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FROM : UftSHINGTON BIBLIOGRAPHIC SUC, PHONE NO, : 301 595 9279 



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Thermal Analysis 



Vol. 2 Inorganic Chemistry /Metallurgy 
Earth Sciences 

Organic Chemistry /Polymers 
Biological Sciences/Medicine/Phannacy 

Editor 

W. Hemminger 
Institut fur Werkstofflcunde 
Universitat Braunschweig 
Federal Republic of Germany 



1980 



s 



Birkhauser Veriag 
Basel • Boston • Stuttgart 



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Proceedings of the Sixth International 
Conference on Thermal Analysis 

Bayreuth, Federal Republic of Germany 
July 6-12, 1980 

Vol. 1 Theory 

Instrumentation 
Applied Sciences 
Industrial Applications 

Vol. 2 Inorganic Chemistry/ Metallurgy 
Earth Sciences 

Organic Chemistry/Polymers 
Biological Sciences/Medicine/Pharmacy 




Vol.2 



Inor 
Eart 
Org: 
Biol 

Edit 
W.l 
Insti 
Unr 
Fed 



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CIF-Kumi(daufnahmc dcrDeuttchen 
Bibo'othck 



formal analysis - Base), Boston, Stuttgart: 
Birkhiwr. 

W. 1971 mit d, Enchonunfiscran: Basel. 
Stuitgm. - Bd. 1977 im VW. Heydctt. Lo* 
don,BcUnuiwr(NJ). Rheine* 
ISBN 3-7643-1202-5 
1980. 

Vol. 2. Inorganic chemistry, metallurgy, 
earth sciences, organic chejmijiry, polymers, 
biological sciences, modidne, pharmacy: 
proceeding of the 6. Internal Conference 
on Thermal Anaryiis, Bayreuih, Fed. 
Republic of Germany, July W2, 1980/cd. 
w.Hemnuagcr.«19R0, 
ISBNJ.7643-108M fi 



All rights reserved. No pan of thi* nublica- 
ooo may be reproduced* stored in a 
retrieval system, or transmitted in my form 
or by any xncana, electronic, mechanical, 
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oui the prior pomiittioo of the coDyrifihi 
owner. 

> Birlch&user Verlag Basel. I9S0 
ISBN 3-7643-1 086-3 
Printed in Switzerland 



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251 



THERMAL BEHAVIOUR OF COMPOSITIONS TN THE SYSTEMS 
x BaTi0 3 ♦ <l-x) Ba(tn 0 S B 0 s )0 3 

V.5. Chincholkar* and A.R. vyavahare 
Department of Chemistry/ Institute of Science, Nagpur 

ABSTRACT 

The effect of temperature on the dielectric constant (£) , 
tan 6 (loss tangent) and the ferroelectric properties of 
compositions in the systems x BaTlO^ ♦ (1-x) Ba(Ln Q 5 B Q 5 )0 3 
(0«3c*i. i*n 3 * o a rare earth cation and Y j4 , B 5 * = Ta,i*b,v) 



reveal that in the Ta S * system at * - 0.8, the 

T ) and T (the Curie-point) exhibit an increasing trend 

with decreasing ionic radii of the In ions, whereas in 

che analogous Nb^* system , an almost linear behaviour has 

been observed. In the v 5 * system* the pure phases (x * O) 

exhibit increasing trend of fc„„ and T values with de- 

max c 

creasing rare earth cation size. Phases with x = 0.8, exhibit 



a break at Nd 



3* 



in 



£ values, in contrast to an increasing 
max 

trend in T values with decreasing rare earth cation size, 
c 

Similar behaviour is observed for the polarization data. The 
increasing trend in the T £ values in the direction Ta 54 -Nb 5+ - 
V** at x - 0.8 is perhaps reminiscent of the nephelauxetic 
effect. 

The T c values for these first order transitions have been 
confirmed by recording DTA curves against inert a-Al 2 0 3 , the 
enthalpy change , however, being appreciably low in the pre- 
sent series. 

INTRODUCTION 

Recently emphasis has been placed on laser research and a 
concentrated effort has brought new and improved materials 
which can be used as hosts for transition. An important part 
of this effort has been directed towards finding potential 
laser materials having fluorescent energy states with long 
life times. In order to determine^ if symmetry conditions in 

THCRRIAL ANALYSIS . ICTrt 80 . 8X8KHACUSCA VCRlAC. BASEL , BOSTON, STUTTGART 



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crystals also affect the life time of rare earth ion fluores- 
cence, a series of ordered per ovs kite compounds having the 
general formula A(B£ 5 B^ 5 )0 3 were studied [1J-[7J. However, 
temperature effects and doping characteristics were not stu- 
died. The present work concerns with the formation and the 
thermal characteristics of compositions in the systems 
x BaTi0 3 r n-x) Ba(Ln 0 5 B Q ^) o 3 where 0* 1 , La** « a rare 
earth cation and y, 0 s * = Nb 5 *, Ta 5 * and V 5 *, 

