Effect of Nano-Silica and GGBS on the Strength Properties of Fly Ash-Based

Geopolymers

Abstract
In this study, the roles of reactive alumina and process variables such as sodium
content and molarity on the alkaline activation of nano-silica and ground-granulated
blast-furnace slag are explored. Reactive alumina content of fly ash is the key
parameter that determines the maximum compressive strength achieved from the
alkaline activation. This paper also investigated the role played by nano-silica in fly
ash-based geopolymer binders. The principal source of alu- minosilicate is low-
calcium fly ash, which was slowly blended with blast furnace slag to accelerate
curing at ambient temperature. Then, different rates of colloidal nano-silica were
added to the total binder on the days 3, 7, and 28 of curing.
1 Introduction
Geopolymers are aluminosilicate binders made using materials rich in alumina and
silica. The typical materials used include blast furnace slag, metakaolin, rice husk
ash, aluminum-rich waste, fly ash, and red mud [1–7]. In the Asian sub-continent, fly
ash, an industrial waste product, is one of the most attractive source materials due to
its large availability. However, the quality of this highly available fly ash is of low
grade with little reactive content [8]. Several factors influence the mechanical
properties and microstructure of fly ash-based geopolymers. Some of these factors
include reactive oxide contents, NaOH concentration, particle size, temperature,
oxide ratios of SiO2, Al2O3, and Na2O, and alkali activator to binder ratio [6, 9, 10].
SiO2/Al2O3 and SiO2/Na2O ratios are the dominant factors in strength prediction of
geopolymers. The compressive strength of fly ash-based geopolymers has been
observed to increase when the concentration of NaOH is increased in the activating
solution [11]. It should be noted that the quantity of required NaOH depends on the
type of fly ash used [12]. At low SiO2/Na2O, geopolymers are usually less stable
compared to their stability at high SiO2/Na2O [9]. It has been reported that the
highest value of compressive strength of geopolymers is obtained when SiO 2/Na2O
is 0.69 [13]. The compressive strength is affected by the increase in the weight ratios
of Al2O3/Na2O and SiO2/Na2O in the activating solution [11, 14]. In addition, it also
depends on the vitreous portion of SiO2/Al2O3 ratio [15].
The combinations of sodium silicate (Na2SiO3) and sodium hydroxide (NaOH)
are the most commonly used activators. The solution ratios derived from fly ash with
highly reactive silica content does not require additional Na 2SiO3 for achieving high
strength. Instead, a few researchers have considered a vitreous portion of SiO2 and
Al2O3 [15]. Solutions need to be derived using the composition and contents of
reactive silica and alumina in fly ash. The present study explores the role of colloidal
nano-silica content in the development of strength of geopolymers. The study also
included various experiments on geopolymer concrete (GPC) by the addition of
different nano-silica proportions cured at ambient temperature.
2 Materials
The present study only considered fly ash and ground-granulated blast-furnace slag
(GGBS) as the main materials for preparing GPC. In addition, the aggregates
occupied 75–80% of the total mass of GPC. NaOH concentration maintained at 12
M and Na2SiO3 solution containing 16.37% Na2O, 34.35% SiO2, and 49.72% H2O
were used as alkaline activator solutions. The following sections discuss constituent
materials used for manufacturing GPC. Tables 1 and 2 show the physical and
chemical properties of these constituent materials, respectively.
2.1 Nano-Silica
Colloidal nano-silica having brand name CemSyn®-XLP was procured from Bee-
Chem Chemicals Ltd. (Kanpur, India). Its different properties are presented in Table
3.
3 Experimental Procedure
3.1 Specimens Preparation
For all the specimens, the ratio of alkaline solution to binders (fly ash and GGBS)
was kept constant at 0.45. Initially, the NaOH molarity was kept constant at 12 M.
The NaOH solutions were prepared 24 h prior to using it so as to account for proper
dissolution of NaOH crystals and heat liberation. Identical mixing process and
castings were followed for the individual mix, irrespective of varying percentages of
nano-silica. The final mix was then transferred into molds measuring 150×150×150
mm in three layers, each with sufficient vibration. For each mix, three cube
specimens were casted.
3.2 Curing
After casting for 24 h, the GPC specimens were cured at ambient temperature (27 ±
2 °C), until further use. However, the non-nano-silica (FA-NS-0) specimens were
cured at 60 °C within a hot air oven for 48 h and then kept at ambient temperature,
until further use.
3.3 Specimens Testing
All the cube specimens were casted and cured at similar conditions as explained
