Cement & Concrete Composites 39 (2013) 131–140

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Cement & Concrete Composites

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The effects of a hydrochloric acid pre-treatment on the physicochemical

properties and pozzolanic performance of rice husk ash
A. Gholizadeh Vayghan a, A.R. Khaloo b, F. Rajabipour c,⇑
a
Faculty member and Director of the Concrete Technology and Construction Materials Laboratories, Alaodoleh Semnani Institute of Higher Education, Garmsar, Iran
b
Faculty of Civil Engineering, Sharif University of Technology, Azadi St., Tehran, Iran
c
Department of Civil & Environmental Engineering, The Pennsylvania State University, 223B Sackett Building, University Park, PA 16802, USA

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

Article history: This paper investigates the effects of acid normality (0.01–6 N HCl) and combustion retention time (0.25–
Received 28 April 2012 16 hours) on the pozzolanic properties of pre-combustion acid-treated rice husk ash. The pozzolanic reac-
Received in revised form 12 March 2013 tivity was quantified by adding ground ash to saturated Ca(OH)2 solutions and monitoring the time-
Accepted 24 March 2013
dependent electrical conductivity and pH of the solutions. Also, the strength activity of ashes from differ-
Available online 6 April 2013
ent processes was measured by testing the compressive strength of mortars. It was observed that acid
treatment results in ashes with higher SiO2 content, lower alkali and unburned carbon content, better
Keywords:
grindability, and smaller particle size, in comparison with ash from non-acid treated husks. Acid leaching
Rice husk ash
Retention time
increased the lime reactivity of the ashes and decreased their sensitivity to prolonged combustion times.
Acid leaching Further, acid treatment with 0.01 N HCl was found to be sufficient, as the use of stronger acids did not
Lime reactivity considerably improve the pozzolanic reactivity of rice husk ash.
Strength activity Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction ash (i.e., nearly 90% when burned under optimum conditions);
and due to a high percentage of ash that is produced from a unit
The growing needs for energy and natural resources, and the weight of rice husk [4]. In 2009, over 680 Mtons of rough rice
resulting environmental pollutions have raised serious concerns was produced in the world [5]. Since the rice husk (RH) accounts
in modern and developing countries. An example related to con- for 20–22% by weight of the harvested rough rice [6], over
struction industry is the annual production of Portland cement in 140 Mtons of RH is annually produced. The energy density of RH
the world that has reached 3400 Mtons (million tons) (approxi- is reported to be approximately 16,720 kJ/kg [7] and, therefore,
mately 485 kg per capita) in 2011 [1]. Of this value, a significant an annual potential energy of approximately 2.17  109 GJ and
portion is contributed by developing countries. For example, in 26 Mtons of potentially highly reactive pozzolan can be obtained
2011, China produced approximately 2000 Mtons of cement (i.e., from RH combustion. Research has shown that controlled combus-
1480 kg per capita), which accounts for 58.8% of the global pro- tion of RH can result in the formation of silica of amorphous struc-
duction [1]. Manufacturing of Portland cement is energy intensive ture, high purity, and very high lime reactivity [8]. However,
(embodied energy  5.3 MJ/kg), and results in a large CO2 footprint conventional heap burning and other industrial combustion meth-
(0.97 kg/kg) [2]. In parallel, large quantities of siliceous waste ods include a steep heating rate, an essentially uncontrolled ulti-
materials (e.g., coal fly ash, blast furnace slag, rice husk ash), are mate temperature and a prolonged retention time. These will
produced by various industries. Some of these waste materials result in the formation of ash of high unburned carbon content,
can be used effectively as partial replacement of Portland cement partially crystallized silica, and as such, low pozzolanic perfor-
to reduce the environmental impact and the life-cycle cost of con- mance. There is a need for development of successful methods to
crete structures [3]. In addition, the proper use of such supplemen- produce rice husk ash of superior performance at industrial scale.
tary cementitious materials (SCMs) has been proven to enhance One of the newer methods to obtain rice husk ash of high silica
the durability and mechanical properties of concrete [3]. purity and improved pozzolanic properties is acid leaching pre-
Among agricultural wastes, the best performance as an SCM has treatment [9,10]. The method was first proposed by Chakraverty
been reported for rice husk ash due to a high silica content in the et al. [11]. This process can essentially remove metallic impurities
such as Al2O3, Fe2O3, CaO, MgO and, more importantly, deleterious
alkalis like K2O [7,12,13]. In the case of non-acid leached rice husk,
⇑ Corresponding author. Tel.: +1 814 863 0601.
the existing K2O decomposes during the combustion at 620 K, leav-
E-mail addresses: [email protected] (A. Gholizadeh Vayghan),
ing elemental potassium (whose melting point is 343 K) on the
[email protected] (A.R. Khaloo), [email protected] (F. Rajabipour).