EXPERIMENTAL PROCEDURE 
The compositions were prepared by the solid state reaction 
of the parent compounds (carbonates* oxides) at high tempera* 
ture as described elsewhere [8] , [9] • Room temperature X-ray 
structure was determined using Debye-Scherrer camera (14 cm 
diameter) and nickel-filtered Cu-Kq radiation. Temperature 
effects on the dielectric constant (capacitance) and loss 
tangent (tan 6) were measured using a 716-C GR capacitance 
bridge together with type 1340-B type audiobeat frequency 
generator and type u null detector and amplifier with 

1231 P 5 type variable filter in a sample holder designed in 
this laboratory [10]. 

Modified [11 J Sawyer-Tower type circuit was used to record 
hysteresis loops as a function of temperature io the above 
sample holder and a MOM Derivatograph was used to record DTA 
curves against a-Al 2 0 3 as reference. 

RESULTS AND DISCUSSION 
Tables 1-3 show the room temperature £ values as also the 
£ max and the Cur ie«point (T e ) values evaluated from the capa- 
citance measurements for compositions in the various systems. 
The temperature study e was restricted to k = 0.8 compositions 
in the Ta 5 *i Nb 5 * systems and over the entire composition 
range in the V S * system which exhibited the transition in the 
whole range of compositions. Table_4 shows these parameters 

system. In all the sy- 



stems an increasin 
with decreasing rar 
scent of the lantha 



£ , P„ and T vaj 
max s c 



Composition 





1 Ta 0. 


Ti 


8a(Nfl 0 


1 T *0. 


i T1 o.a 


Ba (So Q 


1 Ta 0. 


Ti 


Ba(G V 


i*»o. 


i Ti o.e 


Ba|Oy 0 


1 Ta 0. 


1 T1 0.B 


Balv o,i* 


Ta 0.1 


W 0.6» 


€ n*x' > 


„ and 


T VE 




s 


c 


Ba(x.a Q 


1 Nb 0. 


1 Ti 0.l 




1 Mb 0. 


1 Ti 0.< 


Ba(S» 0 


1 Nb 0. 


1 T1 0.» 


Ba(Gd o ; 


1 0. 


1 K 0.- 


Ba(Dy 0 


.Kb. 
1 0, 


1 Ti 0. 




0.1 


Ti 0.8 



■• |L Vi v o.i»o.i 

Ba(Nd 
B&(Sffl 



Ba(Nd 0.lVl Ti 0.B 
0.1 V 0.1 Ti 0.E 
Ba(<5d 0.1 V 0.n Ti 0.E 
B * (D *0. 1 V 0.- I T1 0.E 

Ba <*o.iVi T W 



at x = 0 for compositions in the V 5 * 



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itu- 

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fith 
ih 

:d 
re 

DTA 



stems, an increasing trend in €^ a* also T Q i 3 obsorved 
with decreasing rare earth cation size, and is perhaps remini- 
scent of the lanthanide contraction. 



max' 



Table 1 

p 5 and T c v *lues tor compositions in the Ta 



5* 



system 



Composition 


25 °C 




'max 


T c 






[Mc/cm*] 




f*C] 


Ba(t Vi Ta o.i Ti o.*> 0 3 


200 


4.5 


780 


85 


Ba(Nd o.i Ta o.i Ti o. fl )0 3 


250 


6.0 


850 


90 


Ba,S Vl Ta 0.1 Ti 0 .8>°3 


342 


6.1 


1050 


92 


Ba{<3d 0.1 Ta 0 .1«0 .8 ,0 3 


480 


8.5 


1120 


96 


Ba(Dy 0 lT a 0 ^ 6 )0 3 


530 


8.9 


1400 


100 


"• w o.i T *o.i»o.e ,0 3 


580 


9.6 


1830 


110 




Table 


2 






Siax' p s and T c value9 for compositions in 


the systems Nb S * 


Baa Vt Nb 0.i Ti 0.8>°3 


232 


5.3 


S80 


90 


Ba(Nd 0.1 Nb 0.1 Ti 0.8>°3 


260 


6.2 


900 


100 


ta,to o.i»o.i w o.e )0 3 


290 


8.4 


1100 


107 


Ba(Gd 0.1 M Vl Ti 0.8 ,O 3 


380 


9.2 


1220 


110 


Ba( %.1* b 0.1 T W°3 


415 


5.8 


1350 


115 


^'Vi^o.i^o.e^a 


S30 


10.2 


1600 


118 



Table 3 



r.8* 





aaa ViVi Ti o.e ,0 3 


170 


4.S 


1100 


93 


apa- 


Ba(Hd o.iVi Ti o.e ,0 3 


225 


3.5 


840 


124 


ems* 


Ba(s Vi v o.i Ti o.8»°3 


280 


7.5 


1130 


130 


tions 


Ba(Cd 0.1 V 0.1 Ti 0.8 ,O 3 


350 


8.2 


1290 


135 




Ba(D *0.1 V 0.1 Ti 0.8>°3 


460 


8.2 


1600 


135 


the 
rs 


8a(5f 0.1 V 0.1 Ti fl.8 )O 3 


530 


12.2 


2200 


125 



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Baiu. — V Syste » « 



1* 



Baaa o.s v o. 5 'o 3 

Ba(M 0.5 V 0.5 ,O 3 
8a(Oy 0.5 V 0.5'°3 



60 
20 
30 
35 

25 

40 



7.B 
'0.7 
11.3 
12. S 
17.9 



260 


154 


500 


768 


850 


175 


1020 


200 


1250 


220 


to increase with 



T ^le S snows the tr. and ah ' * 



Table S 




of k AH values reveal di lution of the vaj 

of the 120'c transition of BaTio us , . lU * 

addition of Ta 5 * phases no 1 3 C • 1/Bol * , »•! by the 
nW* ^ Phases, no change with addition of ,0,** 

