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|FEB. 22- 2005 10:43AM Mail l^GATE-IE INFO EXPRESS - 
ARKIV FOR KEMI Band 1 nr 54 



NO. 4215 P. 2/19 



Communicated 15 



' g ^W 19 49 by Abke Wksxcbsh a»d Abks Tibbie 



V;':. 



'*•« ;'. 

V r". 

W*t - 



ftfixed bismuth oxides with layer lattices 

L The structure type of CaJSbaBisOa 
By Bengt AumvnJtJTJS 

With 5 figures in the text 

b th. course o£ a eompreheBjive •jr^ft tSS "a°p^ 
foand. X-ray to tt« W Pbne. 

perowskite layers are inserted. compounds vhere the Bi a O? + layers 

An attempt was then made to synthe^e compoun ^ 

alternate with fiw compounds with this 

■ could be expected to be: (M^Wfy- Sr Pb B: Ti Nb Ta. 

structure could be prepared with MeNaWft «rr flMjb(matea were 
- Procedure: Weighed amounts of the apP^^ 1000 <> a a number 

r-ffltod and heated in platinum, or S^^^^iT" were prepared. Out 
?of compounds with *"J^*^&^^ 

orthoxhombic. -———=== 



Composition 



Orthorhombic description 



Pseudo -tetragonal 
description 




m 



BEST AVAILABLE COPY 




FEB. 22. 2005 10:43AM Mai 10OGATE-IE INFO EXPRESS A NO. 4215 

B . aubiviilitjb, Mixed bismuth oxides with layer latticus 

We crystals were prepared from the and Bi,NbTi0 9 phases.-fi 

Single crysxais w ™\* K nH and life I (pseudo-tetragonal cell) were taken. ;&§sL-. 
Weissenberg ^photographs of Okl g^Jg^ 6a) the reflections 1 1 0, m$$&, 
In the ponder PhotographB ^ Bi^bTi0 9 £ ab ^ ^ found for ^|#. r 

SST? wa Lc5J Tthi thi s^ucture be described by means 

this it was con.cmo«u the pseudo-tetragonal celk4|S5j % 

^ a. v£ rt1i« Weissenberc photographs register A At and A, A +2,1,.^ , 

s^sst; of w K» js-* - *• — <* 

orthorhombic unit cell. - wfe3*> 



3/19 



The cryBt« 
in the vioinit; 
0 f maxirnum 
tetragonal ind 
10?, 1H 2( 
jjave been dei 



^^anS occur between the interns of the spots as found in* 
A tew cuscrepanuBo ^ ^ powder photographs. In*;^ • 

the Weissenberg Pjotograpl* ,W found between reflec-^ . 

the Weinberg r gw^Wta *J^XwS» *» *»* 024 E 
t^fil S^m^dllKn 11. The reason might b^|| 
the orientation of the powder. 



PbBisNbsO, pkse 



«- Powder "^S^Mtt ^^m. 

indicated a lower Laue syrometry ihan D« xne ? ^ 

with A, t, J all odd or all even, erections were found, i ^ 

characteristic of the space groups Da*. i>a and i/a». V,^! - 



Positions of the metal atoms 



t 4. ~ +ViA Vh and the Bi atoms are almost the same^£f|^. 

The intensities of the reflections seemed to depend mamiy ^ 
(see Table la). It therefore seemed PJ *»* + 0 ol The sum ofi^ , 

ot^mfl are Dlaced along the lines: (000; i £0, i u t> ^? W T i-w fe 

I™, « «3i jv« «•»«*-■ ^ ■» «■«- tk, -i , 

Patterson function aloi 00,. In Fig. la these sums are platted ^^^fl^ 
oiTTi^n from the graph that high maxima occur for ,-0.20 and ; g|. 

