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Full Chapter International Congress On Energy Efficiency and Energy Related Materials Enefm2013 Proceedings Antalya Turkey 9 12 October 2013 1St Edition Ahmet Yavuz Oral PDF
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Springer Proceedings in Physics 155
International
Congress on Energy
Efficiency and Energy
Related Materials
(ENEFM2013)
Proceedings, Antalya, Turkey,
9–12 October 2013
Springer Proceedings in Physics
Volume 155
Mehmet Ozer
Editors
International Congress on
Energy Efficiency and
Energy Related Materials
(ENEFM2013)
Proceedings, Antalya, Turkey,
9–12 October 2013
123
Editors
Ahmet Yavuz Oral Mehmet Ozer
Department of Materials Science and Department of Physics
Engineering Istanbul Kultur University
Gebze Institute of Technology Istanbul
Gebze, Kocaeli Turkey
Turkey
The first International Congress on Energy Efficiency and Energy Related Mate-
rials (ENEFM2013) provided all scientists the opportunity to meet, present their
work, discuss, and mutually interact in order to enhance and promote their research
work.
This volume, published by Springer, includes all the papers presented at this
Congress, held in Antalya, Turkey, October 9–12, 2013.
On behalf of the organizing committee we would like to thank all the plenary
and invited speakers for their valuable contributions.
We would also like to thank TURA Tourism for their support in the organi-
zation of the Congress, as well as our sponsor Doga Nanobiotech Inc. Finally, we
would like to thank the publishers for the quality of this edition.
v
Organization
Organizing Committee
vii
viii Organization
Sponsors
ix
x Contents
xvii
xviii Contributors
Abstract MTiX samples with different atomic metal percentage were synthesised
by sol-gel method and calcined at 400 C under air. The anatase-rutile transfor-
mation in TiO2 in the presence of transition metals (Cr, V and Mn) was investi-
gated. The kinetics of anatase-rutile transformations were determined by XRD
over the temperature range 500–800 C. It was found that the presence of V and
Mn accelerate the transformation anatase-to-rutile. However, the anatase phase
stability increases as the chromium content increases.
1.1 Introduction
There are many studies on the anatase-to-rutile transformation [1–6]. This transition
depends on several parameters such as the preparation techniques used, preparation
conditions, thermal treatments, alkoxide nature, particle size, aging, nature and
content of possible doping agents [7–11]. The doping metal oxides can be added by
different ways such as further impregnations or mixed powders [12–14], but the best
effect is obtained by a close contact between the stabilizing element and oxide.
To optimize this interaction, many studies focused on doped TiO2 prepared by
various methods. Li et al. [15], have prepared titania-silica samples by sol-gel
hydrothermal (SGH) method and sol-gel (SG) method. The results showed that the
A. Bellifa (&)
Laboratory of Materials, Application and Environment, University of Mascara,
Mascara, Algeria
e-mail: abellifa@yahoo.fr
A. Choukchou-Braham
Laboratory of Catalysis and Synthesis in Organic Chemistry, University of Tlemcen,
Tlemcen, Algeria
C. Kappenstein L. Pirault-Roy
Laboratory of Catalysis in Organic Chemistry, University of Poitiers, Poitiers, France
samples prepared by SGH had better thermal stability compared with the SG
samples which retard the anatase-rutile transformation. On the other hand, Zhang
[7] has used the titanium oxide doped with silica for photodegradation of toluene. It
has found that the embedding of small amount of silica into anatase titania matrix
enhanced the thermal stability of nanophase titania particle resulting in the sup-
pression of the phase transformation from anatase to rutile phase. A clear under-
standing of the key factors that control the phase stability, the growth, and the phase
transformation kinetics in materials is critical to quantification of materials
behaviour. Consequently, new understanding of the factors that dictate the sequence
of the phase transformations may provide insights into how phase composition,
microstructures, and properties of titania-based materials can be manipulated [3]. In
this, paper we report the sol-gel synthesis of MTiX mixed oxides with X = 0, 5, 10
and 20 of Cr, V and Mn atom percentage. We study the effect of the weight metals
content on the temperature of the anatase-rutile transition and the kinetics of the
transformation by in situ XRD.
