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International Journal of Minerals, Metallurgy and Materials

Volume 16, Number 6, December 2009, Page 720 Materials

Preparation of fly ash and rice husk ash geopolymer

S. Detphan and P. Chindaprasirt


Department of Civil Engineering, Khon Kaen University, Khon Kaen 40002, Thailand
(Received 2008-12-07)

Abstract: The geopolymer of fly ash (FA) and rice husk ash (RHA) was prepared. The burning temperature of rice husk, the RHA
fineness and the ratio of FA to RHA were studied. The density and strength of the geopolymer mortars with RHA/FA mass ratios of
0/100, 20/80, 40/60, and 60/40 were tested. The geopolymers were activated with sodium hydroxide (NaOH), sodium silicate, and
heat. It is revealed that the optimum burning temperature of RHA for making FA-RHA geopolymer is 690ºC. The as-received FA
and the ground RHA with 1%-5% retained on No.325 sieve are suitable source materials for making geopolymer, and the obtained
compressive strengths are between 12.5-56.0 MPa and are dependent on the ratio of FA/RHA, the RHA fineness, and the ratio of so-
dium silicate to NaOH. Relatively high strength FA-RHA geopolymer mortars are obtained using a sodium silicate/NaOH mass ratio
of 4.0, delay time before subjecting the samples to heat for 1 h, and heat curing at 60ºC for 48 h.

Key words: geopolymer; fly ash; rice husk ash; sodium hydroxide; sodium silicate

[This work was financially supported by the National Science and Technology Development Agency (NSTDA) through the Reversed
Brain Drain Program (No.01-49-005), Thailand.]

1. Introduction small electricity generating plant and other applica-


tions. Although the increased use of rice husk is evi-
The manufacture of Portland cement is an energy dent, much of the husk is disposed of by open-field
intensive process and releases a large amount of green burning. Therefore, making cement from rice husk has
house gas of approximately 13500 million ton annu- attracted interest worldwide. Rice husk, when burnt, is
ally [1]. The effort, therefore, focuses on how to re- found to contain a very high percentage of silica,
place the Portland cement with other environmentally which is one of the main constituents in producing
friendly cementitious materials. Recently, the other geopolymer. With proper burning and grinding, the
form of cementitious material using silica and alumina amorphous reactive rice husk ash (RHA) could be
activated with high alkali solution and low heat has produced and used as pozzolan [6-7]. The SiO2 rich
been developed. This material is usually based on fly RHA can also be used to adjust the SiO2 content of the
ash (FA) as a source material and is termed geopoly- geopolymer. The use of high silica to alumina ratio
mer or alkali-activated FA cement [2-4]. In Thailand, results in geopolymers with higher elasticity [8]. In
around 3 million tons of annual output of FA from addition, the bulk density of RHA is lower than the
Mae Moh Lignite Coal Power Station is produced. cement and FA. The use of RHA should, therefore,
This FA contains high calcium content and is being result in the lighter weight cement and hence lighter
used quite extensively for construction. It can also be mortar and concrete, which is desirable.
used as a source material for making high strength
The study on FA-RHA geopolymer mortars focuses
geopolymer mortar [5].
on the preparation of RHA, the mix proportions, and
It is also well known that the Asian countries pro- the manufacturing methodology. The knowledge
duce a large amount of paddy. Rice husk, a by-product, would be instrumental and lay some foundations for
is used as a fuel in a boiler in the rice mill or in the the future research in this field.

