Fly Ash Based Nano Geopolymeric

Materials for Broad application

Spectrum

Dr. S.S. Amritphale

Chief Scientist and Head
Materials for Radiation Shielding and
Cement Free Concrete
CSIR-Advanced Materials and Processes
Research Institute, Hoshangabad Road,
Bhopal (M.P.) 1
An environmental alternative to
CO2-producing Portland Cement
2
 Characteristics of Geopolymers Compared with OPC
Energy Saving , Environmental Protection and Production Cost :
Synthesis of geopolymers occurs at very low temperature.
Resulting in 3/5th less energy consumption than OPC. 80% less CO2
emission. Due to this reason they are called GREEN MATERIALS.
Low production cost as they are based on aluminosilicate raw
materials naturally occuring on earth crust or derived from

3
industrial waste
Portland cement Geopolymeric cement

5CaCO3+2SiO2 3CaO.SiO2+2CaO. SiO2+5CO2 Al2O3+SiO2 in raw material

20-90ºC
1450ºC +additives

Clinker Phases -Si-O-Al-O-

Hydration ( curing with non curing

water)

C-S-H + Ca(OH)2 Alumino silicate 3D framework

 Proposed mechanism of geopolymerisation takes
place in four steps
i) Dissolution of Si and Al from solid alumino silicate raw
materials using additives
ii) Formation of Si and Si/Al oligomers in aqueous phase
iii) Polycondensation of oligomers to from three dimensional
alumino silicate framework
iv) Bonding of the solid particles into geopolymeric framework
and hardening of whole system into a final solid
polymeric structure
Characterised by the formula Mn[-(-Si-O)z-Al-O]n.wH2O
Where M is K, Na or Ca , n is the degree of
polycondensation, z=1,2,3 or more than 3 is formed
4
Geopolymers (earthly originated inorganic polymeric
materials)
 New family of synthetic aluminosilicate materials Mimicking synthesis
of natural volcanic Zeolitised rocks .
 Formed by activation of solid alumino silicate raw materials.
 Penetration of Al into Si-O-Si structure is a unique feature of the reaction

Geopolymeric structure Three basic forms of geopolymer

showing Al-O-Si bonds

Polymeric structures from

polymerisation of
5
monomers
Amorphous (gel like), partially amorphous
or crystalline
Network configurated of SiO4 and AlO4
tetrahedrons united together by oxygen
bridges.

Davidovits model of Barbosa model of geopolymer

6
geopolymer structure structure
 Materials in Geopolymers
Industrial Minerals:
Kaoline
Bentonite
Feldspar
Industrial Bye products:
Fly ash
Red Mud
Metallurgical slag
Latter class are attractive from environmental reasons.
Results in reuse of waste and conservation of natural
resources
7
 Characteristics of Geopolymers

Geopolymers can gain 70% of strength in first four hours of

setting
Geopolymers concrete can withstand thousands of years
weathering attack without too much function loss e.g.
Egypt Pyramids
Geopolymers can withstand 10000C to 12000C without
loosing functions.

Very good resistance to freeze thawing cycles.

Geopolymer concrete is resistant to chemically aggressive

species and corrosion
8
Contd…
 Application Spectrum of Geopolymers
The type of application according to the Si:Al ratio
S.N. Si:Al Ratio Application
1 1 Bricks
Ceramics
Fire protection
2 2 Low CO2 cements and concretes
Radioactive and toxic waste encapsulation
3 3 Foundry equipments,
Heat resistant composites 200oC to 1000oC
Tooling for aeronautics titanium process
4 >3 Sealants for industry, 200oC to 600oC
Tooling for aeronautics
5 20-35 Fire resistant and heat resistant fibre
composites 9
 Advanced Applications
Immobilisation of Hazardous and Radioactive Wastes: Toxic
metals present in the waste materials mix with geopolymer
and tightly locked into the 3D network of the bulk matrix
Automotive and aerospace industries: Carbon-fiber reinforced
geopolymer composites did not ignite, burn, or release any
smoke even after extended heat flux. Therefore, they are
suitable as aircraft cabin materials for cargo liners, ceiling,
floor panels, partitions and sidewalls, and wire insulation etc.
to eliminate cabin fire in air craft accidents.