1.2 Experimental
The preparation of MTiX was carried out in a 100 mL beaker. Titanium butoxide
was dissolved in absolute ethanol. The mixture was stirred for 30 min with
addition of an aqueous solution of metal and then a solution of ethanol and nitric
acid was added drop ways in the mixture. A white gel was obtained which is dried
and calcined in a muffle furnace at 400 C for 4 h under air atmosphere. The
samples were called MTi5, MTi10 and MTi20 for 5, 10 and 20 of metal atom
percentage respectively.
Table 1.1 Surface area, porous volume and pore size of the samples
Sample SBET m2g-1 Pore volume cm3g-1 Average pore size/nm
TiO2 68 0.06 3.60
CrTi5 180 0.22 5.00
CrTi10 230 0.19 3.30
CrTi20 152 0.10 2.60
VTi5 76 0.07 3.50
VTi10 129 0.11 3.50
VTi20 98 0.10 4.00
MnTi5 102 0.10 3.60
MnTi10 204 0.33 5.75
MnTi20 246 0.36 5.00
VTi5 VTi20 R
R
A 700 °C
A
700 °C
600 °C
* * *
600 °C
500 °C 500 °C
400 °C 400 °C
20 22 24 26 28 30 32 20 22 24 26 28 30 32
2 Theta /° 2 Theta /°
Fig. 1.1 X-ray diffraction (XRD) patterns of VTiX; A anatase; R rutile; asterisk V2O5
The experimental results on BET surface area, mean pore diameter, and total pore
volume of all synthesized materials are shown in Table 1.1. As obviously seen, the
surface area increased with increasing of Mn content from 5 to 20 %. In the other
hand the surface area increased with increasing both V and Cr content from 5 to
10 %. With increased Cr and V content (20 %), the observed loss in surface area
could be attributed to probable segregation of chromium and vanadium [17–19].
The average pore size of anatase phase decrease with increasing of Cr content. In
the case of VTiX samples, the average pore size remains constant with increasing
of V content. Wearies an increasing of average pore size was observed with
4 A. Bellifa et al.
MnTi5 R MnTi20 R
800 °C
MnO2
800 °C
A
700 °C
700 °C
600 °C
600 °C 500 °C
500 °C 400 °C
400 °C
20 22 24 26 28 30 32 20 22 24 26 28 30 32
2 Theta /° 2 Theta / °
A
CrTi5 R CrTi20 A
R
800 °C
800 °C
700 °C 700 °C
600 °C
600 °C
500 °C 500 °C
400 °C 400 °C
20 22 24 26 28 30 32 20 22 24 26 28 30 32
2 Theta /° 2 Theta /°
increasing of Mn content. The pore volume varied with varying metal and metal
content. The biggest pore volume was signalled for MnTi20. So the presence of
Mn content increased both pore size and pore volume.
The results of XRD analysis are shown in Figs. (1.1, 1.2 and 1.3). The diffrac-
tograms were recording in situ for MTiX samples. In this work we present only the
Table 1.2 Crystallite size versus temperature
Crystallite size (nm)
T/C 400 500 600 700 800
Sample A R A R A R A R A R
TiO2 10 / 16 / 27 41 37 36 / 40
CrTi5 07 / 10 / 16 / 22 32 32 37
CrTi10 06 / 13 / 13 / 22 / 32 39
CrTi20 06 / 07 / 09 / 20 / 30 35
VTi5 09 / 11 / 24 34 41 42 / 47
VTi10 09 / 12 / 37 40 / 57 / 60
VTi20 10 / 19 28 36 31 / 40 / 41
MnTi5 12 / 12 / 15 / 24 31 / 37
MnTi10 11 / 11 / 14 13 / 25 / 36
MnTi20 / / / / 18 09 / 18 / 35
1 Study of the Effect of Transition Metals on Titanium Dioxide Phase Transformation
5
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opportunity to slay their game at noon, but are very apt to hide the
carcass and come back to devour it in the cool of the evening.
The craving for hot spices, for strong meats, and such abominations
as fetid cheese and fermented cabbage have all to be artificially
acquired; and in regard to the selection of our proper food the
instincts of our young children could teach us more than a whole
library of ascetic twaddle. Not for the sake of “mortifying the flesh,”
but on the plain recommendation of the natural senses that prefer
palatable to disgusting food, the progeny of Adam could be guided in
the path of reform and learn to avoid forbidden fruit by the symptoms
of its forbidding taste.
[Contents]
B.—REWARDS OF CONFORMITY.