Corresponding author: S. Detphan, E-mail: rc_statics@yahoo.com Also available online at www.sciencedirect.com


© 2009 University of Science and Technology Beijing. All rights reserved.
S. Detphan et al., Preparation of fly ash and rice husk ash geopolymer 721

2. Experimental procedure 5%, 3%, and 1% retained on No.325 sieve (5RHA,


3RHA, and 1RHA) with corresponding Blaine fine-
2.1. Materials nesses of 12000, 14000, and 18000 cm2/g. Chemical
Lignite FA from Mae Moh power station in the compositions of the FA and RHA are given in Table 1.
north of Thailand was used. The FA has a mean parti- The RHA contains 91.93wt% SiO2, and the specific
cle size of 65 μm, a Blaine fineness of 2800 cm2/g, a gravities were between 1.95-1.99. The specific gravity
specific gravity of 2.21, and a percentage retained on slightly increases with the increase in the temperature
No.325 sieve of 34%. RHA was obtained from of burning due to the collapse of the cellular structure
open-field burning in small heaps. The burning was of RHA [9]. The FA contains 16.55wt% of CaO and
carried out on a perforated steel plate that is lifted to a 74.76wt% of SiO2+Al2O3+Fe2O3, which are common
small distance above the ground. The maximum tem- for the lignite FA [10]. The physical properties and
peratures at the middle of the heaps of 580, 610, 690, LOI of RHA are shown in Table 2. The scanning elec-
710, and 940°C were recorded for the burning of 10, tron microscope (SEM) photos of the as-received FA
15, 20, 25, and 50 kg rice husk heaps. The obtained and the ground RHA indicate that the FA particles are
ashes were whitish gray and the losses on ignitions spherical and those of RHA are irregular with cellular
(LOI) were 1.94%-3.62%, indicating complete burn- porous surfaces as shown in Fig. 1.
ing. The ashes were then ground to three finenesses of
Table 1. Chemical compositions of FA and RHA wt%
Material SiO2 Al2O3 Fe2O3 CaO Na2O TiO2 MgO K2O P2O5 SO3
RHA 91.91 0. 12 0.29 0.69 0.20 0.01 0.08 1.98 0.54 0.78
FA 38.72 20.76 15.28 16.55 1.19 0.44 1.49 2.69 0.16 2.63

Table 2. Physical properties of RHA Commercial grade sodium hydroxide (NaOH) and
Rice husk / Max. burning Specific sodium silicate solutions with 15.32wt% Na2O,
LOI
kg temperature / ºC gravity 32.87wt% SiO2, and 51.81wt% water were used. The
10 580 3.62 1.95 distilled water was used for the whole experiment.
15 610 3.33 1.96 Sodium hydroxide was dissolved in distilled water
20 690 3.25 1.97 prior to the mixing of geopolymer. Local river sand
25 710 2.84 1.99 with a specific gravity of 2.64 and a fineness modulus
50 940 1.94 1.98 of 2.85 was used for making mortar.

Fig. 1. SEM photomicrographs of as-received fly ash (a) and ground RHA (b).

2.2. Preparation of mortar the mixing, flow of mortar was determined in accor-
The mixing was carried out in an air conditioned dance with ASTM C124 [11]. All geopolymer mortars
room at approximately 25°C. FA and RHA were were made with a sand to solid binder (FA+RHA)
thoroughly mixed for 2 min until a uniform color was mass ratio of 2.75. After the determination of flow, the
obtained. Sand was then added and mixed for 3 min. fresh mortar was placed in the 50 mm×50 mm×50 mm
The NaOH, sodium silicate, and extra water were then cube moulds. The specimens were compacted in
added and mixed for another 5 min. Extra water was two-layer with tamping as described in ASTM C109
needed to maintain the workable mortar. Right after [12]. Additional vibration of 10 s was applied using a
722 International Journal of Minerals, Metallurgy and Materials, Vol.16, No.6, Dec 2009

vibrating table. The specimens were wrapped with tested in accordance with ASTM C109. The reported
vinyl sheets to protect moisture loss and kept in the results were the average of three samples.
controlled room at 23±2°C. After a delay period, the 2.3. Series of tests
specimens were then placed in the oven for heat cur-
ing. After the heat curing, the specimens were put in The mortars were mixed using sufficient water to
the laboratory to cool down and demoulded the next produce the flow of 110±5%. The mix proportions for
day and kept in the controlled room. The bulk density making mortars are given in Table 3. In addition to the
and compressive strength of mortars were determined strength test, the mortars were tested for bulk densi-
at the age of 7 d. The compressive strengths were ties.