A carbon-epoxy aerospace composite

Cabin fire in aircraft accidents
is burning while a carbon-geopolymer
10
composite still resists a 1200°C fire.
Geopolymer LTGS bricks :This brick uses a very cheap
material available in great quantity: lateritic clay earth.
Suitable to manufacture structural
elements like beams for doors and
windows. Requires less equipment
and is less expensive to produce and
can be produced in a village or a small
city with less equipment and finance

Breathing House: A house built out

of LTGS brick will be naturally air-
conditioned and fresher. These
geopolymers, which constitutes the
matrix of the brick, have the
property “to breathe. Therefore
provide a cooling of the house and
insulation against the heat 11
Rapid repair and construction of runways
After few hours pyrament runway is
ready for heaviest aircrafts reaching a
strength that conventional concrete can
achieve only after several days
Light weight/fire retardant Materials:Acoustic
panels and Light weight advance materials
Archaeological Analogues: It is proved
that microstructure of hardened
geopolymer materials is similar to that
of ancient constructs such as Egyptian
pyramid Many experts suspected that
they might be cast in place through geo-
-polymerisation rather than from man
made stones. Research is under progress
12
to solve this problem.
Chemistry of Cement Free Nano
Geopolymeric Materials
Developed at CSIR –AMPRI,
Bhopal

13
 Patents
1. A composition for advanced hybrid geopolymeric
functional materials and a process for the preparation
thereof.”
Sudhir Sitaram Amritphale, Deepti Mishra , Ramesh
Kumar Chouhan, Manish Mudgal ,Mohammed Akram Khan
,Swati Lahiri, Navin Chandra, Barada Kanta Mishra.
Filed in India (2301 DEL 2012) and USA (US
20140026787A1). Accepted for grant in USA
2. A novel process for making “ tailored precursor
materials” in a solid powder form, useful for further
broadening the application spectrum of the conventional
geopolymeric system.
Sudhir Sitaram Amritphale, Manish Mudgal, Ramesh Kumar
Chouhan, Deepti Mishra, Navin Chandra.
Allowed for Grant in USA (Application Number 14 /
599,877) 14
Chemistry of advanced
hybrid inorganic organic
nano geopolymeric
functional materials”

15
Mechanism of Conventional Nano Geopolymeric Material

Additives

Conventional Geopolymeric Material 16

Mechanism of Advanced Hybrid Inorganic Organic Nano Geopolymeric
Material Precursors From Fly
Ash

Typical Chemical Analysis of

Fly Ash

Typical Additives
Chemical
Analysis of
Rice Husk

Hydrated
SiO2 and Setting
Precursors
from Rice
Husk 17
Hybrid Inorganic Organic nano geopolymeric Material
Cellulose 35%, Hemicellulose 25% and lignin 20 %)
 FESEM: Nanosized
particle of Si and Al
species in the range of
35 nm to 44 nm.
FESEM of conventional nano
geopolymeric materials

FESEM: Nanosized
particles of Si and Al
species in the range of 17
nm to 46
EDX spectra of Hybrid
Inorganic Organic nano
18
geopolymeric material
 EDX of advanced hybrid organic-
inorganic nano geopolymeric materials

EDX:
Presence
of Si,
Al ,Na, C
and O.
EDX spectra of advanced hybrid organic-
inorganic nano geopolymeric materials 19
Conclusion of FESEM: In advanced hybrid organic-inorganic
nano geopolymeric materials it is possible to obtain size of the
particles as low as 17 nm whereas in conventional nano
geopolymeric materials the minimum size obtained was 35 nm.

Conclusion of EDX: Both the examples indicated presence of

carbon, oxygen, aluminum and silicon. Carbon and oxygen are
predominant in both the samples whereas silicon is predominant
in one sample and aluminium is predominant in another sample.