0958-9465/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconcomp.2013.03.022
132 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140

structure of the burning ash. Potassium element causes surface investigated. This is important for minimizing the energy con-
melting and acts as a crystallization catalyst for silica [13]. When sumption of the process, and to determine the sensitivity of the
rice husk is heated, the carbonization occurs through decomposi- rice husk ash (both NTR and ALR) to variability in the burning con-
tion of the organic matter, such as cellulose and lignin to carbon. ditions. The pozzolanic performance of the resulting husk ashes is
Further increase in the temperature results in oxidation of the car- characterized through measurement of the ash reactivity with a
bon into CO2, if reasonable oxygen supply is provided [6]. However, saturated Ca(OH)2 solution, as well as measuring the strength
the increase in the temperature over the dissociation point of K2O, improvements in mortars containing partial cement replacement
is followed by surface melting of the ash which blocks the path- with rice husk ash.
ways for transport of oxygen and carbon dioxide. This will result
in the entrapment of non-oxidized (i.e., unburned) carbon. More- 2. Materials and experimental methods
over, the surface melting can result in a decrease in the pozzolanic
lime reactivity of the ash due to increased crystallization affinity of 2.1. Materials
silica [13]. When an acid leaching pre-treatment is applied, K2O as
the major silica crystallization catalyst is removed from the rice The rice husks were provided from a northern state of Iran. In
husk, and no surface melting occurs in the silicate structure. There- the case of acid leached rice husk ash (ALR), each time 6 kg of
fore, the carbonized matter in the burning ash is not prevented the husks were boiled in 60 liters of 0.01 N HCl acid solution for
from volatilizing, which leads to less unburned carbon content in 1 h inside a150-liter stainless steel cylindrical tank. This is consis-
the ash. In addition, the volatiles can escape at lower ultimate tem- tent with past research which suggested boiling the husks for 1–
peratures compared to non-acid leached husks [13]. 2 h in the acid solution and, using a husk to solution ratio of 50–
Previous research also indicates that the strength activity of 100 g/l [10,12,15]. Next, the husks were washed completely with
acid leached rice husk ash (ALR) is superior to non-acid treated rice tap water until neutral pH was detected, and then dried in the lab-
husk ash (NTR). Feng et al. [12] reported 17% and 33% improve- oratory air for 3 days. Both types of the husks (ALR and NTR) were
ments in the 28-day flexural and compressive strengths of mortars burned in a static air muffle furnace under well controlled condi-
incorporating 10 wt.% replacement of Portland cement with NTR. tions in small quantities to ensure the accuracy of the applied
Samples with 10 wt.% of ALR showed 21% and 43% improvements pyro-processing. Each time, 100 g of the husks were evenly placed
in the 28-day flexural and compressive strengths, respectively. in a rectangular stainless steel tray (20 cm  28 cm  2 cm), and
The husks were treated in 1 N HCl acid and combusted at 700 °C the pyro-processing was carefully applied as follows. For all sam-
for 4 h. Salas et al. [14] used a similar acid treatment, but altered ples, the rate of heating was 10 °C/min and the ultimate tempera-
the combustion temperature to be at 600 °C for 3 h. For concrete ture was 700 °C. In order to investigate the effect of retention time,
with 10 wt.% replacement of cement with NTR or ALR, the 28-day the ashes were maintained at the ultimate temperature for 15 min,
compressive strength improved by 5% and 11%, respectively [14]. 1, 4, 8, and 16 h. Once the retention time had elapsed, the husks
The majority of the past research has focused on treatment of were removed from the furnace and allowed to cool down to the
rice husk using inorganic acids (e.g., HCl, HNO3 and H2SO4) and room temperature in 5 min. The husks were then ground in a
at relatively high concentrations (1 N up to 18 N) [10–14]. The high 5-literporcelain ball mill for 20 min. The type of mill and the grind-
volume and acidity of the chemical wastes produced during the ing time were similar to previous studies [6,12,16–18]. The typical
treatment and neutralization of the leached husks raise the need time–temperature variation pattern of the applied pyro-processing
to investigate whether treatments using lower acid normality is shown in Fig. 1. The rationale behind the rapid cooling of the
can be also effective in improving the pozzolanic performance of ashes was to promote the formation of amorphous silicate com-
rice husk ash. This is one of the main objectives of the present pa- pounds as opposed to crystalline silicates which are known to be
per, which uses a much weaker 0.01 N HCl acid. In addition, the ef- non-reactive. The ashes were named according to their type and
fect of combustion retention time (0.25, 1, 4, 8, or 16 h retention at retention time. ALR-2 h, for instance, marks the acid leached rice
700 °C) on the properties of the non-treated and acid leached ash is husk ash maintained for 2 h at the ultimate temperature

Fig. 1. Typical time–temperature variations of rice husk combustion.