"3£» ceU of PbBWHb.0. ^""J^ '.tt-b^l 

If the space groups are assumed to be D£, Da « ** a " ^ * 8 .f 0 ld posH, : 
of placing 12 Me atoms on the lines 00* » m one ^^^^ 0 J^ Joj^r 
tion. mL these assumptions the only 4-fold positions possible are 000 or ■ 



4 
6 
8 

10 

12* 

14 

16 

18 

20 

22 

24 

26 

28 

30 

32 



1 

3 
5 
7 
9 
11 

13 
16 
17 
19 
21 
23 
25 
27 
29 
31 



S|FEB. 22. 2005 10:43AM Mai^JFOGATE-IE INFO EXPRESS 



liases, . 
taken. * v 

211, 
:>r the ■ 

From, 
ans of 
I cells ) : : 

Using 
* + 2,i.. 

of an 

md in 
is. In 
reflec- 
might 
ght be.. 



NO, 4215 



AHKXV FOR KEMI. Bd 1 HT 54 



Table la 

Weissenberg Photographs of PbBiaJ^Og. Cu radiation 

The crystals form very thin plates, and therefore considerable absorption occurs. Spots 
jo the vicinity of the lines described by Wells (2) will therefore be weakened* The regions 
0 f maximum absorption are denoted by dotted lines. In the tables 1, 2 and 3 pseudo- 
tetragonal indices are used, and observed and calculated intensities for the reflections: 0 01, 
jOi, H*> 20*, and 2 1 i are given. With orthorhombic description these reflections would 
have been denoted by: 001, 02f or 20i, 221, 13* or 31/. 



ied as : 
o lines : 
= 5.492 : 
tat the 
>graphs- 
ity was - 

ig only , 
This is 



e same, I 
md the »T 
fore no 7? 
by Me. 
lue of I * 
theNb.;;; 
sum of £ 
jent the 

motions 'j. 
20 and:;. 

i. 

aly way*.'$|? 
>ld posi- 'Sj 

or ooj::;vi 



l 






J 00l 


I oba. 
*1U 




2 

4 . 
6 
S 
10 


t 

18 
9.0 
0.1 
25 
350 


1.2 
<34 

8.4 
14 
340 


m~ 

WW 

m~* 
vst 


vw 

m 
m • 
w 


vw 
w 

w~ 
m 


12 
14 
16 
18 
20 
22 
24 
"26 
28 

! * 30 
! 32 


19 

36 
9.6 

45 
280 

22 

71 

27 

85 
190 

25 


0.2 
100 
4.8 
31 
230 

0.04 
200 
14 
26 
130 
8.4 


w 
m* 
vw 
m 

St 

m+ 
w 

m" 

m 

w 


— 

WW 

w 
m+ 

m 

WW 

w 
m 


— 
w~ 

w 
m+ 

vw 
w 


I 


II 


h 




I obs. 
^211 




i 

i 

1 

3 
6 
7 
9 


1.7 
20 
380 
18 
12 


■ 

17 
6.3 
370 
' 0.0 

63 


m 

m 1 
vst 

m 


! 

WW 
St 

w 




11 


3,2 


5.3 








13 
16 
17 
10 

23 
25 
27 
29 
31 


32 
320 
20 
55 
18 
61 
230 
24 
85 
48 


23 
280 

0.2 
160 

7.8 
32 
170 

1.7 
250 
23 


w 

St 

m + 
vvw 
m 
m+ 

m+ 
w 


WW 

w 

1 

w+ 
m 





465 



FEB. 22. 2005 10:43AM Mai 1^1 FOG ATE- IE INFO EXPRESS 

B. aubiviluos, Mixed bismuth oxides with layer lattices 



NO. 4215 -P. 5/19*" 




D 



Of 
It • 

Usi 
sibiliti 



0.2O 8 
In 
the r; 
direct"; 
course 
actual 
areas 
alone. 



22.2005 10:43AM Mai^FOGATE-IE INFO EXPRESS 



NO. 4215 P. 6/19 



ARKJV FOR KEMI. Bd 1 DI 54 



n 



in 




Full curve 



Figure la. Patterson function of Pbv a Bi»NbjO e along 00 z 
1 ^ J OOl 008 2n , lz 



Dotted curve: coa ^ n ^ z (orthorhombic indices). 




Figure lb, Patterson function of Bi^NbTiOa along 00* 



Of 8-fold positions only + 00s is possible. 
It was assumed arbitrarily that 4 Me occupy the position 000. 
Using the distances found with the aid of the Patterson function, two pos- 
£*\ Abilities for placing the Nb atoms arose : 



1. 8 Nb in + 00 0.20 

2. 8 Nb in ±00 0.40 



4 Me in 000 
4 Me in 000 



8 Me in ±00 0.40 
8 Me in ± 00 0.20 



-rs3 ■ 



The two curves on the graph were added and the areas under the peaks at 
0.20 and 0.40 calculated. The ratio 1.5:1 was found for 0.20/0.40. 