Presence of carbon in both the samples indicated participation

of organic molecules from rice husk and silicon and aluminium
indicated participation of glassy silicoaluminous phase from fly
ash as well as amorphous silica from rice husk. Thus
confirming formation of nano hybrid inorganic -organic
geopolymer matrix.
20
Novel Concept of CSIR-AMPRI, Bhopal for making Advanced Hybrid
Inorganic Organic Nano Geopolymeric Material .
-OH moieties of
Conventional Tetra and organic precursors Novel Penta coordinated
penta coordinated silicon silicon complexes
In-Situ Synthesis of
complexes
additives OCH2 M+
CH2O
CH2O OCH2 Si
Si
CH2O OCH2
CH2O OCH2
OCH2
Conventional nano
Advanced Hybrid Inorganic
Geopolymeric Material CH2O -----n
Organic geopolymeric Material

Advanced Hybrid Inorganic Organic nano geopolymeric Material enables

improved Engineering Properties.
Reference:
1.Synthesis of pentacoordinate silicon complexes from SiO2, Richard M. Laine,
Kay Youngdahl Blohowiak, Timothy R. Robinson, Martin L. Hoppe, Paola Nardi,
21
Jeffrey Kampf & Jackie Uhm, Nature 353, 642-644 (17 October 1991)
 -109.67
-92.14
-82.02
-88.54

-96.63
29Si MAS @8KHz
Sample:1
20/07/12

-109.44
-90.11
-96.18

1. Si NMR of conventionally developed

29

nano geopolymeric material

2. 29
Si NMR of advanced hybrid organic-
inorganic nano geopolymeric material
developed by patented process

29Si MAS @8KHz

Sample:2
21/07/12

-20 -40 -60 -80 -100 -120 -140 -160 ppm

 Si NMR of conventionally
29

-109.67
-88.54
-82.02

-92.14
-96.63
developed nano geopolymeric
material

29Si MAS @8KHz

Sample:1
20/07/12
-109.44
-90.11
-96.18

29
Si NMR of advanced hybrid
inorganic- organic nano
geopolymeric material
developed by patented process

29Si MAS @8KHz

Sample:2
21/07/12

-20 -40 -60 -80 -100 -120 -140 -160 ppm

29Si NMR Signals at -82 ppm, indicates
tetracoordinated geometry and signals at
indicates pentacoordinated geometry
around silicon atom in conventional nano
geopolymeric material.
29Si NMR Signals at indicates
pentacoordinated geometry around silicon
atom.
 Absence of NMR signals at -82 ppm,
indicates absence of tetracoordinated
geometry around silicon atom in hybrid
inorganic-organic nano geopolymeric
24
material..
 27Al MAS@10kHz
27Al MAS@10kHz LSA

59.20

-2.11
CG

59.20
05/03/14

-2.11
NAME 27Al-Ext-Feb-14
NAME 27Al-Ext-Feb-14 EXPNO 4
EXPNO 3 PROCNO 1
PROCNO 1
Date_ 20140305 Date_ 20140305
Time 14.35 Time 15.31
INSTRUM spect INSTRUM spect
PROBHD 4 mm MAS BB H8 PROBHD 4 mm MAS BB H8
PULPROG zg PULPROG zg
TD 3072 TD 3072
SOLVENT None SOLVENT None
NS 3898 NS 4000
DS 0 DS 0
SWH 125000.000 Hz SWH 125000.000 Hz
FIDRES 40.690105 Hz FIDRES 40.690105 Hz
AQ 0.0123380 sec AQ 0.0123380 sec
RG 228 RG 228
DW 4.000 usec DW 4.000 usec
DE 10.00 usec DE 10.00 usec
TE 303.0 K
D1 2.00000000 sec TE 303.0 K
TD0 1 D1 0.50000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 27Al ======== CHANNEL f1 ========
P1 0.38 usec NUC1 27Al
PL1 4.90 dB P1 0.38 usec
SFO1 78.2046920 MHz PL1 4.90 dB
SI 8192 SFO1 78.2046920 MHz
SF 78.2044669 MHz SI 8192
WDW EM SF 78.2044669 MHz
SSB 0 WDW EM
LB 75.00 Hz SSB 0
GB 0 LB 75.00 Hz
PC 0.20 GB 0
PC 0.20

400 300 200 100 0 -100 -200 -300 -400 ppm

400 300 200 100 0 -100 -200 -300 -400 ppm

27
Al NMR of conventional Al NMR of hybrid 27

nano geopolymer inorganic organic

nano geopolymer
Conclusion: The presence of 27Al NMR signal at 55 ppm
which is characteristic of geopolymer formation is found in
both conventional nano geopolymer as well as in hybrid
inorganic-organic nano geopolymer and thus confirmed the
formation of geopolymeric material in both the materials. 25
 X-ray diffraction pattern of fly ash
4000
Peak Assigned to Peak Assigned
No. No. to*
3000