 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140 133

Table 1
Chemical compositiona and physical properties of materials.

Characteristics Materialsd
Cement NTR-1/4h ALR-1/4h NTR-1h ALR-1h NTR-4h ALR-4h NTR-8h ALR-8h NTR-16h ALR-16 h
SiO2 (%) 21.24 87.14 97.59 94.41 97.89 94.91 97.94 95.22 98.33 95.1 98.51
Al2O3 (%) 4.92 0.04 0.03 0.03 0.02 0.05 0.02 0.09 0.02 0.05 0.04
Fe2O3 (%) 4.01 0.23 0.11 0.25 0.16 0.25 0.14 0.19 0.26 0.11 0.09
CaO (%) 64.08 1.21 0.22 1.01 0.27 0.98 0.26 1.16 0.32 1.17 0.21
MgO (%) 1.68 0.3 0.13 0.37 0.09 0.44 0.11 0.39 0.04 0.41 0.07
Cl (%) – 0.09 0.02 0.09 0.02 0.06 0.02 0.07 0.05 0.09 0.03
SO3 (%) 2.42 – – – – – – – – – –
K2O (%) 0.64 1.6 0.17 1.69 0.18 1.61 0.2 1.73 0.14 1.66 0.19
Na2O (%) 0.34 0.06 0.02 0.07 0.03 0.07 0.05 0.06 0.03 0.05 0.03
Equiv. Na2O (%) 0.761 1.113 0.132 1.182 0.148 1.129 0.182 1.198 0.122 1.142 0.155
P2O5 (%) – 0.31 0.08 0.36 0.13 0.35 0.1 0.29 0.05 0.44 0.06
Loss on dryingb (%) 1.87 5.64 3.83 4.01 2.66 1.53 2.86 1.12 2.55 1.01 2.57
Loss on ignition (%)-after dryingc 0.67 9.02 1.63 1.72 1.23 1.28 1.13 0.8 0.76 0.92 0.77
Specific surface, Blaine (m2/kg) 295 – – – – – – – – – –
BET surface area (m2/g) – – – 57.1 284.3 – – – – – –
a
Conducted by X-ray fluorescence (normalized values).
b
The amount of evaporable water absorbed by each ash after 1 week exposure to ambient air (25 ± 2 °C, 50 ± 5%RH, laboratory condition).
c
The LOI of the ashes was measured according to static method as described by Yalcin and Sevin [15].
d
ALR and NTR respectively stand for ‘‘acid leached rice husk ash (at 0.01 N HCl)’’ and ‘‘non-treated rice husk ash’’.