above. The compression testing for the GPC specimens was conducted at 3, 7, and
28 days of curing.
4 Results and Discussion
4.1 Compressive Strength of Only Fly Ash GPC
The compressive strengths of only fly ash-based GPC with the addition of 0–10%
nano-silica are shown in Fig. 1. The compressive strength of the control mix on 28
days was 33.9 MPa, which was found to increase to 42.69 MPa with nano-silica
addition. As shown in the figure, the mixes containing 4–10% nano-silica had
significantly higher compressive strengths than that of the control mix. Compared to
the mix FA-NS-0, the mixes FA-NS-6, FA-NS-8, and FA-NS-10 had 20.59%,
15.58%, and 12% higher compressive strength on the 28th day. This indicates that
the strength of the binder increased with the increase in the nano-silica concen-
tration in the mixes.
The mix FA-NS-6 showed the highest 28-day compressive strength. However,
with the increase in nano-silica concentration for more than 6%, the strength
increase of the binders reduced. This is mainly maybe because the 6% concentration
of nano-silica was sufficient for reaction due to its high surface area. Any further
increase in the concentration of nano-silica did not get involved in the reaction
process, and thus, there was no further increase in the strength. As shown in Fig. 1,
the same trend of 28-day compressive strength with respect to nano-silica con-
centration was also observed for the compressive strengths at 3 and 7 days of age.
Fig. 1 Variation in compressive strength of only fly ash-based geopolymer concrete
with nano-silica
4.2 Compressive Strength of GGBS-Blended Fly Ash GPC
Figure 2 shows the variations in compressive strengths of GGBS-blended fly ash-
based geopolymers on the addition of 20% nano-silica. At 28 days of curing, the mix
FA-S-NS6, which contains 6% nano-silica, showed a compressive strength of 63.45
MPa, which is 46.54% higher compared to 33.9 MPa of FA-NS0 (control mix). In
addition, it was observed that 6% nano-silica showed the maximum effect on the
strength; this was also found in the other series. It was further observed that the
increased strength began to decline when the concentration of nano-silica exceeded
6%. This is due to the excess amounts of unreacted particles in the geopolymer
matrix that resulted in cracking and excessive self-desiccation, even- tually reducing
the strength. This finding implies that the concentration (6%) of nano-silica in the
GGBS-blended fly ash-based geopolymer reacted completely and any further
increase in the concentration of nano-silica did not improve the strength. This nano-
silica effect was also observed for only fly ash-based GPC. Thus, the optimum
concentration of nano-silica for the improvement of strength of the GPC should be
considered. The GGBS-blended geopolymer mixes have a higher strength at the
molecular level due to its lower binding energy. Thus, the addition of GGBS in the
geopolymer mix led to an increase in the reactivity of the source material and
strength of the binder.
4.3 Split Tensile Strength of Concrete
Figure 3 shows the 28-day split tensile strengths of only fly ash geopolymer con-
crete and GGBS-blended fly ash GPC with 0–10% nano-silica. The split tensile
strength values of the two series first gradually increased when nano-silica was
added up to 6% concentration and then decreased.
The maximum split tensile strength at 28 days of only fly ash geopolymer
concrete with 6% nano-silica was 4.41 N/mm 2, which was 29% more than the
control GPC mix. Similarly, the maximum 28-day split tensile strength of GGBS-
blended fly ash GPC with 6% nano-silica was 6.35 N/mm2, which was 50% more
than the control GPC mix. These effects are presented in Fig. 3.
4.4Flexural Strength of Concrete
The flexural strengths of both the mixes with 0–10% nano-silica at 28 days of age
are presented in Table 4. It was found that the 28-day flexural strength of both the
series gradually increased when the nano-silica was added up to the concentration of
6%. Any further increase in the concentration of nano-silica resulted in a decrease in
the flexural strength values. The maximum 28-day flexural strength of only fly ash
geopolymer concrete with 6% addition of nano-silica was 6.82 N/mm 2, which was
36.8% higher than the control GPC mix. Similarly, the maximum 28-day flexural
strength of GGBS-blended fly ash GPC with 6% addition of nano-silica was 7.84
N/mm2, which was 50% higher than that of control GPC mix. These observations
are shown in Fig. 4.
Table 4 Test results of beams
Only fly Fly ash with nano- GGBS-blended fly ash
Parameters
ash beam silica beam with nano-silica beam
Peak load 33.4 41.9 52.2
Max
displacement 7.67 8.37 12.02
(mm)
Disp. at peak
7.67 8.37 12.02
load (mm)
Strain at peak
0.03 0.04 0.04
stress
Flexural
strength 69.58 79.30 93.63
(N/mm2)
Max flexural
0.03 0.04 0.04
strain (%)
Modulus (N/
16.37 16.7 21.97
mm2)