Table 3. Mix proportions of geopolymer mortars


Content / (kg·m3)
Sodium silicate/NaOH Specimen
FA RHA NaOH Sodium silicate Extra Water Sand
100FA-A 635 0 51 280 96 1747
Series A 80FA20RHA-A 507 128 51 280 128 1747
Sodium silicate/NaOH=5.5 60FA40RHA-A 381 253 51 280 189 1747
40FA60RHA-A 253 381 51 280 253 1747
100FA-B 635 0 70 280 96 1747
Series B 80FA20RHA-B 507 128 70 280 128 1747
Sodium silicate/NaOH=4.0 60FA40RHA-B 381 253 70 280 189 1747
40FA60RHA-B 253 381 70 280 253 1747
100FA-C 635 0 110 280 96 1747
Series C 80FA20RHA-C 507 128 110 280 128 1747
Sodium silicate/NaOH=2.5 60FA40RHA-C 381 253 110 280 189 1747
40FA60RHA-C 253 381 110 280 253 1747
100FA-D 635 0 149 280 96 1747
Series D 80FA20RHA-D 507 128 149 280 128 1747
Sodium silicate/NaOH=1.9 60FA40RHA-D 381 253 149 280 189 1747
40FA60RHA-D 253 381 149 280 253 1747

(1) Temperature of burning of the rice husk (b) Duration of heat curing. In this test, the periods
To test RHA burnt at different temperatures, the of heat curing were 6, 12, 18, 24, 48, 60, and 72 h.
specimens of 80FA20RHA-B and 80FA20RHA-C The specimens were placed in the oven at 75°C using
were used with no delay time and curing at 75°C for delay time of 1 h based on the result of delay time test.
48 h, and 3RHA was used in the specimens. (c) Temperature of heat curing. The curing tem-
(2) Effect of the sodium silicate to NaOH mass ra- peratures of 60, 75, and 90°C were assigned in this
tio and SiO2/Al2O3 molar ratio test. The specimens were placed in the oven using a
delay time of 1 h, and the duration of heat curing of 48
To test the effect of the sodium silicate to NaOH
h in the oven based on the result of the duration of
mass ratio, all the specimens shown in Table 3 were
heat curing test.
used with SiO2/Al2O3 molar ratios of 4.1, 6.1, 9.5, and
16.3, no delay time, and curing at 75°C for 48 h and (4) Fineness of RHA
3RHA was chosen for the specimens. In this test, the 3 different RHAs, namely, 1RHA,
(3) Effect of curing 3RHA, and 5RHA, were used in 80FA20RHA-B. The
specimens were placed in the oven with a delay time
The effects of delay time, temperature of heat cur- of 1 h and a duration of heat curing of 48 h at 60°C
ing and period of heat curing were investigated. Series based on the temperature of heat curing test.
B was used with 3RHA.
(a) Delay time before heat curing. Delay time is the 3. Results and discussion
time duration before placing the specimens in the oven.
3.1. Burning temperature of rice husk
In this test, the delay time of 1, 3, 6, 12, 24, 36, and 48
h were used. After the delay time, the specimens were The results of strength of mortars made from RHA
placed in the oven at 75°C for 48 h. burnt at different temperatures as shown in Fig. 2 in-
S. Detphan et al., Preparation of fly ash and rice husk ash geopolymer 723

