METHODOLOGY

FLY ASH BASED GEOPOLYMER CONCRETE

Fly ash rich in silica and alumina constituents shows pozzolanic characteristics and binding
properties. The fly ash is used in the GPC, which provides better workability and higher solid
to liquid ratios than the other pozzolanic materials like slag, metakaolin, and rice husk ash
due to its small particle size, and spherical and porous properties . In the GPC, the bottom ash
usage increases the strength and workability of the increasing surface for reactivity and
collapses the pores in the matrix due to their higher fineness . The increase in ultrafine fly ash
dosage decreases the setting time, but up to 15% dosage, ultrafine fly ash usage and the
setting time are longer for the fly ash-based GPC. The use of ultrafine fly ash increases by
10%, reducing the matrix’s porosity of the GPC . The fineness of fly ash is the deciding
factor for the amount of fly ash required for the mix design of GPC, because increasing the
fineness of fly ash decreases the quantity requirement for mix design . The fineness of fly ash
plays a vital role by reducing the porosity and water absorption capacity of both concrete
GPC and OPC concrete . The fineness of the fly ash increases the workability, density, and
strength of the GPC. It slightly affects the alkalinity of the GPC but is similar to the OPC
concrete . the effect of the fineness of the fly ash on the density of the concrete mix. The
GGBF/fly ash ratio is 20/80, which is the optimum point of mechanical strength.
GGBS BASED GEOPOLYMER CONCRETE
In the GPC, increasing the dosage of GGBFS decreases the mix’s workability due to the
angular particles of samples compared to the spherical particles of fly ash. It decreases the
ambient temperature curing setting time due to the reaction of calcium present in the slag.
The slag’s usage with fly ash in the GPC presents a similar compressive strength to ambient‐
cured specimens to the water‐cured OPC concrete. The specimen strength gains slow down
after 28 days but strengthen up to 180 days. In the GPC, the strength in‐ creases with the
dosage of GGBFS in the mix design and eliminates heating conditions for curing . The mix
design’s slag/fly ash ratio increases, showing less mass loss at the elevated temperature. The
heat‐cured fly ash‐based GPC gives a higher strength, but this could be achieved by replacing
some fly ash with the GGBFS at ambient‐curing conditions.
EFFECT OF MOLAR RATIOS OF ALKALINE SOLUTION
The compressive strength of GPC increases with an increase in the molarity of sodium
hydroxide, but the workability declines. The GPC uses sodium hydroxide to increase the
mechanical properties compared to the OPC concrete, which results in its higher strength and
performance. Instead of the sodium silicate, KOH generates a much more heterogeneous
structure, with higher porosity and lower strength developed after hydration. Sodium
hydroxide with sodium silicate is used as an alkaline activator of the binder in a 1:1 ratio in
the mix design to produce GPC strength of 40 MPa and above, and verify the potential of fly
ash to replace the cement . The fly ash/slag-based paste setting time reduces as the slag’s
dosage, sodium silicate, and sodium hydroxide molarity increase. The initial time is 55 min,
and the final time is 160 min for the fly ash/slag-based paste at a room temperature of 17 ◦C .
The compressive strength of 30 MPa was quickly achieved with the range of molarity of 9.5–
14 M of NaOH at room temperature in 28 days. The geopolymer matrix developed in GGBFS
is similar to the matrix developed in the absence of GGBFS. If the NaOH concentration is
low, the calcium content of the GGBFs participates in the development of amorphous CSH
gel and the formation of calcium-based geopolymer. If the concentration of NaOH is high, the
precipitation of calcium hydroxide develops.
The addition of sodium silicate extensively increases the hybrid geopolymer system’s early
strength development. The interface between aggregate and geopolymeric paste is not
apparent after the high soluble silicate dosage in the salt-free geopolymeric mortar. In the
geopolymerisation process, soluble silicates are very useful in degrading alkali saturation in
the GPC pore solution even after using a high alkali concentrated activating solution and
promoting the higher inter-particle bonding binder well as the aggregate surface.
Geopolymerisation leads to reliable geopolymer results like binders, mortars, and concrete.
The ratio of sodium silicate to sodium hydroxide (by mass) increases with the increasing
GPC compressive strength. If the alkaline solution content increases in the mix, then the
setting time and workability increase with the reduction of the compressive strength. The
alkaline ratio increased from 1.5 to 2.5, and the alkaline solution increased from 35% to 45%
of the mass of binder, and the optimum point was found at 2.5 alkaline ratio and at 40%
alkaline solution in the mix. The Na2CO3 activator is the cheapest activator in terms of the
relative cost per ton and strength of geopolymer mortars. The yield point of the compressive
strength of mortar and paste found at the molar ratio of Na2O/SiO2 is 0.40 and shows the
paste’s denser morphology. If the Na2O/SiO2 molar ratio increases, then the consistency of
the paste decreases. It forms an alumino-silicate gel with the fly ash content and is
responsible for the higher workability and the mechanical properties of the GPC samples in
the hardened state. The increased ratio of Na2SiO3/NaOH decreases the fine aggregate
requirement in the mix design and increases the extra water requirement in the mix.