4.5 Test Results of Beams

The results of the beams are tabulated in Table 4, and from the obtained results, the
load-deflection curves were plotted as shown in Fig. 5. It was observed that the
flexural strength increased in fly ash with nano-silica beam and GGBS-blended fly
ash with nano-silica beam compared to that of only fly ash beam (control beam). As
shown in Fig. 4, the deformation capacity for the concrete material is important
because structural applications mainly require high deformation and energy dissi-
pation capacity. It was observed that the incorporation of GGBS with nano-silica in
GPC results in increased deformation capacity of concrete due to the formation of
hydrated products at a larger scale.
It is, therefore, deduced that GGBS with nano-silica results in the formation of
hydrated products at a larger scale. These hydrated products heal the shrinkage
cracks and pores in concrete matrix and also enhance the load carrying capacity and
strain capacity of concrete.
5 Conclusions
Given below are the conclusions of this study:
i. The 28-day strength properties of only fly ash-based GPC with nano-silica had a
considerable improvement over the control GPC mix.
ii. It was observed that the addition of 6% nano-silica in only fly ash-based GPC
cured at ambient temperature improves the compressive strength at 25.9% over
the control GPC mix. Similarly, the split tensile and flexural strengths improved
at 29.02% and 36.80% over the respective control GPC strengths.
iii. Strength properties of GGBS-blended fly ash-based GPC mix with nano-silica
showed a significant improvement over the control GPC mix.
iv. It was observed that the addition of 6% nano-silica in GGBS-blended fly ash-
 based GPC cured at ambient temperature improves the compressive strength,
split tensile strength, and flexural strength by 46.54%, 50.72%, and 48.29%,
respectively, over the control GPC mix.
v. Compared to the control beam (only fly ash beam), 22% improvement in
ultimate strength was observed in only fly ash-based GPC with nano-silica
beam.
vi. Compared to the control beam (only fly ash beam), 41% improvement in
ultimate strength was observed in GGBS-blended fly ash-based GPC with nano-
silica beam.
Experimental Investigation on Compressive Strength of LD Slag
Aggregate Concrete

Abstract
This paper aims to study the compressive strength of concrete made using Linz-
Donawitz (LD) slag as a replacement for natural fine and coarse aggregate with both
getting replaced up to 100% at an interval of 20% respectively. Concrete of grades
M20, M25, M30, M35 and M40 has been considered for studying their compressive
behaviour when natural aggregates are being gradually replaced with LD slag. The
results obtain showed an increase in compressive strength of the concretes with the
increase in percentage replacement of natural fine and coarse aggregates with LD
slag.

1 Introduction
Concrete is a versatile material widely used for structures and for other applications.
The demand of concrete is increasing day by day due to the growing population,
housing, transportation and other amenities. As a result the demand for concrete
making materials also increases leading to the scarcity of naturally available fine and
coarse aggregate required for making concrete. Additionally, the speedy
development of industrialization contributed to different types of waste by-products
which are environmentally dangerous and creates problem in disposal.
Hence, utilization of suitable waste by-products in construction industries has
become an inevitable option in recent days [1–15]. The use of industrial waste as
aggregates in concrete provides good platform to utilize the waste as alternatives to
naturally available aggregates in concrete as aggregates are the main constituents of
concrete making about 75% of its total volume [16–22]. Linz-Donawitz slag (LD
Slag) is one of the alternative materials which can be used as both coarse and fine
aggregate for replacement of river sand and crushed rock ballast in concrete by
altering the physical form. Slag is a by-product, obtained after a desired metal has
been separated from its raw ore. Commonly obtained when raw iron ore is con-
verted to steel products and the slag are discarded as waste products. Molten by-
product slag is quenched in water or steam, dried and ground into powder. It can be
used as a replacement of aggregates. Very limited efforts have been made
worldwide to use LD slag as an alternate civil engineering material. Hence, an effort
is being carried out to utilize the local LD slag as an alternate civil engineering
material. The findings based on the limited laboratory tests of the basic material
properties, physical properties, strength parameters suggest that LD slag has the
potential to be used as an alternate fine aggregate and coarse aggregate in concrete.
2 Material Properties
Portland slag cement of Lafarge brand Conforming to IS 455-1989 has been used as
binder [23]. Locally available sand collected from Kharkhai River has been used in
the research work. Non-flaky, non-elongated angular coarse aggregate passing
through 20 mm sieve and 10 mm sieve has been used. LD Slag used has been
supplied by TATA Steel LTD. Jamshedpur. LD Slag is a waste product from steel
 industries. LD Slag used as fine and coarse aggregate are of same chemical com-
position. Physical properties of the materials used in this work are shown in Tables
1, 2 and 3.
Table 1 Physical properties of cement [24, 25]
S.
Particular of tests Results Standards
No.
IS:4031 (part-IV)-
1 Consistency 30.5%
1988
IS:4031 (part-I)-
2 Fineness 4%
1996
IS:4031 (part-XI)-
3 Specific gravity 2.92
1988
Initial 108 min IS:4031(part-I)-
4 Setting time
Final 258 min 1996
Soundness(by Le-Chatelier 1 mm
5 IS:269-2015
apparatus) (expansion)
3 days 17.8 N/mm2
Compressive 7 days 24.85 N/mm2 IS:4031 (part-VI)-
6
strength 28 1988
36.75 N/mm2
days