dicate that the strength is dependent on the burning contained in the geopolymer pore system and de-
temperature of rice husk. The optimum temperature of creased the strength and performance of geopolymers
RHA burning at 690°C provided the highest strengths [14]. The results of Fig. 4 and Table 1 indicate that the
of 22.5 and 37.0 MPa for the sodium silicate/NaOH increase in the RHA content results in the increases in
mass ratios of 2.5 and 4.0, respectively. The burning the SiO2/Al2O3 molar ratios. The normal FA mortar
temperature of less than 700°C produces amorphous consisted of SiO2/Al2O3 molar ratio of 4.08. For the
silica, which is reactive [13]. Although low burning mortar containing RHA of 60wt%, the SiO2/Al2O3
temperature produced amorphous silica, at very low molar ratio increased to 16.32 with a slight decline in
temperature, the burning is incomplete. This results in the strength of mortars owing to the increased water
the undesirable high amount of the unburnt materials. requirement and the increase in the silica to alumina
As shown in Table 2, the LOI of RHA decreased from molar ratio [8].
3.6 to 1.9 as the temperature of burning increased. On
the other hand, the higher temperature of burning
produces a larger amount of crystalline silica, which is
less reactive [7, 13].

Fig. 3. Relationship between compressive strength and the


mass ratios of sodium silicate to NaOH (3RHA, no delay
time and curing at 75°C for 48 h).
Fig. 2. Relationship between compressive strength and
maximum burning temperature of rice husk (3RHA, no
delay time and curing at 75°C for 48 h).

3.2. Ratio of sodium silicate to NaOH


Fig. 3 shows that the strengths of mortar are greatly
affected by the ratios of sodium silicate to NaOH. The
optimum mass ratio is 4.0 for all mix series. The
strength increases significantly with the increase of
the mass ratios of sodium silicate to NaOH from 1.9 to
4.0. The increase in the ratio of sodium silicate to
NaOH in this range results in a higher concentration Fig. 4. Relationship between compressive strength and
of silicate in the solution and thus increases the molar ratio of SiO2 to Al2O3 (3RHA, no delay time and cur-
strength of the geopolymer. Further increasing the ing at 75°C for 48 h).
mass ratio of sodium silicate to NaOH from 4.0 to 5.5 3.4. Effect of curing
results in a very viscous mix. Extra water is needed to
produce a workable mortar and hence the strength of (a) Delay time before heat curing
the mortar is low in this range [5]. The results of delay time before heat curing are
3.3. Molar ratio of SiO2/Al2O3 shown in Fig. 5. The patterns of strength development
of geopolymer mortars with different dosage of RHA
The results as shown in Table 3 indicate that the
are similar. A delay time of 1-6 h slightly increases
water requirements of fresh geopolymer mortars in-
the compressive strength of the mortars. An increase
creased with the increase in the amount of RHA. The
in delay time beyond this results in a small reduction
water contents of mortars are 96, 128, 189, and 253 kg
in strength. The delay time adopted for FA geopoly-
corresponding with FA:RHA (mass ratios) of 100:0,
mer paste and mortar is generally between 1-24 h
80:20, 60:40, and 40:60, respectively. The RHA still
[15-16]. A period of delay time allows the dissolving
maintained its cellular structure, and the mix with
of silica and alumina, which are important for the
RHA thus required a larger amount of extra water to
alumino silicate geopolymerization.
produce mortars with the same flow. This adversely
affected the strength of the mortar as extra water was (b) Duration of heat curing
724 International Journal of Minerals, Metallurgy and Materials, Vol.16, No.6, Dec 2009

The relationship of the duration of heat curing and mortars. The strengths of mortars made with 5RHA,
strength is shown in Fig. 6. The strength increases 3RHA, and 1RHA were 34.5, 37.0, and 43.0 MPa, re-
with an increase in curing time from 6 to 48 h. Heat spectively. The increase in the fineness of RHA in-
curing beyond 48 h had little effect on the strength of creased its surface area and its reactivity and hence
the geopolymer. An increase in heat curing duration is resulted in an increase in strength of geopolymer
expected to improve the strength characteristics of the mortars. Increases in strength with the use of fine
geopolymer. Similar strength development with high RHA in the partial replacement of Portland cement
temperature curing has been reported [15, 17]. have also been reported [9-10]. RHA with 1%-5% re-
tained on No.325 sieve were suitable source materials
for making geopolymer. Although the very fine 1RHA
gave high strength geopolymer mortars, it required
intense grinding. For practical purpose, 3RHA was
recommended as it gave reasonably high strength geo-
polymer mortars.