In case 1, the ratio was calculated to be 0.91:1 and in case 2, 1.1:1 if 
the ratio /hd//bi was assumed to be 0.46.. These figures cannot be compared 
directly with the observed ratio 1.5 : 1 since the zero level in figure 1 is of 
course uncertain. Case 2 agrees slightly better insofar as the peak at 0.20 is 
actually higher. It seemed, however, that the* uncertainty in determining the 
areas was so large that case 1 could not be excluded by these measurements 
alone. 

467 



r 



I- 
I 
ft 

& 



ii 

I,: 
f 
-a 



v 

a". 

"i-. 



10:43AM Mail 0)GATE-IE INFO EXPRESS £ NO. 4215 P. VV§ 

, ATJRiviLLnJS, Mixed bismuth oxides with layer lattices 




^^ 0 ' ± to«r=Tl4 0 T 4 0.^ be ia Tab,* 1. is compared 

with the observed intensities. :£1 ! 

Case 2 '• J 

• ^ v 4. Ai«n«T,<** around 0 20 The best values were found 
Zm was vaned about 0.40 and zm ^ZJrTnn™ ^ 
to be ^ = 0 412 + 0.004 and ^ = 0.202 ± 0.002 

t0 The doseivel and calculated values are m ^ * 

It was found that arrangement 2 accounted shghtly better fo ^ 
xnStaT data than J. It must however be b*rne » g^J 1 ^"^ 

Sot atd^t tSftefinte The *ft S. $ 

S^flTi^tobe as large as to allow a decosion betweer , 1 and 2 Uym i 
before tried to find possible oxygen positions both for 1 and 2. The results 
were then compared. 



Case 1. Positions of the oxygen atoms 

The positions of the metel j*^™ Z7m% V^mceln ^ 1 

"SS X ISftn be A ~ ^s^ 

and Nb-0 should not be smaller than 2.5, 2.2 ana i.e a. °*ys 
only be situated in the following positions: 

ir»v * w . m 4(J,m 

8 (») i i 5 i i »-» 0-M9 s H £ O.061 0.262 £ » S 0.311 

0.148 £ 0.201 
8(<)l»J;H-»i 8(j) »ifc 

Am attempt was made to find «-*m ^tJ^SSJS 

- r » wilt ^1 firM fa V* «* 



468 



FEB. 22. 2005 10:43AM Mail ^)GATE-1E INFO EXPRESS 




).20 and 2^*p 
ae intensities';^ 

this way the . 
is compared 



s were found;^: ? 



: the expert ^ ■ 
the intensity-/'^ L 
; the oxygen;.^: 
le differences 
d 2. It was .;^ 
The Tesults ^ 



; oh; *ofc«S 

ace all point 's; 
VI and Cg o * V? 

. atoms could .ty 



: 0.122 
~ 0.311 



: a giving ap- . 
vrn structures 
l Nb* + -0»- ' 
A. 

There oxygen 

0-0 would 
)xygen atoms 
r the oxygen 



NO. 4215 P. 8/ 



ARK.IV FOB KBMI. Bd 1 nr 54 



Me 2 -4 0 2 2.75 
Meg -2 0 4 2.55 
Me a -2 O s 2.55 



Nb- 0 3 = 2.34 
Nb-2O 4 = 2.04 
Nb- O 6 = 2.04 
Nb- 0 3 = 1.84 



at oins in contact with Nb, reasonable interatoinic di^ces were obtemed as- 
JSt, 0 • ft O m &la)z* = 0.100 8 0 3 in 8 (ff) H = 0.264 8 0 4 in 8 (h) z 4 — O.loB 
fnTfc S^tf » --0 MB Even if Jmall adjustments of these parameters are 
dmlttod 8 fi } 5TJi& 4 0 there is room only in the position 00* (O,). 
With these assumptions the distances would be: 