1 - 13 Q,M,H
2000

2 Q 14 Q,M
1000

3 - 15 M

0 20 40 60 4 M 16 Q,M,H
2 theta (deg)

5 M 17 Q,M,H
[ Assigned to* following phases:
Q, Quartz, syn: Silicon oxide, SiO2 , Q 18 Q,M
6
JCPDS 46-1045
7 M 19 Q,M,H
M, Mullite, Aluminium silicate, M,H 20 Q,M
3Al2O32SiO2, JCPDS 06-0258 8
9 M,H 21 M
H, Hematite, Iron oxide, Fe2O3, JCPDS 01-
10 Q 22 Q,M,H
1053
11 M 23 Q,M,H
GSA Glassy silico aluminous phase as 26
diffused pattern of amorphous material ] 12 Q,M
X-ray diffraction pattern of conventional nano geopolymeric
materials
Peak Assigned Peak Assigned
No. to No. to*
1 C 17 SASH
2 C 18 M,C
3 Q,SASH 19 C
4 H,C,SAS 20 M,H,C
5 SASH 21 C
6 M 22 C,SAS,SAS
20 40 60
H
0
2 theta (deg) 7 Q 23 H,C
Conventional nano geopolymeric material 8 C,SAS,SASH 24 Q,SASH
10 SAS 25 M,H
C, Cancrisilite :sodium aluminium carbonate
11 SAS,SASH 26 H
silicate hydrate , Na7[Al5Si7O24]CO3.3 H2O 12 SASH 27 M
13 H,C,SASH 28 Q
Q, Quartz: Silicon oxide, SiO2
14 M,C,SAS,SA 29 M
M, Mullite, Aluminium silicate, 3Al2O32SiO2, SH
15 M,H,C,SAS 30 M,H
H, Heamatite, Iron oxide, Fe2O3, 16 C 31 M
17 C,SAS 32 M
SAS: Sodium aluminium silicate, NaAl3Si3O11
27
SASH, Herschelite, sodium aluminium silicate
X-ray diffraction pattern of Hybrid inorganic -organic nano
geopolymeric materials
Peak Assigned to Peak Assigned
No. No. to*
1 C,S, NC 15 C,G
2 Q,SASH,PH,G 16 M,H,C,S,
NC
3 PH,S,NC 17 C,SAS
4 PH,S 18 C,S
5 C,SAS 19 S
0 20 40 60 6 C,SAS,SASH, 20 Q,S
2 theta (deg) S,G
Hybrid inorganic organic nano geopolymeric
7 M,G 21 SASH
material
C, Cancrisilite :sodium aluminium carbonate 8 Q 22 M,H
silicate hydrate, a7[Al5Si7O24]CO3.3 H2O , 9 SAS,NC,G 23 M
10 SAS,SASH,S, 24 Q
Q, Quartz: Silicon oxide, SiO2 ,
G
M, Mullite, Aluminium silicate, 3Al2O32SiO2, 11 M,H,SASH,S, 25 M
H, Heamatite, Iron oxide, Fe2O3, NC
SAS: Sodium aluminium silicate, NaAl3Si3O11 12 M,H,C,SAS,N 26 M,H
SASH, Herschelite, sodium aluminium silicate C
hydrate, NaAlSi2O6.3H2O 13 C,PH,S 27 M
14 C,SAS,S,G 28 Q
S, Sucrose, C12H22O11,
G, α D-Glucose: C6H12O6, 28
NC: Native cellulose, (C6H12O6)x
Conclusion: The XRD studies confirmed
the simultaneous presence of inorganic
phases namely Cancrisilite , Herschelite,
sodium aluminium silicate, quartz,
mullite, hematite and organic phases
namely native cellulose, α D-glucose and
sucrose leading to the formation of
hybrid inorganic organic nano
geopolymeric material.

