COMPATIBILITY ISSUES OF FLYASH BASED CEMENTS WITH

NANOMATERIALS LIKE NANO-SILICA

M Ghosal*, A K Chakraborty* and S Thomas**

*Indian Institute of Engineering Science & Technology, India

**International and Interuniversity Centre for Nanoscience and Nanotechnology, MG University,
India

1.0 Introduction

With 502 million tons per year (mtpa) of cement production capacity as of 2018, India is the
second largest cement producer in the world next only to China. This could not have been
possible without the power and heat consumptions vis-à-vis its efficiencies, that the industry is
witnessing today, though at the cost of a severe environmental problems i.e. due to its ineffective
waste management. On the lines of Basel Convention, Montreal Protocol or Hazardous and Other
Wastes (Management and Transboundary Movement) Rules, 2016, the waste should be utilized as
a raw material or as fuel or both rather than disposing it. Creating a sustainable economic model
like circular economy which could usher in a ‘EPR’ (Extended Producers’ Responsibility) regime
sharing on the vision of ‘Polluters to Pay’ principles is the need of the hour where industry would
have to take up leadership roles on the lines of Ellen Mac Arthur Foundation [13] in UK, which
work towards the management of waste plastics. In our paper, two most sought after waste of
Indian Cement Industry viz. Fly ash and CO2 is effectively utilized through the addition of
nanosilica and could be gainfully used in cement concrete production.

For decades, major developments in cement-concrete were attained with application of super-fine
particles viz. flyash, silica fume and now, nanosilica, alleviating the problem of scarcity in natural
materials. Also to reduce the carbon emission due to the cement manufacturing, fly ash is partially
replaced in ordinary Portland cement(OPC) and termed as Portland Pozzolona cement (PPC),
which reduces the environmental impact but this replacement of fly ash in OPC deviates its
strength consequently. So, nanosilica as an additive is needed to fill up the deviation, and it is
possible because the silica (S) in the sand reacts with calcium hydrate in (CH) the cement at Nano
scale to form C-S-H bond and its improve the strengthening factor of concrete, which are in turn
helpful in the achieving high compressive strength even in early days [1-7]. Efficiency in the
manufacture of nanosilica has greatly improved in recent decades, leading in a substantial cost
reduction in the use of volumetric chemical admixtures. This has facilitated the penetration of
nanosilica in construction materials, a compound which belongs to the pozzolanic group. This
nanoparticle is the most economical (as it is found in nature in various forms from sand to plant
stems), the most studied and also, the most consumed in cement worldwide [11]. Personal
communication with the manufacturers of Nanodur UHPC (Dyckerhoff) –nanosilica enabled
concrete, suggests that these materials contain nanosilica particles at the point of production [12].

Fig. 1: Nanosilica enabled Concrete manufactured by Dyckerhoff GmbH, Germany

** Based on Author’s request at later stage, S Thomas has been added as Co-author

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
The nanosilica market is majorly driven by growing demand from rubber, concrete, agriculture &
medicine and other applications. Properties such as high tensile strength, bonding strength, and
chemical resistance enhance its use for use in concrete industry. These advantageous properties
are expected to drive the market growth over the forecast period. Stringent regulations regarding
environment compliance for nanosilica precursor material coupled with rising emphasis on
improving the nanosilica applications in the rubber, healthcare & medicine, agriculture, and other
are likely to drive the demand over the forecast period. The growing trend of using nanosilica
would push the market upward resulting in increased demand. In addition, the growing demand
for coatings, concrete, plastics, and electronics is projected to result in significant market growth
of nanosilica over the forecast period, 2016-2025. Rice husk, olivine, bagasse, pyrophyllite along
with sulfuric or hydrochloric acid are the key raw materials that used for the manufacturing of
nanosilica. Nanosilica production is concreted in the Asia Pacific where China is one of the major
producers of nanosilica. Companies including Chirag Minerals, Triveni Chemicals, AkzoNobel
N.V., and Cabot Corporation are some of the key raw material manufacturers of raw materials.
The other important companies engaged in the manufacturing of nanosilica and related products
include NanoPore Incorporated, Bee Chems and so on. The ready products are then supplied to
consumers engaged in manufacturing rubber, coatings, healthcare & medicine, electronics, and
others [14].

Fig. 2: Future projections of Nano-Silica Market (Source: www.grandviewresearch.com)

Coal, which has been the dominant source of fuel for power generation in India (almost 75% is
currently coal-based), will continue to be a critical source for generating baseload electricity and
various estimates indicate that electricity generated from coal is expected to grow twofold to
threefold by 2030. GOI has prescribed 100% flyash utilization way back in 2016 but utilization as
per Central Electricity Authority’s (CEA) reports is round 68% [8] with India ranking 4th in the
world in the production of this waste after USSR, USA & China [9].In India during mid-seventies
and early eighties, engineers/scientists responsible for making standards/specifications/codes had
understood the useful properties of the ash and necessary provisions were made in various
standards such as IS: 456-1976-Code of Practice for Plain & Reinforced Concrete, IS;
1489(Part1)-1976-Specifications for Portland Pozzolona Cement, IS: 2250-1981-Code of practice
for preparation of masonry mortar. In January 2016, IS: 383-2016-Specifications for Coarse &
Fine aggregates for concrete, etc. also recommended use of Bottom Ash as partial replacement of
Coarse Aggregates [10] as a waste reduction approach.