(700 °C), and NTR-1/4 hcorresponds to the non-treated rice husk zolan powder. Also, the long-term (i.e. within the first hour) drop
ash with a 15-min retention time at 700 °C. Table 1 shows the in the EC and pH of the solution represents the lime reactivity of
chemical composition and physical properties of the ashes. In addi- the ash.
tion, a series of ALR ashes were similarly produced by leaching rice In this work, for all rice husk ashes, the time dependent varia-
husk in HCl solutions of different concentrations: 0.1 N, 1 N, 3 N tions of the electrical conductivity of saturated lime-pozzolan solu-
and 6 N. This was to investigate the effect of acid concentration tions were recorded at 40 °C, as proposed by Luxan et al. [21], using
on the lime reactivity of the resulting rice husk ash. The retention a portable conductivity meter Model Hach, sensION5. Additionally,
time adopted for this part of the investigation was 1 h. The ashes the pH variations were measured simultaneously by a portable pH
were named based on the acid normality used for their pre- meter Model Hach, sensION1. Analytical grade CaO was used for
treatment. ALR-1N,for example, refers to the ash leached in 1 N this investigation. The powdered CaO was used to produce satu-
acid. rated lime solution (Ca(OH)2). According to laboratory measure-
Type II Portland cement conforming to the specifications of ments, the solubility of CaO in distilled water at 40 °C is
ASTM C 150 was used for this study. The physical and chemical approximately 0.124 g/100 ml. The electrical conductivity and pH
characteristics of the cement are shown in Table 1. Washed manu- of saturated lime solution at 40 °C were found to be 7.15 mS/cm
factured sand conforming to ASTM C 33 specifications, with a fine- and 11.95, respectively. In this work, the exact amount of CaO to
ness modulus of 2.77, and a sand equivalency larger than 97% produce saturated solution without residual Ca(OH)2 was added.
(measured per ASTM D 2419) was used as mortar aggregates. It should be noted that if CaO is added more than needed for satu-
The superplasticizer (SP) used for this study was a polycarboxyl- ration, the extra Ca(OH)2 will precipitate as a solid phase and acts
ate-based admixture with an allowable dosage of 2 wt.% of cement. as a pH buffer in the solution. This condition should be avoided in
this test.
For all ashes, 5.000 g of the ash was uniformly added to 200 ml
2.2. Experimental methods
stirring saturated lime solution in 10 sec and the EC and pH
changes were recorded starting 30 sec after NTR/ALR addition.
2.2.1. Electrical conductivity and pH measurements of lime-pozzolan
The variations were recorded each 10 sec up to 3 min, and after
solutions
that, at 1–5 min intervals (depending on the reactivity of the ash)
When a pozzolanic powder is added to a saturated Ca(OH)2
up to 1 h. The tests were performed inside 500 ml beakers covered
aqueous solution, the amorphous silicate structure dissolves in
with paraffin papers in which three holes were punctured for
the solution, at a rate that is dependent on the pH [19]. These dis-
insertion of the sensors and a thermocouple. The temperature of
solved silicate phases react with the available Ca2+ and OH ions,
the solution was maintained at 40 ± 1 °C before addition of the
and precipitate in the form of calcium–silicate–hydrate (C–S–H)
ash and during the test, by placing beakers inside a water bath
[20]. If no solid Ca(OH)2 is available to replenish the consumed
equipped with a PID controller.
Ca2+, the pH and electrical conductivity (EC) of the solution will
drop, proportionally with the formation rate of C–S–H. As such,
these measurements can provide useful information for monitor- 2.2.2. Mixture proportions for mortars
ing the reaction rates of pozzolanic materials such as rice husk Mortar mixtures were prepared to evaluate the strength activity
ash. The faster the drop in the EC and pH of the solution, the higher of rice husk ashes. A control mortar mixture with a water to ce-
is the lime reactivity of the ash. It should also be noted that due to ment mass ratio of 0.45 and a fine aggregate to cement mass ratio
the presence of electrostatic forces and the high tendency of ions to of 2.0 were made as reference. For each of the ten different ashes
be physically adsorbed on surfaces prior to chemical reactions, a (i.e. both NTR and ALR with 1/4h, 1h, 4h, 8h, and 16h retention
sharp drop in the EC of solutions is often observed soon after the times), three mixtures were produced by replacing 5%, 10%, and
pozzolan powder is added to the lime solution. The magnitude of 15% (mass based) of cement with each of these ashes. In total, 31
the short-term drop (i.e. within the first 2 min; as suggested by mortar mixtures were produced to investigate the effects of acid
Luxan et al. [21]) is proportional with the surface area of the poz- leaching and retention time on the pozzolanic performance of rice
134 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140

Table 2 trons to generate characteristic Cu Ka X-rays which, after passing

Details of mortars mixture proportioning. through a beryllium monochromator filter, were radiated towards
Mixture labels Materials proportions (kg/m3) the sample at incident angles (h) ranging from 2.5° to 40° (2h = 5–
Water PC NTR ALR Agg. SP 80°).
RT-C 290 644 – – 1290 –
RT-5-NTR 290 611.8 32.2 – 1290 As appropriate 3. Results and discussion
RT-10-NTR 290 579.6 64.4 – 1290 As appropriate
RT-15-NTR 290 547.4 96.6 – 1290 As appropriate
3.1. Chemical composition and physical properties of the ashes
RT-5-ALR 290 611.8 – 32.2 1290 As appropriate
RT-10-ALR 290 579.6 – 64.4 1290 As appropriate
RT-15-ALR 290 547.4 – 96.6 1290 As appropriate The physical and chemical characteristics of NTR and ALR ashes
are presented in Table 1. It is observed that the acid leaching leads
Keys: PC = Portland cement; Agg. = aggregates; SP = superplasticizer; and RT-x = all
mortar mixtures in which the cement replacement percent is x%.
to higher SiO2 contents in the yield ashes. It also decreases the