29
 100

80

60

40

20

3500 3000 2500 2000 1500 1000 500

Wavenumber, cm-1

FTIR Spectrum of fly ash

Wave number, cm-1 Assigned to

3448 Si-OH stretching vibrations
2360 H-O-H stretching vibrations
1628 H-O-H stretching vibrations
1091 Si-O-Si and Al-O-Si asymmetric stretching
559 Si-O-Si and Al-O-Si asymmetric stretching 30
 FTIR-Conventional nano geopolymer
Wave Assigned to
number, cm-1
3339 Si-OH
2160 O-H, H-O-H streching
100
1641 O-H bending
90
1374 Si-O-X (Si,Na)
80
1062 Si-O-Si stretching
70
vibration
60 1010 Alkaline aluminosilicate
50 gel band
(T-O, T=Si or Al)
confirming fusion of both
Al-O and Si-O
asymmetric stretching i.e.
3500 3000 2500 2000 1500 1000 500
geopolymerisation
Wavenumber, cm-1
886 Sodium bicarbonate
deformation band
FTIR spectrum of 841 Al-O-Si asymmetric
conventional nano stretching
geopolymeric material 772 Quartz double band
557 Mullite band
516 O-Si-O bond band 31
 FTIR-Hybrid inorganic organic nano
geopolymer
Wave Assigned to
100
number,
90 cm-1
3461 Si-OH vibration,O-H stretch
80 (Phenol)
1643 H-O-H bending , C-C stretch
70
in ring
60 1463 C-O-C, C-C stretch in ring,
CH2+ OCH, CCH (glucose
50
and sucrose)
40 1386 CH bending , C-CH3, OCH,
COH CCH (glucose and
sucrose)
1022 CH deformation (cellulose) ,
CO (glucose ) and Alkaline
aluminosilicate gel band (T-
3500 3000 2500 2000 1500 1000 500 O, T=Si or Al) confirming
Wavenumber, cm-1 fusion of both Al-O and Si-
O asymmetric stretching i.e.
geopolymerisation
FTIR spectrum of novel hybrid 850 Si-O bending (cancrisilite),
C-H (Phenol) , CH (glucose
inorganic -organic nano and sucrose)
geopolymeric material 789 Si-O stretching
(cancrisilite), + (glucose)
565 Si-O-Si and Al-O-Si
symmetric stretching
32
vibration
Conclusion: Thus additional peaks due to
organic molecules are observed in IR spectra of
hybrid inorganic -organic nano geopolymeric
material in addition to inorganic phases
observed in conventional nano geopolymeric
material.

Thus participation of organic molecules from

rice husk in presence of alkali during
geopolymerisation is also confirmed by IR
spectra in addition of XRD of hybrid inorganic
organic nano geopolymeric material.
33
Chemistry of a novel process for
making “ tailored precursor
materials” in a solid powder form
in nano size , useful for further
broadening the application
spectrum of the conventional
nano geopolymeric system.

34
FESEM studies of nano tailored precursor material consisting of fly ash, rice
husk and additive in solid powder form after grinding of 8 hours, 16 hours and 24
hours.

Size of nano particles of solid tailored

precursor material observed in the range of
40.9 nm to 77.4 nm after 8h grinding
SEM after grinding of 8 duration.
hours

Size of nano particles of solid tailored

precursor material observed in the range of
29.7 nm to 40.9 nm after 16 h grinding
duration.
SEM after grinding of 16
hours
Size of nano particles of solid tailored
precursor material observed in the range of
23.3 nm to 29.3 nm after 24 h grinding
duration.
SEM after grinding of 24 35
hours
 Si NMR studies of nano tailored precursor material consisting of fly
29

ash, rice husk and additive in solid powder form after grinding of 8
hours, 16 hours and 24 hours.

-103.352
-84.830
-93.350
FA NaOH RH 24h

-105.863
-94.461
-84.180

FA NaOH RH 16h
-105.28
-85.63
-98.97

FA NaOH RH 8h

100 50 0 -50 -100 -150 -200 ppm

36
Conclusion:

Signals centred at -85 ppm for grinding duration of 8 hours, at -84 ppm for
grinding duration of 16 hours and of 24 hours respectively indicated
tetracoordinated geometry around silicon atom.

 Signals centred at for grinding duration of 8 hours, 94 ppm and 105 ppm
for grinding duration of 16 hours and at for grinding duration of 24 hours
corresponds pentacoordinated geometry around silicon atom.

Thus complete transformation of tetracoordinated silicon to

pentacoordinated silicon is not possible without the presence of aqueous
additives.