Table 2 Physical properties of natural sand and LD slag fine aggregate [26–28]
S. LD slag fine
Particular of tests Natural sand Standards
No. aggregates
IS:383-
1 Fineness modulus 2.83, Zone -II 1.93, Zone-III
2016
IS:2386
2 Specific gravity 2.59 2.53 (Part-III)-
1963
IS:2386
3 Free moisture 0.20% 3.9% (Part-III)-
1963
IS:2386
4 Water absorption 0.80% 6.46% (Part-III)-
1963
Bulk Compacte IS:2386
1610 kg/m3 1920 kg/m3
5 densit d (Part-III)-
y Loose 1560 kg/m3 1787 kg/m3 1963
Maximum
Maximum
bulking of
bulking of LD IS:2386
natural sand is
6 Bulking of sand Slag is 15.70% (Part-III)-
23.1% at
at moisture 1963
moisture
content of 10%
content of 3%

Table 3 Physical properties of natural coarse aggregate and LD slag [26–28]

S. Natural coarse LD slag coarse
Particular of tests Remarks
No. aggregate aggregates
 1 Fineness modulus 6.60 6.94
2 Specific gravity 2.83 2.92
3 Free moisture 0.10% 0.60% IS:2386
4 Water absorption 0.35% 0.84% (Part-III)-
Compacte 1963
Bulk 1782 kg/m3 2109 kg/m3
5 d
density
Loose 1606 kg/m3 1948 kg/m3
6 Crushing strength 17.6% 13.35% IS:2386
(Part-IV)-
7 Impact value 16.4% 13.06%
1963

3 Experimental Program
Concrete cubes for compressive strength test has been cast. Specimens have been
cast using normal fine aggregate and normal coarse aggregate and replacing fine
aggregate with LD slag (up to 100% starting from 0% with an interval of 20%) and
replacing coarse aggregate with LD slag (up to 100% starting from 0% with an
interval of 20%). All tests have been performed after 28 days of curing. Concrete
specimens for M20, M25, M30, M35 and M40 have been prepared for all types of
specimen mentioned above [29, 30].
4 Results
The workability of fresh concrete was tested by using Slump Cone Test method and
compressive strength of different grades of concrete was also found out for different
proportion of fine and coarse aggregate replacement with LD slag. The results of the
experiments done have been given (Table 4).
The workability of the concrete decreased with the increase in percentage
replacement of fine aggregate with LD slag. The reduction in workability of M20,
M25, M30, M35 and M40 after full replacement of natural sand with LD Slag was
noted as 31.43, 40.21, 52.13, 60.61, 67.37%, respectively, which shows that the
reduction in workability of concrete is more in higher grades as compared to lower
grades. The reduction in workability of concrete may be primarily due to the lower
particle size of LD Slag as its fineness modulus is much lower than that of the
natural sand (Fig. 1 and Table 5).
Table 4 Workability of concrete at different percentage of fine aggregate
replacement
Workability (mm)
S. Percentage of fine aggregate
M2 M2 M3 M3 M4
No. replaced with LD slag
0 5 0 5 0
1 0 105 97 94 99 95
2 20 97 91 89 91 83
3 40 94 85 78 79 70
4 60 87 78 69 66 56
5 80 81 67 58 51 41
6 100 72 58 45 39 31

Table 5 Workability of concrete with different percentage of coarse aggregate

replacement
 Workability (mm)
S. Percentage replacement of coarse
M2 M2 M3 M3 M4
No. aggregate with LD slag
0 5 0 5 0
1 0 105 97 94 99 95
2 20 101 94 88 92 88
3 40 97 90 83 84 81
4 60 91 85 76 77 73
5 80 87 78 71 71 67
6 100 82 72 64 65 54