2.0 Methodology Adopted

The materials used were cement - OPC (43 Grade) conforming to IS: 8112-1989, PPC
conforming to IS: 1489-1991, Fine Aggregate (FA) – Natural River sand conforming to Zone II of
IS:383 – 1970, Potable water, Admixture-viz. Nano Silica(nS) supplied by M/s Bee Chems.

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
2.1 Tests on Cement Mortar Composites

Mortar Cubes of 70.7mmx70.7mmx70.7mm size were casted with 1 part of cement + 3 parts of
sand with water added as per the normal consistency formula of Indian standards, IS:4031, i.e.,
according to the standard formula P’= (P/4 +3) (1part Cement+3parts Sand). Here, P’=Quantity of
water & P=Consistency of Cement used. i.e. amount of water used to make 300gms cement paste
to support a penetration of 5-7mm in a standard Vicat mould with a Vicat needle. Nano Silica
were added in various proportions ranging from 0%,0.5%, 0.75%, 1.0%, 1.25%, 1.5% as per
literature review w.r.to cement wt. keeping the w/c ratio fixed at 0.4.The cubes were then ordinary
cured under water at a constant temperature of (27+ 2)°C and tested for compressive strength and
tested at 3 days, 7 days, 28 days , 90 days, 180 days & 365 days, as shown in Fig. 7.

3.0 Numerical Study

Different process of synthesis of nano materials produces different properties. Table 1 and Figure
3 & 4 shows the specific properties of materials used as per our supplier’s literature.

Table 1: Material properties of Nano-Silica used

Item Description
Active Nano Content 35 – 40%
Particle Size 5 – 40 nm
pH (20°C) 9 - 10
Specific Gravity 1.08- 1.32

Fig. 3: Cement Supplier’s Test Certificate of OPC

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
 Fig. 4: Cement Supplier’s Test Certificate of PPC

4.0 Results and Discussion

The Crystalline phases in the nanosilica samples were identified by XRD diffractometry, by using
the diffractometer X’Pert PRO of Panalytical, with /2 geometry, primary Kα1, and ultrafast
detector X’Celerator multichannel, with 0.02° scan step and 6s integration time. The phase
identification was first obtained by using the Match! Software version 1.10 together with the
JCPDS database.

Fig. 5 XRD image of Nanosilica used

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
The Tables 2 & 3 shows the strength development at various ages for various types of cement
composites with Nano-Silica.

Table 2: Strength (N/mm2) for various proportions/ages of nano added OPC mortar (% increase
w.r.to ordinary control cement cubes)

Sl % Nano 3 day Avg. 7 day Avg. 28 day 90 day 180 day 365 day
No. additions in strength strength Avg. Avg. Avg. str. Avg. str.
Cement (% (% strength strength (% (%
(OPC) increase ) increase ) (% (% increase ) increase )
increase ) increase )
1 0 23.72 21.08 31.89 31.20 30.01 30.01
2 0.5% nS 27.16 23.85 35.51 41.3 27.47 26.76
(14.50%) (13.14%) (11.35%) (32.7%) (-9.2%) (-4.29%)
3 0.75% nS 30.10 27.73 42.27 49.85 32.52 31.5
(optimized at (26.89%) (31.54%) (32.55%) (59.8%) (8.4%) (4.96%)
28 days)
4 1.0 % nS 19.38(- 25.07 37.36 42.98 33.68 32.41
18.29%) (18.93%) (17.15%) (37.7%) (12.2%) (8.0%)
5 1.25% nS 27.54 23.17 30.85 39.45 35.24 31.3
(16.10%) (9.91%) (3.26%) (26.4%) (17.4%) (4.29%)
6 1.50% nS 23.35 (- 23.81 37.79 33.42 31.23 29.12
1.56%) (12.95%) (18.5%) (7.12%) (4.07%) (-2.96%)

Table 3: Strength (N/mm2) for various proportions/ages of nano added PPC mortar (% increase
w.r.to ordinary control cement cubes)

Sl % Nano 3 day 7 day 28 day 90 day 180 day 365 day

No. additions in strength strength strength strength str. (% str. (%
Cement (% (% (% (% increase) increase)
(PPC) increase) increase) increase) increase)
1 0 9.97 11.36 22.44 25.96 27.08 23.52
2 0.5% nS 12.68 8.93 (- 27.16 22.45 (- 26.11 (- 21.26 (-
(27.18%) 21.39%) (21.0%) 13.52%) 3.58%) 9.61%)
3 0.75% 18.36 23.66 27.45 33.17 27.0 (- 35.5
nS(optimized (84.15%) (108.2%) (22.32%) (27.77%) 0.29%) (50.94%)
at 28 days)
4 1.0 % nS 17.37 18.97 27.56 32.08 31.35 27.77
(74.22%) (66.99%) (22.81%) (23.57%) (15.77%) (18.07%)
5 1.25% nS 16.10 19.15 26.20 28.11 22.78 (- 31.69
(61.48%) (68.57%) (16.75%) (8.28%) 15.88%) (34.74%)
6 1.50% nS 16.96 19.26 22.92 32.30 26.53 (- 20.41 (-
(70.11%) (69.54%) (2.14%) (24.42%) 2.03%) 13.22%)