till * *~ ^ — v s- 

Another significant of ^ $ 

vation of increaeing x (T , values „ Y " **? obfier ~ 

keeping the Ui i on • ^ **ng » radix, 

Considering the energy level diagram of an octahedron " 
rounded ^ ion ^ eonfig UMtien (^S^^tir 



fc e more ionic 
fc his the elec 

be less 
3u«tifi ed by 
these ions r 
Wrgensen has 
that the elec 
^'-v 5 * and 
transition me- 
cal bond >ec« 
°«r results aj 



Fifth ionizatj 



Ion 



V 5 * 
Mb 5 * 



Ta 



5* 



Report OA* 

I 2 ) F. Galassc 
51 (1959) 

I3J F. Calasse 
13 (1961) 

143 F. Gaiasso 

T51 p. Galasgo 

I*] F. Galosso 

(7] F. Gaiasso 

(*) V.s. chine 



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o 



5* , ,5* 

be more ionically bonded than Nb and V 



41 
O 



h 

or 



to 



As a result of 

this the electron density in the t- -orbital of the Ta 5 * ion 
will be less than that in the case of Nb , V . This is also 
justified by considering the fifth ionization potential of 
these ions T (Table 6 J which also increases in this sequence. 
J^rgensen has concluded from the electron transfer spectra 
that the electron affinity increases in the sequence Ta 5 *- 
Nb 5 *-v 5 * and from the reduced Racah parameters of several 
transition metal ions (nephelauxetic effect) that the chemi- 
cal bond becomes more covalent in the sequence 5d-4d-3d group. 
Our results are consistent with the observations of Jftfrgensen- 

Table 6 

Fifth ioniration potential and electron configuration of B 

metal ions 





Xon 




Electron configuration i$ UV) 








3s 2 3p* €5 




*b st 


4a 2 4p € - 52 








Ss 2 Sp* 4$ 








REFERENCES 




m 




Galasso, United Aircraft Corporation Laboratory, 


e 




Report UAR-B10, Jan 1963 


e 


12] 


F - 


Galasso r L- Kat2, and R. Ward, J. Amer.Chem.Soc. 




n 


(1959) B20 




131 


f. 


Galasso, J.R. Bar r ante, and L. Katz, J.Amer -Chem.Soc. 






83 


(1961) 2030 




[4] 


F. 


Galasso, and W.J* Darby, J.Fhys.Chem- 66 (1962) 131 


©r- 


[5] 


F. 


Galasso, and J. Pyle, J.Fhys.Chem. 67 (1963) 533 


dli, 


(6] 


F- 


Galasso, and J. Pyle f J.Phys.Cheaw 67 (1963) 1561 




[7] 


F, 


Galasso, and J. Pyle, Xnorg.Chem. 2 (1963) 482 


r- 


[8] 


V.S. Chincholkar, J.lnorg.Wucl.chem- 34 (1972) 2973 



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|SUC. PHONE NO. : 301 S9S 



Feb. 17 2005 85:04Pn Pig 



9] K. Cade, and V.S- Chincholkar , J.C>u:m.Soc. (Dalton) 
U (1979) 1959 

{10] V.S. Chincholkar, Z.Angew.Chem. 26 (1970) 288 

pi) v.s. Chincholkar, Ph.D. Thesis. Punc University, 1967 

(12) R.S.Roth, J. Research N&S 58 (19S7) 75 

(13] J „ volgerr Philips Res. Rep. 7 (1952) 21 

(14] C.K-J<Srgenscn, "Absorption spectra and chemical bonding 
in complexes" Pergamon Press , 19S2, pp, 147, 306 and 



" Present: address: Forensic Science Laboratory, Bombay-* 8 



STUDIES 
Bhabha 



The foxaaation of 
bj Solid State re 

*«2 (C 2 0 4 ) 3 , La ( 
The reaction oocu 
depending upon, tft 
kinetics of fona 
and MoOj la evelu 
controlled mechat 
activation energy 
mole" 

A reversible phae 
oha erred at 82J ] 
r-ray diff ractiox 




She a olid etate i 

to gala better tu 
general and the a 
formation of tr±i 
particular. 
Several Xng (MoO, 
been extensively 
eleotrical, magiu 
kinetics and see] 
reported eoantil; 
reactivity of th 
re-ezaaine this 
detail* 

TKCRfllAl flNfttYSIS . IC! 



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