husk ash. For all mixtures, the water to binder mass ratio (w/b) and
aggregate to binder mass ratio (Agg/b) were maintained as 0.45
and 2.0. The flow of each mortar was kept within ± 3 mm of the
flow of the control mortar (184 mm or 84%; measured per ASTM
C 1437) by adding proper amounts of superplasticizer (SP). This
was to ensure that all mortar cubes can be similarly consolidated
to the same degree and to prevent variation in compressive
strength due to differences in consolidation. This is in accordance
with the requirements of ASTM C 311 for measuring the pozzolanic
activity. Table 2 shows other details of the mixture proportions.
The label of each mixture starts with RT which stands for ‘retention
time’ followed by a number indicating the cement replacement
percent by the ash (i.e., 5%, 10%, or 15%). This is followed by the la-
bel of the ash used in the mortar (e.g. ALR-2h) as SCM. For example,
RT-5-ALR-1/4h corresponds to a mortar in which 5% of cement is
replaced with ALR-1/4. Also, RT-C indicates the control mortar
mixture (100% PC).
Mixing was performed in a 3-liter Hobart mixer as follows. First,
the cementitious materials were dry-mixed for 3 min in a separate
bowl, and added to the water–superplasticizer solution weighed in
the mixing bowl. The mixing was started at slow speed and contin-
ued for 1 min. Then, the mixer was stopped and the materials col-
lected to the side or bottom of the bowl were scraped down into
the batch. The paste was then mixed for another 1 min at the same
speed. Next, the aggregates were slowly added over a 20 sec period
and the mixing was continued for an additional minute. After an-
other scraping, the mortar was mixed for a final 2 min at medium
speed. Once the mixing procedure was complete, the flow of the
mortar was measured per ASTM C 1437 and, if the mortar did
not reach the target flow, a new batch was prepared with a modi-
fied SP dosage. For each mixture, three cubic specimens
(50  50  50 mm3) were cast in accordance with the specifica-
tions of ASTM C 109/C 109M. All specimens were kept covered
with wet burlaps and plastic sheets for 24 h and then removed
from the molds. The cubes were cured in a saturated lime water
bath for additional 27 days at 23 ± 2 °C. The cubes were tested
according to ASTM C 109 using a loading rate of 0.9 KN/Sec.

2.2.3. X-ray fluorescence (XRF) and X-ray diffraction (XRD) analyses

The XRF analyses were performed for cement and all ashes
using a spectrometer model ARL 8410. Powder samples were
analyzed for major elements using fused glass disks following
methods similar to those of Norrish and Hutton [22]. XRF measure-
ments were performed in a helium (He) atmosphere using a 40 kV,
5 mA X-ray source.
Using a diffractometer model Philips PW 3710, the XRD analy-
ses were performed on 3 g of ALR-4h, ALR-8h, ALR-16h, and ALR-
32h and all of the parallel non-treated ashes (i.e. NTR-4h, NTR-
8h, NTR-16h, and NTR-32h).The powder was mounted in a sample
holder, which was then placed in a goniometer. Using a 40 kV,
30 mA power supply, a copper filament was bombarded by elec- Fig. 2. SEM micrographs of the ashes before grinding: (a) NTR-1 h; (b) ALR-1 h.
 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140 135

amount of alkali contaminants such as K2O and Na2O. The presence crystallization during vigorous and prolonged combustions, which
of these alkalis reduces the melting temperature of silicates in the are typical to traditional and heap combustions. Due to their lower
ash, and also serves as an accelerator for crystallization of SiO2 dur- K2O content, and consequently higher melting temperature of SiO2,
ing combustion. In addition, the presence of alkalis may increase surface melting of the silicate skeleton is substantially reduced for
the alkali-aggregate reaction potential of the mixtures incorporat- the acid leached ashes. As such, the resulting ash preserves its por-
ing the ashes. Although past research [23] suggested that rice husk ous microstructure even for prolonged retention times. This is ob-
ash can be used to mitigate alkali-silica reaction, caution should be served in Fig. 2a and b which respectively show the SEM
exercised when using rice husk ash with high alkali content along micrographs of NTR-1h and ALR-1h ashes after combustion but be-
with aggregates containing reactive siliceous minerals. fore grinding. It is qualitatively observed that while the surface of
The substantial decrease in the K2O content observed in Table 1 the NTR ash has melted, the porous microstructure of the ALR ash
for acid leached ashes is expected to make SiO2 much less prone to is better maintained. Consequently, it is expected that under a
same grinding energy, the acid leached (ALR) ashes are ground to
finer particles with higher surface area compared to NTR ashes.
Fig. 3a and b show the SEM micrographs of NTR-1h and ALR-1h
ashes after a similar 20-min grinding in the ball mill as described
in the materials section. It can be observed that the ALR ash was
ground to a smaller particle size.
Using these micrographs, the particle size distribution of the
NTR-1h and ALR-1h ashes was quantified using digital image anal-
ysis. A thresholding technique was used to create binary images,
and particles having dimensions less than 1 lm were considered
to be noise, and omitted from the analysis. The pixel size in both
images was 0.15 lm. Fig. 4a and b show the histograms of the par-
ticle size distribution of the ground NTR-1h and ALR-1h ashes,
respectively. The histograms include both the diameter and the
maximum dimension of the particles. The diameter of the particles
is calculated by dividing four times the surface area to the perim-
eter. It is observed thatALR-1his ground to a finer particle size, hav-
ing an average particle diameter of 1.14 lm, compared to that of
NTR-1h having an average particle diameter equal to 2.37 lm.
Moreover,ALR-1hparticles show less variability in the particle size