The workability of the concrete decreased with the increase in percentage

replacement of coarse aggregate with LD slag. The reduction in workability of M20,
M25, M30, M35 and M40 after full replacement of natural coarse aggregates with
LD Slag was noted as 21.9, 25.7, 31.91, 34.3 and 43.16% respectively. This result
indicates that the reduction in workability of concrete is more in higher grades as
compared to lower grade concretes. The reduction in the workability may be due to
the surface texture and porosity of LD slag (Figs. 2, 3, 4, 5, 6, 7 and Tables 6, 7). All
the grades of concrete have shown more or less similar kind of trend when
replacement of aggregates has been done. In the case of fine aggregate replacement
with LD slag, maximum compressive strength for all the grades of concrete has been
observed at 60% replacement. Graph shows a decreasing trend after 60%
replacement in case of fine aggregate replacement. Maximum compressive strength
of cubes has been observed at 80% replacement of coarse aggregate for all the
grades. Graph shows a downtrend after 80% replacement in case of coarse aggregate
replacement.
Table 6 Compressive strength of concrete with different percentage of fine
aggregate replacement
S. Percentage replacement of fine Average compressive strength (N/mm2)
No. aggregate with LD slag M20 M25 M30 M35 M40
25.4 40.4
1 0 30.7 35 46.8
9 4
26.6 32.5 38.5 43.2 47.5
2 20
8 0 5 5 6
27.5 33.1 40.3 45.2 47.9
3 40
6 7 4 4 7
29.8 34.0 41.4 45.9 50.2
4 60
0 5 2 0 4
28.1 33.6 40.1 43.7 49.2
5 80
2 5 2 2 3
26.2 41.4 48.1
6 100 31.6 36.8
4 4 5

Table 7 Compressive strength of concrete with different percentage of coarse

aggregate replacement
S. Percentage replacement of Average compressive strength (N/mm2)
No. coarse aggregate with LD slag M20 M25 M30 M35 M40
 25.4 40.4
1 0 30.7 35 46.8
9 4
27.1 31.2 36.1 41.2 47.2
2 20
3 4 2 5 4
28.1 32.5 36.7 42.7 48.8
3 40
2 6 8 4 0
29.4 34.1 37.8 43.0 49.2
4 60
6 5 6 2 4
29.8 35.6 39.1 43.6 50.2
5 80
4 8 8 5 4
27.4 34.8 37.4 41.5 48.1
6 100
5 4 2 6 4

5 Concluding Remarks
Based on the results it is to be concluded that the LD slag is a potential replacement
material for aggregates in concrete.
1. Replacement up to 60% of natural fine aggregate with LD slag results in
enhancement of compressive strength after which the strength starts decreasing.
2. The workability of concrete decreases with the increase in slag content,
especially, in higher grades.
3. Replacement of natural coarse aggregate with LD slag up to 80% results in
enhanced compressive strength after which the strength reduces slightly.
4. It can also be seen that the compressive strength of mixes obtained by full
replacement of fine and coarse aggregates separately are in accordance with the
compressive strength of different mixes.
5. The compressive strength of concrete with fully replaced natural fine aggregate
by LD slag was found to be greater than the normal concrete.
6. The compressive strength of concrete with fully replaced natural coarse aggregate
by LD slag was found to be greater than the normal concrete.
Mineralogical Study of Concretes Prepared Using Carbonated Flyash as Part
Replacement of Cement

Abstract
Cement production is excessive energy intensive, responsible for depletion of
natural layers and high carbon foot print. Thus search for an envi- ronmentally
benign cement substitute still is an on-going process. Fly ash is a well-established
concrete admixture enhancing the strength, durability and micro-structural
properties. As well as it is a good reagent to sequester atmospheric carbon dioxide.
Concretes prepared through part replacement of cement by car- bonated fly ash
demonstrate good resistance against chloride, acid and sulfate attack. In the present
research mineralogical study of CFC (Carbonated Fly ash concrete) has been
conducted through XRD analysis. XRD of control concrete (CC) and fly ash
concrete (FC) have also been carried out to study the comparative distributions of
mineral crystallites present in concretes. The tests have been con- ducted in the
concrete specimens cured in water for 28 days and 90 days to study the effect of
hydration and extent of pozzolanic reaction on the mineralogical composition. Two
replacement levels of 25 and 40% were considered for experi- mentation. The
qualitative XRD investigation yielded a higher intensity of CaCO3 in the concretes
prepared using Carbonated Fly ash. The presence of CaCO 3 helped the concretes in
developed chemical resistances dense and improved microstructure. The
thermogravimetric analysis further confirmed the presence of higher Carbonates in
the CFC specimens.