The OPC mortar compressive strength determined as per IS:4031 shows a 32.55% increase in
strength at 0.75% nS (optimized addition) at 28 days, with the rate of strength gain increasing up
to 59.8% at 90 days but then falling by 8.4% & 4.96% at 180 & 365 days, at same optimization
(Table 2). This optimization varies with Portland Pozzolona Cement (PPC) with 1% nS w.r.to
cement wt. where it is observed that the consistency in gain of strength at 28 has been retained in
the long term of 365 days, showing strength of 35.5N/mm2 which is more than 12% increase over
that of OPC (31.5N/mm2) at same optimizations (Table 3).

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
 60
50
Ctrl Samp.
40
Ccompressive Strength,MPa 30 Ns=0.5%
20 nS=0.75%
10 nS=1.0%
0
nS=1.25%
7 days 28 days 90 days 180 365
days days nS=1.5%
Age

50
40
Ctrl Samp.
30
Ccompressive Strength,MPa

Ns=0.5%
20 nS=0.75%
10 nS=1.0%
0 nS=1.25%
7 days 28 days 90 days 180 365
nS=1.5%
days days
Age

Fig. 6: Strength Development trends of Nano-Silica added OPC (top) & PPC (bottom)
Mortar

Fig. 7: Casting, Curing & Testing of Nano-Silica added Cement Mortar Cubes

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
5.0 Conclusions

1. Optimizations for Nano Materials are nS=0.75% for OPC and also for PPC at 28 days.
However for long terms, the strength rate is seen falling for Nano-silica added OPC while fly-
ash based PPC with Nano-silica additions arrests this rate fall as shown in Fig.6 & Fig.8.
2. As increasing fineness causes an increased rate of hydration and subsequent high strength.
Here as per Fig.3 & 4, the specific surface area of PPC is more than that of OPC i.e. 396
m2/Kg  327m2/Kg. So, PPC has long term advantage than OPC with constant strength gain
rate and with Nano-silica addition, the nucleation effects, pozzolanic effects and pore-filling
effects are enhanced thus contributing to PPC’s constant long term strength gain rate.
3. Nano concrete could control the carbon dioxide emission from the earth thus reducing GHG
emissions and controlling climate, by using fly ash concrete products instead of cement
concrete.
4. As per Suppliers specifications shown in Table 1, the Nano particles is of particle sizes 5-
40nm, and is in the form of partly crystalline silica (as per Fig.5). So it can easily react with
cement particles which are normally in Nano scale and initiate the CSH reaction and hence
accelerate the compressive strength of concrete.
5. Thus, Nano-silica at the nano-scale level, consumes calcium hydroxide crystals, reduces the
size of the crystals at the interface zone and transmute the calcium hydroxide feeble crystals
to the C-S-H crystals, and improves the interface zone and cement paste structures.
6. For special concrete structures such as petrol tanks, bunkers and silos, oil well we may use
this type of special concrete to get more strength and performance.

Strength Development with OPC/PPC (with

Compressive Strength,MPa

or without nS)
50
45
40
35
30
25
20
15
10
5
0
7 days 28 days 180 days 365 days
OPC 21.08 31.89 30.01 30.01
OPC+nS 27.73 42.27 32.52 31.5
PPC 11.36 22.44 27.08 23.52
PPC+nS 23.66 27.45 27 35.54

Fig. 7: Bar Chart showing the variations in maturity of OPC/PPC Mortars (with or without
nS) at different ages

References:

1. Yuvraj,S.et al., Experimental Research On Improvement Of Concrete Strength And

Enhancing The Resisting Property Of Corrosion And Permeability By The Use Of Nano
Silica Flyashed Concrete. International Journal of Emerging Technology and Advanced
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2. Said, A.M.; Zeidan, M.S.; Bassuoni, M.T.; Tian, Y. Properties of concrete incorporating
nano-silica.Constr. Build. Mater. 2012, 36, 838–844.

16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA
3. Chithra, S.; Senthil Kumar, S.R.R.; Chinnaraju, K. The effect of colloidal nano-silica on
workability, mechanical and durability properties of high performance concrete with copper
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Overview, Current Science, Vol.100, No.12, page 1791-1794,2011.
10. IS:383 – 2016, Indian Standard Code of Specification for coarse and fine aggregates for
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16th NCB International Seminar on Cement, Concrete and Building Materials

03 - 06 December 2019, New Delhi, INDIA