC/RHA
30% RHA-FA, 1.87. While slightly lower due to the presence of silica and OPC/FA compressive strength values; X is the replacement ratio
in the RHA-FA mixture in the C-S-H gel, the values in the addi- of the addition; Y = Z is the sum of the fraction of OPC (0.85 or 0.70)
tioned mortars lay within the usual 1.2–2.3 range found in C-S-H and the addition in the binary system (0.075 or 0.15, assuming val-
gel [56]. ues of 0.925 for the OPC + 15(RHA-FA) = 7.5RHA/7.5FA and of 0.85
The unreacted fly ash clearly visible in Fig. 10c and e was for the OPC + 30(RHA-FA) = 15RHA/15FA systems).
observed more frequently in the mortars with 30 wt% RHA-FA. The figure shows that the experimental values for the ternary
The matrix microstructure was similar in OPC and OPC + 15% systems were higher than the theoretical calculations, attesting
RHA-FA. In contrast, the mortar bearing 30 wt% of the addition to the synergistic effect observed in the saturated lime test dis-
exhibited a larger proportion of macropores because the poz- cussed earlier. Such synergies amounted to 17% for OPC + 15RHA-
zolanic reaction products occupied a smaller volume than the ini- FA and 6% for OPC + 30RHA-FA. The inference is that the synergistic
tial fly ash, leaving voids, as observed in earlier studies [44,61,62]. effect (SE) in the RHA-FA blend was greater when it was suitably
That finding was consistent with prior mercury intrusion batched. Under the conditions studied here, the optimal RHA-FA
porosimetry (MIP) results and reports by other authors who replacement was 15%. At higher percentages, the synergies were

Fig. 11. 28 d binary and ternary system compressive strength and theoretical values.
 C. Medina et al. / Construction and Building Materials 187 (2018) 65–76 75

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[28] European Standard. EN 196-1:2005, Methods of Testing Cement - Part 1:
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