Bond lengthing through higher coordination is well known effect in silicon

chemistry . The bond length increases upto 5 % in pentacoordination which
imparts improved flexibility , reactivity and thus functionality in solid tailored
precursor material leading to improved flexural strength and compressive
strength.

 The confirmation of α-d -glucose in XRD studies is responsible for

formation of pentacoordinated silicon.   37
27
Al NMR studies of nano tailored precursor material consisting of fly
ash, rice husk and additive in solid powder form after grinding of 8
hours, 16 hours and 24 hours.
.

68.237
54.845
24 hours grinding duration duration

FA NaOH RH 24h
68.333
54.248

16 hours grinding duration

FA NaOH RH 16h
52.932
66.962

8 hours grinding duration

FA NaOH RH 8h
200 150 100 50 0 -50 -100 -150 -200 ppm 38
Conclusion:

The presence of 27Al NMR signal at 52 ppm & 66 ppm

for grinding duration of 8 hours, 54 ppm & 68 ppm for
grinding duration of 16 and 24 hours, indicated four
coordinated aluminum in silico aluminates.

Further it has also been reported by Davidovits that in

27
Al spectra of the silico aluminates, four coordinated
aluminum resonates approximately at about 50+20
ppm. Thus it is concluded that the nano solid
tailored precursor material formed is confirming to
geopolymeric characteristics
39
X-ray diffraction studies of nano tailored precursor material consisting of
fly ash, rice husk and additive in solid powder form after grinding of 8
hours
Peak Assigned to Peak Assigned to*
No. No.
1 SAO 13 Q,M,H,SAO,S
ASH,G
2 Q, SAS,SASH,G 14 Q,M,SAO,SAS
H,SS,G
3 SAS., SASH,SS,G 15 Q,M,H,SAO,S
ASH,SS,G
Assigned to* following phases:
4 SAO 16 M,SAO,SASH,
[Q, Quartz: Silicon oxide, SiO2 , Cat No.02-0458
G
5 Q,M,SS,G 17 Q,M,H,SAO,S
M, Mullite, Aluminium silicate, 3Al2O32SiO2, Cat No.-
ASH,G
02-0452.
6 M,SAS,SAO,SAS 18 Q,SASH,G
H,SS,G
H, Hematite, Iron oxide, Fe2O3, Cat No.01-1053.
SASH,G 19 G
SAO- Sodium Aluminium Oxide, NaAl6O9.5 :Cat No.47- 7
0320. 8 M,H,SAO,SASH, 20 M,H,SAO,SAS
SS H,G
SASH- Sodium aluminium silicate hydrate, 9 M,H,SAS,SAO,SA 21 Q,M,SAO,SAS
NaAlSi2O6.3H2O, Cat No.19-1178. SH,SS,G H,G
10 Q,M,SS,G 22 M,SAO
SS- Sodium silicate, Na2Si3O7, Cat No.38-0019 11 SASH,G 23 Q,M,H,SAO
12 Q,M,SAO,SASH,
SAS: Sodium aluminium silicate, SS,G
Na39.8Al70.4Si41.20207.9 Cat No.47-0356 40
X-ray diffraction studies of nano tailored precursor material consisting of
fly ash, rice husk and additive in solid powder form after grinding of 16
hours
Peak Assigned to Peak Assigned
No. No. to*
1 SAO 13 Q,M,SAO,SASH,
SS,G
2 Q,SASH,G 14 SS,G
3 SAS., 15 Q,M,SAO,SASH,
SASH,SS,G G
Assigned to* following phases: 4 SAO,G 16 Q,M,H,SAO,SAS
H,G
Q, Quartz: Silicon oxide, SiO2 ,Cat No.02-0458 5 Q,M,SS,G 17 Q,M,SAO,SASH,
M, Mullite, Aluminium silicate, 3Al2O32SiO2, Cat G
6 M,SAS,SAO,S 18 SS,SASH,G
No.02-0452. ASH,SS,G
H, Hematite, Iron oxide, Fe2O3, Cat No.01-1053. 7 SASH,G 19 Q,M,H,SAO,SS,
G
SAO- Sodium Aluminium Oxide, NaAl6O9.5 :Cat
8 SASH, G 20 M,SAO,G
No.47- 0320. 9 SAO,SASH,SS, 21 M,H,SAO,G
SASH- Sodium aluminate silicate hydrate, G
10 M,H,SS,G 22 Q,G
NaAlSi2O6.3H2O, Cat No.19-1178.
11 M,H,SAO,SAS 23 M,H,SAO,G
SS- Sodium silicate, Na2Si3O7, Cat No.38-0019 H,SS,G
SAS: Sodium aluminium silicate, a39.8Al70.4Si41.20207.9,
12 G 24 Q,M,SAO,G
25 Q,H,SAO 41
Cat . No.47-0356
X-ray diffraction studies of nano tailored precursor material consisting of
fly ash, rice husk and additive in solid powder form after grinding of 24
hours
Peak Assigned to Peak Assigned to*
No. No.
1 SAO 13 Q,M,SAO,SASH,S
S,G
2 Q,SASH,SAS, 14 G
G
Assigned to* following phases: 3 SAS., 15 Q,M,SAO,SASH,G
Q, Quartz: Silicon oxide, SiO2 , Cat No. 02-0458 SASH,SS,G
4 M,SAO,SS 16 Q,M,SAO,SASH,S
M, Mullite, Aluminium silicate, 3Al2O32SiO2, Cat S,G
No.02-0452. 5 Q,SS,G 17 Q,M,SASH,SS,G
6 M,SAS,SAO, 18 Q,M,H,SAO,SASH,
H, Hematite, Iron oxide, Fe2O3, Cat No.01-1053. SASH,SS,G G
7 SASH,G 19 Q,M,H,SAO,SASH,
SAO- Sodium Aluminium Oxide, NaAl6O9.5 :Cat G
No.47-0320. 8 SASH,SAO,S 20 M,H,SAO,SASH,G
SASH- Sodium aluminate silicate hydrate,
S
NaAlSi2O6.3H2O, Cat No.19-1178. 9 M,H,SS,G 21 Q,M,SAO,SASH,G
10 M,H,SAS,SA 22 Q,M,H,SAO
SS- Sodium silicate, Na2Si3O7, Cat No.38-0019 O,SASH,SS,G
11 Q,M,SS,G 23 Q,M,H,SAO
SAS: Sodium Aluminium Silicate, 12 SAO,SASH,S
Na39.8Al70.4Si41.20207.9 Cat No.47-0356 S,G 42
Conclusion:

Increase in intensity of peaks of Quartz, Mullite and Hematite with increase in

grinding duration from 8h to 24h shows that the glassy phase present in fly ash is
consumed in formation of nano geopolymeric precursors. However, There is marginal
increase in intensity of these peaks with increase in grinding duration from 8h to 16h.
But significant increase in observed in intensity for these phases on increase in
grinding duration to 24 hours.

Some of the peak due to quartz mullite and heamatite present in tailored precursor
material of 8h and 16 h grinding duration get disappeared in nano tailored precursor
material of 24h grinding duration. This indicated conversion of some portion of these
crystalline phases of fly ash to amorphous silico aluminous phase. This is further
confirmed by presence of more number of peaks of sodium silicate in nano tailored
precursor material of 24h grinding duration. As amorphous silico aluminous phase
obtained reacts with solid powdered NaOH to form sodium silicate.

Presence of peak of α-D-glucose indicated participation of hemicelluloses from rice

husk. This α-D-glucose is responsible for formation of penta coordinated silicon
complexes as confirmed in 29 Si NMR of solid tailored precursor materials in nano size.

Peaks due to native cellulose, sucrose, phenol were observed in the developed
material are absent in present invention indicates novelty of our nano solid tailored
precursor material.
43
 
 Conclusion:
The nanosize of solid tailored precursor material decreases
with increase in grinding duration from 8h to 16 h and 24
hours.
Smallest size of nano particles with very narrow size
distribution is observed in the range of 23.3 nm to 29.3 nm
after 24 h grinding duration.
The nano size of Sodium Aluminium Oxide, Sodium aluminium
silicate hydrate, ,Sodium silicate, Sodium Aluminium Silicate,
α-D-Glucose phases obtained in grinded solid powder form
increases
amorphous nature
helps in continuous growth of silicon- aluminium oxygen
polymeric chains and
Thus leading to homogeneous, densified , strong and flexible
matrix with improved engineering properties
44
 Nano particle incorporated
advanced nano geopolymeric
materials for corrosion
resistant coating applications