Effect of Calcination Temperature
The geopolymer manufactured from calcinated clays shows better mechanical properties than
a geopolymer obtained from un-calcinated clays. Calcination conditions (calcination
temperature, heating rate, calcination time, atmosphere, and cooling rate), to achieve
dehydroxylation of a given clay mineral, affect the pozzolanic reactivity, hydration kinetics,
and consequently, strength and durability of geopolymer concrete. The geopolymer derived
from clay minerals calcinated at temperature of 900 ◦C shows better characteristics, such as
compressive strength, water absorption, and stability in the aggressive environment of
chloride ions, than the clay minerals calcinated at lower temperature than 900 ◦C
Effect of Particle Size Fraction and Types of Aggregates
In the GPC, the aggregate size has a critical effect on the elevated temperature; the spalling of
GPC reduces with the increase in the maximum aggregate size of the GPC mix design. The
size of the fracture process zone increases with the aggregate size by shielding the crack tip.
The maximum aggregate size increase in mix design provides higher resistance to fire by
improving stability. The GPC has better stability against elevated temperatures and better
compatibility between the aggregates and pastes. The geopolymer aggregate was developed
from the mine tailings of fly ash and is used as a lightweight aggregate in mortars and
concrete. The geopolymer aggregate shows better mechanical properties than the LECAs in
the mix
design solid state, whereas the rheological properties are the same. The geopolymer aggregate
shows a better crushing value and excellent bonding due to its rough surface. The geopolymer
sand dosage in the mix design shows better mechanical properties up to 40% replacement of
natural sand, but beyond 40%, the mix’s mechanical properties decrease with the increasing
content of geopolymer sand. The concrete strength increases with the dosage of m-sand in the
mix by replacing natural sand up to 20%, but beyond 20%, strength slightly decreases
compared to the nominal mix. The GPC uses 100% m-sand to replace natural sand, which
shows adequate strength, and it is an economical, environment-friendly material that reduces
carbon footprints by up to 80%. In the GPC, the dosage of the RCA in the mix design by the
partial replacement of the natural sand shows an adverse effect on the compressive strength,
splitting strength, sorptivity, chloride ion penetration, water absorption, and volume of voids,
but the properties are better than the OPC concrete. The ductility of the GPC structural
element is shown to increase with the partial replacement of natural sand in GPC design mix
by waste aggregate of lime stone.
Effect of Ratio of Activator Liquid to Fly Ash/Slag
If the activator to binder ratio decreases from 0.40 to 0.35, then the fresh mix’s workability
decreases, but extra water enhances the workability and strength are reduced. The strength
reached up to 51 MPa at 28 days of GPC, containing 20% slag and 80% fly ash as a binder
and cured at 20 ◦C. In the fly ash-slag based GPC, the slag/fly ash plays an essential role in
the mechanism of the geopolymerisation for strength development. If the slag content in the
mix design is over 50% of the binder, this demonstrates the calcium silicate hydrate gel’s
primary reaction with the Na and Al, leading to the formation of the C–N–A–S–H bond. If
increasing the fly ash content in the binder, then the form of N–C–A–S–H type gel as a
primary reaction bound the water tightly in the composition and got a higher degree of
crosslinking compared to the composition formed of C–A–S–H type gel in the slag binder.