Fig. 3. SEM micrographs of the ashes after 20 min grinding: (a) NTR-1 h; (b) ALR-
1 h. Fig. 4. Particle size distribution histograms of the ashes: (a) NTR-1 h; (b) ALR-1 h.
136 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140

compared to NTR-1h; the standard deviation of particle diameter non-acid leached ashes. Therefore, ALRs should have higher loss
for ALR-1h and NTR-1h are measured as 0.43 lm and 1.13 lm, on drying (LOD) compared to NTRs, which is observed for retention
respectively. The resulting coefficient of variation is 37.7% for times higher than 4 h. However, an inverse pattern is found in the
ALR-1h and 47.7% for NTR-1h.Interestingly, the average roundness case of ashes with low retention time. This is probably due to the
factor of the particles of ALR and NTR are almost the same, and high carbon content in NTRs of short retention time, whose specific
equal to 62.1% and 63.8%, respectively. The image analysis data surface area is reported to be about 1000 m2/g [24] and is highly
show the same trend observed by nitrogen BET measurements of moisture absorbent.
ALR-1h and NTR-1h ashes (Table 1). The BET specific surface area
and the total pore volume ofALR-1hwere found to be 284.3 m2/g 3.2. Electrical conductivity and pH measurement results
and 0.333 cm3/g, respectively. The corresponding values for NTR-
1h were 57.1 m2/g and 0.158 cm3/g. This shows not only an in- Fig. 5a and b show the electrical conductivity (EC) variations of
crease in the surface area of the ground ash, but also an increase the saturated lime-NTR and the saturated lime-ALR solutions,
in its nano-porosity; resulting in the ash’s brittleness and better respectively. The magnitude of decrease in EC during the test is
grindability. This further supports the hypothesis that removal of an indicator of the pozzolanic reactivity of the ashes. For all reten-
K2O by acid leaching reduces surface melting and preserves the tion times, it is observed that the drop in the EC of the ALR solu-
pore structure and grindability of rice husk ash. tions is much greater than that of NTR solutions; which signifies
The accelerated surface melting due to the presence of K2O in the higher adsorption potential and reactivity of the acid leached
NTR, leads to the entrapment of the carbonized organic matter ashes. This is likely due to a higher surface area (lower particle size
and prevents it from oxidizing. Hence, at any given retention time, and higher nano-porosity) of ALR ashes. However, the silica struc-
the non-acid treated ashes contain higher amount of unburned car- ture of ALRs may also be more disordered (i.e., amorphous) and as
bon content compared to acid leached ashes (LOI of NTR and ALR such, more reactive. This is discussed further in the XRD section.
ashes are reported in Table 1); and this could have negative conse- Considering that the long-term drop in the EC of the solutions rep-
quences on air entraining of concrete mixtures. Due to the higher resents the pozzolanic lime reactivity of each ash, Fig. 5a shows
porosity of the acid leached ashes, it is expected that the natural that an increase in the retention time of NTR ashes (from 15 min
moisture content of these ashes would be higher than that of to 16 h) results in a decrease in the lime reactivity of these ashes.

Fig. 5. The time-dependent electrical conductivity (EC) of saturated lime solutions: Fig. 6. The time-dependent pH variations of saturated lime solutions: (a) NTR-
(a) NTR-added solutions; (b) ALR-added solutions. added solutions; (b) ALR-added solutions.
 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140 137

Table 3
Short-term and long-term variations of the electrical conductivity EC and [OH ] of the NTR/ALR added solutions.
3
Ash Retention [OH ] variations (10 mole/l) EC variations (mS/cm) Correlation coefficientb
type time (h)
Short Reduction Long Reduction Short Reduction Long Reduction Between a Between b
term rate (a)a term rate (b)a term rate (c)a term rate (d)a and c and d
NTR 1/4 1.668 0 3.392 0 1.83 0 3.37 0 0.997 0.983
1 1.584 5.0 3.158 6.9 1.70 7.3 2.79 17.2
4 1.060 36.4 2.699 20.4 1.36 25.8 2.38 29.4
8 0.652 60.9 2.152 36.6 1.09 40.5 1.78 47.2
16 0.460 72.4 1.800 46.9 0.98 46.5 1.57 53.4
ALR 1/4 4.015 0 8.789 0 4.5 0 6.69 0 0.540 0.971
1 4.931 22.8 8.738 0.6 4.11 8.7 6.67 0.4
4 3.664 8.7 8.678 1.3 3.99 11.3 6.65 0.6
8 4.235 5.5 8.643 1.7 3.82 15.1 6.61 1.3
16 3.158 21.3 8.589 2.3 3.4 24.4 6.57 1.7
a
Expressed in % reduction of [OH ] or EC compared to that of the same type of ash with 1/4 h retention time.
b
Pearson’s linear correlation coefficient.