1 Introduction
Concrete, the most demanded construction material, plays an important role in
construction industries due to its contribution to strength and durability of the
structures. Cement being the key binding material, the economic and ecological
concerns of concrete is greatly influenced by cement. As cement production is
excessive energy intensive, responsible for depletion of natural layers and high
carbon footprint [1, 2], the search for a suitable cement substitute as full/partial
replacement in concrete has evolved as interesting and challenging research area.
Fly ash, the power plant waste due to its spherical shape, favorable particles size and
excellent pozzolanic properties has been successfully utilized in concrete [3–5].
Additional strength gain due to secondary hydration products, low w/b ratio
requirement, micro-filling and packing effect help fly ash concrete to exhibit better
strength and durability over control concrete [6, 7].
In addition to the application potential of fly ash in various fields, its capacity to
sequester carbon dioxide through Carbon Capture and Storage (CCS) technology is
also remarkable [8–10]. The ash generated in such carbonation processes is called as
the carbonated fly ash which is also a waste material. Reutilization of the car-
bonated fly ash in different fields such as amieolerant in soil, filler in mines and as
land filling materials, etc., were reflected in researches. To investigate the suitability
of carbonated fly ash as a part replacement of cement in concrete, two levels (25 and
40%) of replacement has been considered and the durability in terms of chemical
attack [11] and pore-structure analysis [12] has been experimented. As per the result,
the carbonated fly ash concrete is proved to be suitable cement substitute that is
economical, environmentally benign and more eco-friendly.
The performance assessment of the carbonated fly ash concrete in comparison to
fly ash concrete and control concrete indicated better chemical resistance and pore-
structure characteristics. The present research aims at the mineralogical analysis of
the carbonated fly ash concrete and compare to that of fly ash and control concrete.
For the mineralogical study the powder XRD test offers idea of crystallite
composition in a concrete and thereby helps researchers to predict and analyze
concrete in a better way. In the research undertaken XRD test has been conducted to
investigate the influence of water curing days and replacement levels on concrete
durability properties. The study also intends to assess the thermo- gravimetric
analysis of the all types of concrete to evaluate the presence of CaCO 3 affecting
concrete durability. In order to achieve the objectives, five types of con- crete,
namely control concrete, low fly ash concrete (25% replacement of cement), high fly
ash concrete (40% replacement of cement), low carbonated fly ash concrete (25%
replacement of cement by carbonated fly ash) and high carbonated fly ash concrete
(40% replacement of cement with carbonated fly ash) have been cast. For the sake of
brevity, these are designated as CC, LFC, HFC, LCFC, and HCFC, respectively.
2 Experimental Program
The materials used for the experimentation are ordinary portland cement (43 grade),
low calcium class F fly ash collected from Kaniha, NTPC, Odisha, crushed granite
as coarse aggregate (20 mm downgrade), river sand as fine aggregate (zone III) of
nominal maximum size of 4.75 mm, normal tap water and commercially available
poly-carboxylate super plasticizer.
The characterization of the acquired materials has been carried out by the authors
in their previous work [5, 11] where in the tests on the physical properties of cement
have been conducted as designated in IS: 8112-1989; the particle size analysis, X-
ray florescence analysis (XRF), X-ray diffraction analysis (XRD) and thermo-
gravimetric analysis (TGA) have been carried out for cement and fly ash; and the
physical properties and sieve analysis of aggregates have been carried out in
accordance with IS: 383-1970.
The carbonated fly ash has been prepared through mineral sequestration of CO2
from the atmosphere by enriching fly ash with calcium and sulphate [12, 13]. Then
the five types of concrete specimens (150 150 150-mm cube) of M30 grade have
been prepared as per IS: 516-1959 to perform the comparative strength and
durability study with W/C ratio 0.38, SP = 0.2% and the trial Mix ratio 1: 2.18:
3.16. In order to carry out the mineralogical analysis and the thermogravimetric
analysis, a total number of 20 cube samples (4 of each type concrete) were prepared
and water cured for 28 and 90 days. After the required water curing, the samples are
taken out and some chunks from the core, free from coarse aggregates are collected.
Then, the powdered samples of respective concrete specimens followed by meshing
through 45l sieve are prepared for both the XRD and TGA analysis. The X-Ray
diffractometer, ‘X’Pert Pro Powder model of PAN analytical make present at
IMMT, Bhubaneswar and the thermo gravimetry analyser (TGA apparatus Q 50, V
20.13, Build 39 of TA Instruments make at LRPM, CIPET, Bhubaneswar have been
used for XRD and TGA analysis purpose.
3 Result and Discussion
3.1 X-ray Diffractometer Analysis (XRD)
The XRD analyses reveals the different chemical transitions in the concrete spec-
imens and the test results of each type of concrete specimen have been presented
with the analysis of the crystallites. The various crystallite phases present in each of
the concrete specimen water cured for 28 and 90 days are shown in Figs. 1 and 2
respectively. To match the identification of minerals present in the concrete samples
the JCPDS data file have been used. Table 1 presents the mapping of symbols to the
crystallites.
It is observed that the Alite, Belite, Hatrurite, Portlandite are the major crys-
tallites observed in the 28 days water cured CC, along with some intensities of
Sillimanite, Larnite and Zeolite. However, in the 90 days water cured CC samples
the Alite, Belite, Portlandite and Sillimanite are not noticed. This clearly indicated
the occurrence of phase transformation over the water curing period. As Hatrurite is
present in greater intensities in the 90 days cured sample of the CC, it can be
attributed that unreacted or un-hydrated Alite and Belite after sufficient hydration
with water curing completely transform into the Hatrurite.
The major crystal peaks observed in LFC water cured for 28 days are Quartz,
Mullite, Alite, Belite, Hematite and Sillimanite. The other elements include
Hatrurite, Ettringite, Larnite and Gypsum with few peaks of Calcite and Aroganite.
In case of the 90 days water cured samples the Alite and Belite peaks are absent as
they may have been transformed into Hatrurite. In addition to that some peaks of
Ettringite and Zeolite also has been noticed. Mullite is a stable crystalline phase of
Al2O3–SiO2 under atmospheric condition which is the most predominant crystallite
of fly ash. It can be observed from the XRD graph that the compound Sillimanite
and Mullite remained stable throughout the water curing age, as expected.
Table 1 Mapping of symbols to the crystallites
Symbol Constituent Symbol Constituent
a Mullite (Al6Si2O13) d Portlandite (Ca(OH)2)
m Allite (3CaO.SiO2) s Aragonite (CaCO3)
Sillimanite
k u Quartz (SiO2)
(Al2SiO5)
l Belite (Ca2SiO4) q Gypsum (CaSO4.2H2O)
η Calcite (CaCO3) v Larnite (b-Ca2SiO4)
Ettringite
h Hatrurite (Ca3SiO5) c
(Ca6Al2(SO4)3(OH)12·26H2O)
e Zeolite (Si32O64) w Hematite (Fe2O3)