This study provides critical evidence of the different mechanisms of the geopolymerisation
based on the slag/fly ash ratio content as a binder in the mix design. If the small dosage of the
slag in the fly ash is in the mix, the reactions slow down the formation of the C–A–S–H
binding gel and the formation of the hybrid C–N–A–S–H gel due to the overtime release of Si
and Al in the reactions. Increasing the dosage of fly ash in the mix promotes the zeolite
development in the hybrid gels after 28 days of higher temperature curing with a lower
activator concentration. After the long curing period, the gel microstructure formation
predicted the mechanical capability and durability performance of the GPC samples. If the
15% ACS replaces the GGBFS in GPC, it leads Crystals 2022, 12, 514 9 of 24 to the thermal
stability of the GGBFS-based GPC up to 1000 ◦C and shows the amorphous nature to resist
the heat treatments used in the formation of refractory bricks. Increasing the dosage of ACS
by up to 25% decreases the thermal stability of the geopolymer. If the GGBFS is replaced by
silica fume by 10%, it increases the strength at a high level and shows thermal stability up to
500 ◦C, whereas the ACS dosage shows thermal stability up to 800 ◦C . If the dosage of slag
and sodium silicate is increased, it increases the autogenous shrinkage and chemical
shrinkage, and if the water binder ratio decreases, drying shrinkage decreases and autogenous
shrinkage increases in the AFS mortar. The GPC’s slag content above 70% in the mix reflects
the rapid setting and cracks generated due to the autogenous shrinkage and shows the
hydration products’ denser matrix. The geopolymer matrix is not affected by using
superplastizisers in the mix design. If the GGBFS, OPC, and CH in the fly ash increase the
concrete’s compressive strength, it is applicable when no extra water is added to the alkaline
solution. With the increasing GGBF dosage, the GPC’s workability and setting time would
decrease. When GGBFS dosage was up to 30% of binder, the design mix got 55 MPa of GPC
and 63 MPa of geopolymer mortar at 28 days. In the GGBFS/fly ash-based GPC, the
formation of C-S-H gel at 27 ◦C by activating GGBFS shows minimal interaction between
the fly ash and GGBFs due to different reactions occurring. The mix design strength was
developed by the C-S-H gel formation products. The presence of the CSH gels and
geopolymeric gels in the matrix enhances the system’s strength with the usual quantity of
GGBFS. The geopolymer matrix’s CSH gel formation worked as a micro-aggregate and
resulted in excellent mechanical strength [36]. In the GPC, the fly ash to activator ratio plays
an essential factor regarding strength and fire-resistant matrix and silicate to hydroxide,
binder age and curing period show negligible effects on the early strength of the GPC. The
optimum point of strength and fire-resistance is found at Na2SiO3/KOH = 2.5 and
FA/activator = 3.0. In the GPC, water in the fresh concrete mix and removed through
evaporation causes a crack. The workability of the fresh concrete increases with the
increment of water dosage in the mortar mix. In the GPC, when the molarity of sodium
hydroxide is above 10 M, it shows an increment of workability with fewer effects on strength
by increasing the water content in the mix. The strength of the GPC decreases with the
increase of the water to geopolymer solids ratio by mass. This leads to the loose
microstructure of the geopolymer paste in the concrete.
Effect of Curing Conditions
The curing temperature plays a vital role in the setting and hardening of the GPC. The GPC
samples cured at higher temperatures obtain concrete in 4 h at ambient temperature, but at an
ambient temperature below 10 ◦C, the setting of fresh concrete takes up to 4 days without
losing quality. The GPC specimens cured at the higher temperature reached mechanical
strength within 1 day, but the hardening of the fresh concrete at ambient temperature
increased quality strength after 28 days compared to strength gain in 1 day. Curing time also
plays an essential role in gaining strength with temperature. The compressive strength of the
GPC increases with the increasing curing temperature from 30 ◦C to 90 ◦C . If the curing at
the ambient temperature is impossible due to the delayed time of fly ash-based GPC, the
temperature for curing is favourable for gaining higher strength, and the long curing time
enhances the geopolymerisation process. GPC samples cured at higher temperatures for a
long time lead to microcavities developing in the microstructure, creating cracks in the
sample due to water evaporation from the matrix. The GPC flexural strength is higher than
the OPC concrete of the same compressive strength. In the natural pozzolanic-based GPC, the
compressive strength increases with increasing time and temperature. The GPC applications
are cured in both conditions; atmospheric pressure up to 100 ◦C and autoclave curing above
100 ◦C. It enhances the mixed samples’ compressive strength by eliminating the micro-cracks
in the samples. If the curing time increases from 6 h to 96 h, it increases the compressive
strength of the GPC, but beyond 48 h of curing, the compressive strength of the samples is
not significant. Pre-curing at an ambient temperature above 95% humidity at room
temperature before heat curing is beneficial for strength development. Temperature curing is
responsible when the specimens cured for 1 h at elevated temperatures do not reach
remarkable strength. The longer curing time is responsible for the strength development at
early periods, by accelerating the reaction rates. The curing age enhances the polymerisation
process from 4 h to 96 h and increases the compressive strength, but the strength
development of the samples is achieved at 24 h of curing, so there is no need to cure beyond
24 h. The geopolymerisation reaction increases with the increase in curing temperature and
develops the early strength of the GPC. The GPC samples cured in the fog show the high
absorption of moisture. The end products of GPC had a mostly open microstructure when
steam cured. In the GPC, the oven-cured specimens reached 90% strength in 3 days and 28
days of compressive strength, but the ambient-cured samples reached up to 82% strength in
28 days. The ambient-cured specimens’ ultimate strength was higher than the oven-cured
samples because the strength rate beyond 7 days is not significant. The elastic modulus of
GPC is directly affected by curing temperature. The MOE of specimens increases with the
curing’s increasing temperature up to a limit and elated to the water to binder ratio. The
evaporation of the water from the matrix during the temperature curing reduces the elastic
modulus of the GPC specimens.