This may be due to an increased surface melting and reduction in of the lime-NTR and lime-ALR solutions are shown in Fig. 6a and b,
the surface area of the resulting ash, with prolonged retention respectively. It is observed that the pozzolanic lime reactivity of
times. However, given that surface area of NTR ashes other than- ALR is much higher than that of NTR, based on its pH drop. Gener-
NTR-1hwas no measured, this hypothesis cannot be evaluated in ally, a good agreement was found between EC and pH drop results.
the present study. In Fig. 5b, no considerable reduction occurs in The advantages and disadvantages of EC and pH methods were dis-
the lime reactivity of the acid leached ashes as the retention time cussed in a previous work [25].
is increased; although, lower retention time ashes seem to ap- Short term (i.e., 0–2 min) and long term (i.e., 0–60 min) drop in
proach equilibrium quicker (i.e., faster kinetics). The pH variations the electrical conductivity (EC) of solutions containing ALR or NTR

Fig. 7. EC/[OH ] variations versus the retention time: (a) short-term variations; (b) long-term variations.
138 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140

retention time decreases the short-term drop in the EC and pH of

the solutions for both ALR and NTR ashes (Fig. 7a). Based on the
conductivity (EC) results, it is seen that as the retention time in-
creases from 15 min to 16 h, the adsorption potential (i.e., short-
term drop in EC) and pozzolanic reactivity (i.e., long-term drop in
EC) of NTR are decreased by 46.5% and 53.4%, while there are
24.4% and 1.7% decrease in those values for the acid leached ashes.
This is an indicator of the reduction in the sensitivity of acid lea-
ched ashes to the prolongation of retention time compared to
non-acid leached ashes. More support can be found in the corre-
sponding reduction rates of [OH ] (i.e. 72.4% and 46.9% for NTR
and 21.3% and 2.3% for ALR). In most cases, a good correlation
was found between EC and [OH ] reduction rate results (see corre-
lation coefficients in Table 3).
These observations suggest that acid leached ashes are consid-
erably less susceptible to loss of pozzolanic properties caused by a
prolonged combustion. This finding has practical application in
that acid leaching is a suitable pre-treatment method for the tradi-
tional and heap combustion methods of rice husk where there is
little control on the retention time and ultimate temperature. This
adds to the findings of Feng et al. [12] who reported that acid
leaching reduces the sensitivity of rice husk ash to the ultimate
temperature of its combustion.
To study the effect of acid normality on the pozzolanic reactiv-
ity of acid leached rice husk ash, a similar series of experiments
were performed where the short-term (0–2 min) and the long term
(0–60 min) decreases in the EC and pH of saturated Ca(OH)2 solu-
tions were monitored after addition of 5.000 g of rice husk ash to
200 ml of solution. Fig. 8a and b show the results for the pH drop
and the EC drop of the saturated lime solutions. For comparison,
data for the non-acid treated ash (NTR) is also included. It is ob-
Fig. 8. Short-term and long-term changes in the properties of saturated lime
solutions versus acid normality: (a) Electrical conductivity; (b) pH. served that acid leaching of rice husk with a dilute 0.01 N HCl acid
dramatically increases the reactivity of the resulting husk ash.
Higher concentrations of acid did not significantly improve the
ashes were calculated based in Fig. 5a and b, and the values are re- pozzolanic reactivity of ALR ashes beyond what could be achieved
ported in Table 3. For example, the solution containing NTR-1/ by 0.01 N HCl acid leaching.
4hash lost 1.83 mS/cm of its initial electrical conductivity within
the first 2 min of the test and lost 3.37 mS/cm conductivity in the 3.3. XRD results
span of 0–60 min. Similar calculations were performed based on
the [OH ] concentration of the solutions (using pH measurements Fig. 9 shows the XRD patterns of the ashes. Interestingly, no ma-
of Fig. 6a and b) and the results are presented in Table 3. The jor crystalline phases are detected in both types of ashes (NTR and
changes in the EC and pH of the solutions are also graphically pre- ALR) even after 32 h of combustion retention time. This suggests
sented in Fig. 7a and b. A smaller DEC or D[OH ] indicates a weak- that the presence of higher K2O content, observed in the case of
er pozzolanic reactivity. It is observed that an increase in the NTR does not necessarily result in formation of crystalline silica

Fig. 9. X-ray diffraction patterns of the ashes.