45
Synthesis of TiO2 Nanoparticles for preparation of nanoparticles
incorporated geopolymer based coating material.

31.78nm by
Debye
Scherrer’s
formula

46
 XRD of Titanium dioxide Nano-particles

SEM images of
Titanium dioxide
Nano-particles

FTIR of Titanium dioxide Nano-particles

Block diagram of TiO2 nanoparticles incorporated geopolymer
coating using Mild steel by Spray gun
TiO2 Nanoparticle incorporated geopolymer
coating on mild steel by spray gun 49
 Characterization of TiO2 Nanoparticle incorporated
geopolymer based coating

Corrosion test by
Adhesion strength test: electrochemical
measurements

Direct flame test Water stability test Corrosion test by

immersion in 3.5 % NaCl 50
Heat resistant Test in furnance at temperature range of 100 to 7000C
 Quartz, Mullite, Mullite syn (Synthetic
mullite), Chantalite, Aluminium
phosphate, Sodium aluminium oxide,
Titanium oxide, Iron titanium oxide
and Sodium titanium oxide are
present in major phase

 Bohmite, Sodium silicate, Hematite,

Herschelite, Chabazite, Silicon
phosphate, Iron titanium oxide
hydrate, Sodium iron titanium,
Sodium aluminium titanium oxide and
SEM image representing FRT coating
Sodium titanium oxide phosphate are and its interface with mild steel
present in minor phase.

Characterization of TiO2 Nanoparticle incorporated 51

Conclusion :

TiO2 nanoparticles incorporated geopolymer based coating material are stable at

600oC than conventional geopolymeric based coating materials sample which were
stable upto 500oC only .

TiO2 nanoparticles incorporated geopolymer based coating material are passes

direct flame test of ½ hour, while conventional geopolymeric based coating
materials gets disintegrated with mild steel surface and minor cracks are observed
on the surface.

 By the immersion in 3.5 % NaCl for corrosion test for 480 hours, TiO 2
nanoparticles incorporated geopolymer based coating material shows better
corrosion resistance as shows corrosion rate of 0.21769mmpy while conventional
geopolymeric based coating materials shows the corrosion rate of 1.76 mmpy.

By the electrochemical measurement also, TiO2 nanoparticles incorporated

geopolymer based coating material have the better corrosion resistivity than
conventional geopolymeric based coating materials as shows current of 75nm at
0.2V after 21st days while the conventional geopolymer coated sample show the
current of 200nm at 0.2V after 21st days.

In Water stability for 456 hours, TiO2 nanoparticles incorporated geopolymer
52
based coating material shows less change in mass than conventional ones.
Synthesis of Alkaline Iron Oxide
Nanoparticles by Novel
Solvothermal Approach for
Radiation Shielding Application

53
 Characterisation of Alkaline Iron Oxide Nanoparticles

FESEM Size:30.7 nm to 96.9 nm.

Element Weight% Atomic%

CK 35.11 52.50
OK 29.33 32.93
Na K 3.52 2.75
Al K 0.26 0.17
Si K 3.16 2.02
Cl K 2.33 1.18
Fe L 26.29 8.45
Totals 100.00

54
EDX :indicated the presence of C, O, Fe and sodium
 XRD:

 NaFeO2 (tetragonal) major phase

 NaFeO2.H2O orthorhombic)
FeCO3(siderite, rhombohedral),as
the minor phases

FTIR:
O-H ( 3844-3615 and 2360 cm-1)
C═O (1741 and 1691 cm-1) ,
CH3-N (1647cm-1),
CH3 (1461 cm-1) C-H (1515 cm-1)
 C-N (1031 cm-1),
Fe-O ( 877, 520, 447 and 402 cm-1)
55
Studies Carried Out Making Advanced Radiation Shielding
Block Utilizing

1.Red Mud based sintered aggregates 2.Iron Oxide Nano

particles

Size 12X12X3 inch Size 4 X4 X3 inch

Attenuation Factor: 1.25 Attenuation Factor: 2.50
56
 Challenges in the Field of Geopolymers

Different Properties of Geopolymers due to

different source materials
New material while OPC well established
Conservative nature of construction/design
industry
In-depth R & D is needed to ensure wide
spectrum application of the novel advance
material to meet the requirements of new
millennium
57