In the 28 days water cured sample of the HFC, the major crystallites observed are
Allite, Belite, Sillimanite, Quartz, Mullite, Gypsum and Ettringite. The other mineral
peaks appearing in less intensity are Hatrurite, Calcite, Aragonite and Larnite. With
water curing age, the Allite, Belite completely transformed to give rise to Hatrurite
due to phase change. In 90 days water cured sample also Mullite is noticed. High
peaks of Ettringite and Quartz are observed in these types of HFC samples. Absence
of Gypsum has been noticed whereas peaks of Zeolites are found corresponding this
curing age.
Strong peaks of Mullite, Sillimanite, Hatrurite and Calcite dominate in case of the
28 days cured LCFC. Crystallites such as Aragonite, Gypsum and Larnite have been
also noticed. However, the numbers of peaks of them are less. With the water curing
age, more intense peaks of Mullite and Calcite are observed. The absence of gypsum
has been noticed in the 90 days water cured samples. More number of peaks of
Calcite confirms the occurrence of carbonation of fly ash that has been used in the
carbonated fly ash concrete.
In case of the 28 days water cured sample of HCFC, the major crystal peaks
observed are Hatrurite, Calcite, Mullite, Sillimanite and Aragonite. In addition to
this some peaks of Gypsum, Hematite and Larnite are also found. However, their
intensities are very less. In 90 days water cured samples, absence of Gypsum and
Hematite is noticed and Zeolite peaks are observed. In both the water curing days
Hatrurite is detected.
The XRD analysis reveals the strong peak intensities indicating presence of
Allite, Bellite, Hatrurite and quartz in all types of concretes. Number of peaks
pertaining to Portlandite is only noticed in case of the CC. In the fly ash concrete
and the carbonated fly ash concrete, peaks of Portlandite are not detected. The peaks
pertaining to Gypsum and Ettringite are seen to be of strong intensities in the fly ash
concretes. However, the peaks pertaining to these are not observed in XRD of the
carbonated fly ash concrete. Very strong peak intensities pertaining to Mullite and
Calcite are observed in XRD of carbonated fly ash concrete. With increase in water
curing age, variations are marginal, however number of peaks pertaining to
Ettringite in fly ash concrete appears to be increasing with water curing.
Research undertaken by the author using carbonated fly ash as part replacement of
cement in concrete has indicated better durability performance of the carbonated fly
ash concrete. Increased resistance against chloride, acid and alkali were reported by
the author [11]. In case of carbonated fly ash concrete, in addition to the continuous
pozzolanic reaction, secondary hydration and extra CSH gel, the pre- cipitation and
deposition of CaCO3 in the pore fluid adds extra mechanical strength and stability to
the concrete material. The deposition of CaCO3 in case of car- bonated fly ash
concrete helps in filling the micro-pores and micro-cracks with a high rate making
the concrete more dense and impermeable which restricts the penetration of salt and
sulfate ions into the concrete to a great extent. Further the presence of stable CaCO 3
and reduced surplus lime retards the chemical reaction to a great extent [14].
Increased peak intensities relating to carbonate crystals in the LCFC and HCFC
specimens compared to CC, LFC and HFC specimens reveal this aspect. The
crystallization of the carbonates further contributes towards pore-structure
refinement. The research by the author [12] reports refined pore structure in the CFC
specimens. The refinement of the pores is an indication of increased crystallization.
The XRD results substantiate the aspect of higher Calcium Carbonates in the CFC
specimens.
3.2Thermogravimetric Analysis (TGA)
In order to demonstrate a comparative analysis, the data regarding the weight loss %
at specific temperature steps have been taken from the TGA-DTG charts of indi-
vidual concrete specimens and plotted in Figs. 3 and 4 for concrete specimen water
cured for 28 days and 90 days respectively. In addition to this the combined TGA
results of all the five types of concrete specimens representing the mass variations
over temperature range (20 °C to up to 900 °C) are also presented in Figs. 5 and 6,
for the water curing period of 28 days and 90 days, respectively.
It is observed from Fig. 5 that, with the increase in temperature the mass loss
increases monotonically in all types of concrete specimens and then gradually
becomes steady after 700 °C and towards 900 °C. All the curves except the CC