Frugality has cured diseases which defied all other remedies. For
thousands of reformed gluttons it has made life worth living, after the
shadows of misery already threatened to darken into the gloom of
approaching night. Luigi Cornaro, a Venetian nobleman of the
sixteenth century, had impaired his health by gastronomic excesses
till his physicians despaired of his life, when, as a last resort, he
resolved to try a complete change of diet. His father, his uncles, and
two of his brothers had all died before the attainment of their fiftieth
year; but [63]Luigi determined to try conclusions with the demon of
unnaturalism, and at once reduced his daily allowance of meat to
one-tenth of the usual quantity, and his wine to a stint barely
sufficient to flavor a cup of Venetian cistern-water. After a month of
his new regimen he regained his appetite. After ten weeks he found
himself able to take long walks without fatigue, and could sleep
without being awakened by nightmare horrors. At the end of a year
all the symptoms of chronic indigestion had left him, and he resolved
to make the plan of his cure the rule of his life. That life was
prolonged to a century—forty years of racking disease followed by
sixty years of unbroken health, undimmed clearness of mind,
unclouded content. Habitual abstinence from unnatural food and
drink saves the trials of constant self-control and the alternative
pangs of repentance. “Blessed are the pure, for they can follow their
inclinations with impunity.”
[Contents]
C.—PERVERSION.
Yet the ancients sinned with their eyes half open. Their recognition of
dietetic abuses was expressed in the word frugality, which literally
meant subsistence on tree fruits—or, at least, vegetable products—
in distinction from the habitual use of flesh-food. The advantages of
temperate habits were never directly denied; the law of Pythagoras
enjoins total abstinence from wine and flesh, and the name of a
“Pythagorean” became almost a synonym of “philosopher.” In all but
the most depraved centuries of Imperial Rome, wine was forbidden
to children and women. The festival of the Bona Dea commemorated
the fate of a Roman matron who had yielded to the temptation of
intoxicating drink, and was slain by the hand of her stern husband.
Lycurgus recommends the plan of letting the pupils of the military
training-schools witness the bestial conduct of a drunken Helot, in
order to inspire them with an abhorrence of intoxication. The bias of
public opinion [65]always respected the emulation of patriarchal
frugality and frowned upon the excesses of licentious patricians.
[Contents]
D.—PENALTIES OF NEGLECT.
[Contents]
E.—REFORM.
[Contents]
A.—LESSONS OF INSTINCT.
B.—REWARDS OF CONFORMITY.
The English word king, like Danish kong and German König, are
derived from können (practical knowledge), and the first ruler was
the most skilful, as likely as the strongest, man of his tribe. Skill,
whether in the sense of bodily agility or of mechanical cleverness,
established the superiority of man over his fellow-creatures, and is
still in many respects a test of precedence between man and man.
Supreme physical dexterity is always at a premium, in peace as in
war, in the sports of princes, in the pastimes of pleasure-seekers, in
the adventures of travelers, in moments of danger, in camps, in the
wilderness and on the sea, as well as in smithies and workshops.
Conscious skill and agility form the basis of a kind of self-reliance
which wealth can only counterfeit. In a cosmopolitan sea-port town of
western Europe I once overheard a controversy on the comparative
value of protective weapons. Revolvers, stilettos, air guns, slung-
shots, and bowie knives found clever advocates, but all arguments
yielded to the remark of an old sea-captain, who had faced danger in
four different continents. “There’s a use for all that, no [76]doubt,” said
he, “but, I tell you, mynheers, in a close row the best thing to rely
upon is a pair of quick fists.” For the efficacy, even of the best
weapons, depends to a large degree on the expertness of the
handler, the panoply of a weakling being as unprofitable as the
library of an idiot. “Presence of mind” is often only the outcome of
such expertness, and in sudden emergencies theories are shamed
by the prompt expedients of a practical man. In war the issue of a
doubtful campaign has more than once been decided by the superior
constructiveness of an army that could bridge a river while their
opponents waited for the subsiding of a flood. The conquest of
Canada was achieved by the skill of a British soldier who devised a
plan for hauling cannon to the top of a steep plateau. The fate of the
Byzantine empire was decided by the mechanical expedient of a
Turkish engineer who contrived a tramway of rollers and greased
planks, as an overland road for a fleet of war ships. By the invention
of the chain grappling-hook Duilius transferred the empire of the
Mediterranean from Carthage to Rome.
[Contents]
C.—PERVERSION.