Fig. 5. Relationship between compressive strength and


delay time (3RHA and curing at 75°C for 48 h).

Fig. 7. Relationship between compressive strength and


curing temperature (3RHA, delay time of 1 h, and curing
for 48 h).

3.6. Bulk density


The bulk density of mortars was lower with an in-
Fig. 6. Relationship between compressive strength and the crease in RHA content as the density of RHA was
duration of heat curing (3RHA, curing temperature of 75°C, lower than that of FA. The bulk densities of geopoly-
and delay time of 1 h). mer mortars with RHA contents of 0, 20wt%, 40wt%,
(c) Curing temperature and 60wt% of total solid binder were 2320, 2270,
2135, and 2080 kg/m3, respectively. Moreover, the in-
The relationship of curing temperature and strength crease in water content as a result of the increase in
is given in Fig. 7. The influence of curing temperature the water requirement of RHA also reduced the den-
is more significant in the mix containing a large sity of the mortar. The low density of high RHA con-
amount of FA. For example, the strengths of 100FA-B tent suggested that it was suitable for the development
and 80FA20RHA-B mixes with curing temperatures of light weight geopolymer mortars and concretes.
of 60, 75, and 90ºC vary from 39.0-56.0 and 35.0-43.0
3.7. Microstructures
MPa, whereas the strengths of 60FA40RHA-B and
40FA60RHA-B with curing temperatures of 60, 75, The images of SEM and energy dispersive spec-
and 90°C vary within narrower ranges of 28.0-32.5 troscopy analysis (EDX) of 100FA-B and
and 24.0-28.5 MPa, respectively. The optimum tem- 40FA60RHA-B geopolymer mortars are shown in Fig.
perature was 60°C for all series. The use of 75 and 8. The result as shown in Fig. 8(a) indicates the con-
90ºC results in some reduction in strength of the mor- tinuous mass of binder and some unreacted FA parti-
tar. At high curing temperature, the specimens espe- cles. The sample of the matrix with a SiO2/Al2O3 mo-
cially a small one with high surface to volume ratio lar ratio of 2.04 and a Na2O/Al2O3 molar ratio of 1.0
experience losses of moisture and this adversely af- was observed. The strength of this geopolymer mortar
fects the strength [5, 18]. was 41.5 MPa. The SiO2/Al2O3 molar ratio of 2.04
conformed with the previously reported SiO2/Al2O3
3.5. Effect of RHA fineness
molar ratio around 2.0 of FA geopolymer [19]. In
The results indicated that the increase in the fine- general, physical and mechanical properties of geo-
ness of RHA increased the strength of geopolymer polymers were a function of the SiO2/Al2O3 ratio [20].
S. Detphan et al., Preparation of fly ash and rice husk ash geopolymer 725

The result shown in Fig. 8(b) also indicates a con- tio of 3.68 and a Na2O/Al2O3 molar ratio of 2.22 was
tinuous mass of binder, unreacted FA, and a minor observed. The increase in RHA content increased the
phase of sodium silicate of the FA-RHA geopolymer. ratio of SiO2/Al2O3 and resulted in geopolymers with
The sample of the matrix with a SiO2/Al2O3 molar ra- a lower strength and a higher elasticity [8, 21].

Fig. 8. SEM-EDX photomicrographs analysis of 100FA-B (a) and 40FA60RHA-B (b) (3RHA, delay time of 1 h, curing at
60°C for 48 h).

4. Conclusion creased water requirement of the mixes. The lower


strengths are compensated with a reduced bulk density
Based on the obtained data, it can be concluded that of mortars with high silica content.
RHA can be used in conjunction with FA to produce
geopolymer. The workability and strength of geo- References
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