 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140 139

Table 4
Superplasticizer demand, compressive strength and SDR results for mortar mixtures.

Retention time (h) Mixture labels Superplasticizer (l/m3) Densitya (g/cm3) 28-day Compressive strength (MPa) Strength to density ratio (m)
– RT-C – 2.26 45.81 2027
1/4 RT-5-NTR 1.921 2.25 50.88 2261
RT-10-NTR 4.153 2.20 54.41 2473
RT-15-NTR 6.570 2.19 58.27 2661
RT-5-ALR 3.905 2.23 41.42 1857
RT-10-ALR 5.702 2.21 57.51 2602
RT-15-ALR 6.880 2.19 53.26 2432
1 RT-5-NTR 1.921 2.23 51.40 2305
RT-10-NTR 4.153 2.22 55.17 2485
RT-15-NTR 6.322 2.20 59.31 2696
RT-5-ALR 3.892 2.23 43.1 1933
RT-10-ALR 5.667 2.22 59.68 2689
RT-15-ALR 6.801 2.19 54.55 2491
4 RT-5-NTR 1.983 2.25 56.25 2500
RT-10-NTR 4.153 2.23 62.21 2790
RT-15-NTR 6.446 2.22 65.53 2952
RT-5-ALR 3.879 2.25 43.69 1942
RT-10-ALR 5.631 2.22 60.62 2731
RT-15-ALR 6.667 2.19 55.32 2526
8 RT-5-NTR 2.107 2.25 49.88 2217
RT-10-NTR 4.339 2.23 52.80 2368
RT-15-NTR 6.508 2.20 56.91 2587
RT-5-ALR 3.866 2.23 45.87 2057
RT-10-ALR 5.633 2.22 65.52 2951
RT-15-ALR 6.661 2.18 58.72 2693
16 RT-5-NTR 2.169 2.25 46.82 2081
RT-10-NTR 4.339 2.21 48.65 2201
RT-15-NTR 6.508 2.20 55.42 2519
RT-5-ALR 3.862 2.23 51.82 2324
RT-10-ALR 5.641 2.21 68.87 3116
RT-15-ALR 6.722 2.18 61.51 2822
a
The apparent density of the mortars was measured by dividing the SSD weight to the geometric volume of the specimens, immediately after removing the cured
specimens from the water bath.

in the ash, if the ash is rapidly cooled from its maximum combus- that the SP demand of the mortars incorporating ALR is higher than
tion temperature. It would be interesting to study how the cooling that of the NTR blended mortars, which is probably attributed to
rate affect the formation and concentration of crystalline phases in the higher fineness and specific surface area of ALR compared to
the NTR and ALR ashes. NTR. The 28-day compressive strength results of the mortars are
also presented in Fig. 10. The error bars represent ±1 standard devi-
3.4. Strength activity of mortars ation. The following observations can be made:

Table 4 shows the superplasticizer (SP) demand, apparent den- 1. For all mortars containing NTR ashes, strength increases consis-
sity, 28-day compressive strength, and the strength to density ratio tently with the NTR dosage from 0% to 15%. For the ALR mortars,
(SDR) of the NTR and ALR blended mortar mixtures. It is observed 10% is the optimum replacement level of cement with rice husk

Fig. 10. 28-Day compressive strength results of mortars.

140 A. Gholizadeh Vayghan et al. / Cement & Concrete Composites 39 (2013) 131–140

ash. While mortars containing 10% and 15% ALR always show Acknowledgements
better strength than the control (100%PC) mortar, those con-
taining 5% ALR generally show similar or lower strength than The first author is deeply appreciative of the endless and inde-
the control mortar. scribable supports and encouragements of his mother throughout
2. By comparing mortars containing 10% or 15% cement replace- the work, and wishes the best for all mothers all around the globe.
ment, it is observed that both NTR and ALR ashes show practi- Supports from the concrete technology laboratory and the Center
cally similar strength activity in mortars for retention times up of Excellence in Structures and Earthquake Engineering (CESEE)
to 4 h. Longer retention times resulted in better compressive of Sharif University of Technology are greatly appreciated. This re-
strengths in ALR mortars in comparison with NTR mortars. search was partly conducted in the concrete and construction
3. In comparison with the control mortar, the highest strength materials laboratory of Alaodoleh Semnani Institute of Higher Edu-
improvement was found in the case of 10% cement replacement cation (ASIHE). The authors are thankful to Dr. Alireza Akhavan for
withALR-16hash, where 50% increase in the compressive his help with image analysis.
strength, relative to the control mortar, was observed. The sec-
ond highest increase in strength was found in the case of 15% References
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