show a rapid decline up to a temperature of about 130 °C, among which the behavior
is sharper in case of LCFC and HCFC. At this stage the mass loss of the concrete are
due to the dehydration of C–S–H and evaporation of free water from the pore. The
DTG curves of the concrete samples, Fig. 3, at the temperature rangebof 110–130
°C show double peaks which can be attributed to the loss of water in some hydrates
like C–S–H and Ettringite [15, 16]. After 120 °C, the TGA ther- mogram of all the
types of concrete follows a steady slope of mass drop over the temperature range of
400–450 °C. At this stage the mass loss is mainly due to the loss of water from pores
of hydrates as well as due to the first stage of dehydration and breakdown of to
Bermorite gel [17]. At this temperature range the portlandite (C–H) decomposed
into calcium oxide and water, resulting in the rapid weight loss. Furthermore,
another mass drop is observed at the temperature of about 670 °C for all types of
concrete owing to the decomposition of carbonates and releases of CO 2. Finally at
900 °C, all the concrete show steady and flat curve which can be clearly studied
from the TGA curve. It is also worthy to note that the % weight loss is minimum for
the CC and maximum for the HCFC.
The TGA-DTG thermograms as shown in Fig. 4 for the 90 days water cured
concrete specimens shows the existence of couple of peaks for all most all the
concrete within the temperature range of 50–150 °C, among which the LCFC and
HCFC have very sharp and deep peak. These peaks at this temperature range refers
to some weight loss of the concrete sample attributed to the evaporation of free
water and water of the C–S–H, Ettringite, hydrated mono-carbo-aluminates of
calcium [15]. In contrast to the 28 days water cured specimens; in this case, the
LCFC demonstrates slightly higher % weight loss than the HCFC corresponding to
the temperature range of 150–350 °C. Strong peaks are also observed at 420 °C,
among which the CC exhibits the largest and the HCFC shows the smallest. The
small peaks refer to the phase that undergoes a modification at this temperature and
not clearly identified [16, 18]. At this stage the mass loss can be considered as the
loss due to the de-hydroxylation of Portlandite. At about 620 °C, one smaller peak is
noticed in case of all types of concrete, among which the HCFC attains the
strongest. Beyond this temperature range, the variation becomes steady for all types
 of the concrete. From the related TGA curve it is observed that for the 90 days water
cured specimen the maximum % weight loss occurs for the HCFC and the minimum
is noticed in the CC. It is also noticed that, with increase in curing days, the %
weight loss corresponding to higher temperature region decreases as demonstrated in
Fig. 6. This is owing to the greater binding effect with increased water curing. All
types of concretes show this behavior. It can thus be inferred that the binding
strength in the carbonated fly ash concrete increases significantly with increase in
water curing period.
4 Conclusion
The major conclusions drawn from the XRD analysis of the cementitious con-
stituents and all types of concrete specimen are enlisted as follows.
 Presence of calcite (CaCO3) as a more frequently appearing crystallite peak
in case of the carbonated fly ash indicate the confirmation of the carbonation
in flyash as used in the concrete sample as partial replacement of cement.
 The XRD studies made it possible to gain better understanding that with
water curing age some elements disappear due to increase in hydration and
phasentransformation. The crystallites such as Alite and Belite disappear in
case of control concrete and fly ash concrete with water curing age and get
transformed to Hatrurite.
 In almost all the concretes Hatrurite is the common crystallite to be formed
over the water curing ages and incase of fly ash concrete only the Zeolite
crystallite are formed at higher water curing age.
The useful inferences drawn from the TGA of the individual cementitious materials
and the all types of concrete are
 Carbonated fly ash concrete with higher level of replacement has the highest
degree of mass loss during TGA experiment indicating the presence of
high amount of calcite in the concrete sample, thus confirming the highest
degree of carbonated material used as the cement replacement.
 At both the water curing ages (28 and 90 days) carbonated fly ash concrete
has the highest mass loss followed by the fly ash concrete and the control
concrete.
 With water curing age the mass loss percentage reduces irrespective of the
types of concrete.