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Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
Abstract
Free Piston Driven Shock Tube [FPST] is used to heat Ar and
N2 gas mixture to extremely high temperature like 9100
12300 K with reflected shock pressure of about 59-70 bar for
about 2-4 ms duration. Shock heated nitrogen gas under this
extreme temperature goes to both non-equilibrium and
dissociation state. Here argon promotes heating of N2 to
higher temperature. At this extreme thermodynamic
condition shock heated nitrogen gas interacts with the
anatase TiO2 at the end of the shock tube. The surface
composition, electronic structure, crystal structure and
surface morphology of the anatase TiO2 sample was
examined before and after shock loading using X-ray
photoelectron spectroscopy (XPS), X-ray diffraction (XRD),
Scanning electron microscopy (SEM) and High-resolution
transmission electron microscopy (HRTEM). The results
obtained from the experimental investigations shows the
formation of N doped rutile TiO2-xNx. After shock treatment
colour of the top surface of white anatase TiO2 change to
yellow colour indicating nitrogen doping. Under this
temperature anatase TiO2 is subjected to super heating and
cooling in presence of high enthalpy nitrogen and helps to
stabilize the N doped rutile TiO2 structure. In this short
duration, crystallographic phase transformation occurs from
anatase TiO2 to N doped rutile TiO2. An extreme
thermodynamic condition prevalent at the end of the shock
tube makes FPST an important tool for the exploration to
study polymorphic phase transformation of ceramic
materials, materials modification and synthesis of new
materials.
Keywords
Shock Dynamic Loading; High-enthalpy Gas; Solar Eenergy
Materials; Phase Transformation; N-Doped TiO2
Introduction
Titania (TiO2) is one of the most prominent materials
for various kinds of industrial applications related to
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Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
9TiO2(s) +14N2
+ 20 CO2 + 25H2O
Several pellets were made to use in shock tube
experiments. Each pellet was made using 100 mg of
TiO2 powder in pellet pressing machine by applying
pressure up to 70 N and kept for 5 min. These pellets
were used to perform shock tube experiments.
Vacuum pump
High pressure gas inlet
Pc
V3
V5
V6
Pp
Piston
holding
vacuum
system
V1
V2
1
V4
Vacuum pump
gas inlets
Inertial mass
Compression Tube
Gas
reservoir
V8
V9
V10
V7
Shock Tube
P5
P4
Spacer
Pg
P4 Pressure
sensor
0 - 345 bar
1. 20 kg Piston
2 .Metal diaphragm
Nozzle
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Shock speed
and P5 pressure
0 - 345 bar
(a)
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Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
(b)
FIG. 1 (A) SCHEMATIC DIAGRAM OF IISc FREE PISTON DRIVEN
SHOCK TUBE (FPST) WITH ELECTRONIC CONTROLS (B)
ALUMINIUM DIAPHRAGM (3MM THICK, 1/3 GROOVE) BEFORE
AND AFTER RUPTURE
(a)
(a)
(b)
42
(b)
FIG. 3 DATA ACQUIRED FROM PRESSURE TRANSDUCERS
AT THE END OF SHOCK TUBE (A) TIME HISTORY DATA WHEN
THE SHOCK TRAVELS 0.5M DISTANCE (B) REFLECTED SHOCK
PRESSURE (P5) ACQUIRED AT THE END OF SHOCK TUBE
2 (M S ) ( 1)
P2
=
P1
+1
2
2
P5 2 M s ( 1) (3 1)M s2 2( 1)
=
( + 1) ( 1)M s2 + 2
P1
Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
Estimated Values
T
(s)
L=0.5 m
P5
(bar)
190
66
VS
MS
(K)
(m/s)
2630
T5
7.9
10500
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N2: 0.047
=1.48
200
70
2500
7.6
9400
180
61
2770
8.4
12300
210
59
2380
7.3
9100
N2: 0.06
=1.48
Ar: 0.056
Intensity (a.u)
Ar: 0.06
(b)
(a)
N2: 0.056
=1.48
456
Ar: 0.067
N2: 0.046
=1.5
458
460
462
464
466
BE(eV)
FIG. 4 (A) TI(2P) B.E. AT 458.5 eV FOR ANATASE TIO2 AND (B)
B.E. of TI(2P) AT 458.9 eV FOR N DOPED RUTILE TIO2 FORMED
AFTER INTERACTION OF SHOCK HEATED AR + N2
Characterizations
N(1s)
Intensity (a.u)
394
396
398
400
402
BE(eV)
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Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
(a)
(b)
44
Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
211
111
3.53
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3.21
101
ACKNOWLEDGEMENT
110
50 nm
(c)
(d)
2 1/nm
103, 004,
112
200
101
REFERENCES
(b)
Conclusions
In brief, we have demonstrated that the interaction of
high enthalpy shock heated (Ar+N2) gas mixture with
anatase TiO2 in shock tube transformed to N doped
rutile TiO2. Nitrogen doped Titania is achieved by
various methods as reported in the literature. In the
present experimental setup shock compressed
nitrogen gas (66 bar pressure) at high temperature
(about 10500 K) react with anatase TiO2 for short
duration (3.5 ms). This high temperature nitrogen gas
reacts with anatase TiO2, formation of N doped rutile
TiO2 is investigated using XPS, XRD, SEM and
HRTEM. Both N doping and crystallographic phase
transformation occurs simultaneously. Assuming that
the heat transfer rates of 1/3 the total estimated
temperature (10500 K) in 3.5 ms time, the super
heating and cooling occurs at the rate of 106 K/s. At
this rate of heating and cooling, the kinetics and
dynamics of phase transformation, surface reaction,
material properties, and electronic structure of shock
exposed materials are not well understood. In the
present shock tube experiments, materials are
subjected to high temperature gas impact, which is a
unique method developed in our laboratory. This
novel experimental technique is used to study
materials under extreme thermodynamic conditions.
Both theoretical and experimental investigations are
properties,
modifications
and
H.,
Watanabe,
Y.,
Hashimoto,
K.,
Nitrogen-
V.,
Experimental
investigations
gases
of
on
surface
high
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Advances in Ceramic Science and Engineering (ACSE) Volume 2 Issue 1 February 2013
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