Mex-4 Oi = 2.75 
Me! -2 O a = 2.55 

0 4 -4 0 6 = 2.74 
0 3 -2 O 4 = 2.60 
O 3 -2O 6 = 2.60 
0!-2 0, = 2.66 

It is seen that the positions given might equally well be described by 
if the pseudo-tetragonal unit cell (a = 3.89 0 = 25.53 A) is chosen by Di». 
As o ~ b and the positions of the oxygen atoms must be diosen from space considerations, 
the discussion will bYthe same for *. as for <£> Jcr Cfi. H » W ^ A- «»J« 
1ms can be only in the planes y = 0 y = 0-26 ± 0.03 y = * and* = 0^76 ± 0 03. For 
?To or i . must either be 0 or J or lie between the limits 0.049 < |*| < 0-461, others 
L distance 0-0 will be < 2.6 A. For y = 1 or *, * mnst have the values O, |, * or * 
or lie between the limits 0.049 < N < 0-201 0.299 <H < 0.451. 

Si figure 2a sections of the unit cell are made for , = O and „ = *. >^ """" 
with space group Cg a are denoted in the figure by shaded areas. For these areas the distances 
0-0 2s 2.5 . Me- 0 2: 2.2 and Nb -O 2: 1.8 A. 

With space group Cg. it thus seems that no basically new ato^o Positions 
are obtaSed! flthough this symmetry allows the atoms to be slightly shifted 
from the positions of Da- 



or 



The mode of calculation is snown Dy xne f^^" "'f';. : + 
A = 1 0 (0.5 + cos 2 n Zzm. + (/W/m.) cos 2 + (/o//mo (0-5 + cos 2 * J* + 
+ cos2*J* + 2cos2*U ( ). Since the ratios /„//» ^^IZ't^ m 
6H they wie interpolated from values given in the International Tables (1). 

Case 2. Positions of the oxygen atom? 

The positions of the metal atoms were assumed to be: (0 0 0; \ \ 0; 0 \\\ \ 0 \) + 
+ 000 (4 Me,) + 0 0 0.202 (8Mej) ± 00 0.412 (8 Nb). . , 1<Mnni 

mL ft to following positions are available for the oxygen atoms 4(6) 00* 



8(g) + 00z 
0.086 <. z <■ 0.116 
0.288 < z ^ 0.342 

4(c) Hf M*)*H 



8(A) iif, iH" z 
0.039 ^ |z| < 0.161 

16 (&) xys, syz, 

x = 0 1 = 0.25 ± 0.03 
y = 0.25 ± 03 or y = 0 
* ~ 0.135. 



469 



FEB. 22. 2005 10:43AM Mai ^FOGATE-IE INFO EXPRESS 



IP. 9/19 



B. aurtvilups, Mixed bismuth oxides with layer lattices 




xT 



In Figure J 

■ '''■~R-^b denoted b 
VK'^^Ttositiona give) 
' y ^ j£ft-0 be attaii 

■ : :f^^|^ Thus no : 
^ Table 
;;^^The calcula- 
• ^M^ame aa w* 

Figure 2 a (see Case 1 in the text.) ^^ch Cai 

The projection of the positions of the Nb, Me x and Me* atoms on the planes y = 0 ai^i^^-^ell for the 
y = i are denoted by: black circles, white circles and double circles respectively. an d > 







— HI 1^/ J^rf, mr- 














■< 









^.^Although tl 
£ described bj 
dW& . ; ;(see for inst 
•ei# : =107:lO9). 1 
PbBi 2 Nb0 9 



3" Just as f- 
■X to indicate 
'■: graphs (Tab 
• with axes c 
':■ The intei 
"the metal a 



Figure 2 b (see Case 2 in the text.) < 

It was found that oxygen atoms in the positions 4 (c), 4 (d) or 16 (*) could^, 
not be part of an octahedron around Nb. With 0 in the remaining positions,^ ., me meww a 
4(6), 8(g) and 8(A), octahedra around Nb might be achieved in the foUowing\^;- ^ jb) s 
ways: (1.8 ^ Nb-0 s£ 2.5). • ^-jJ are made at 

With oxygen atoms in three 8-fold positions 8 (A), it seemed impossible to ^ 
find positions for the remaining 12 oxygen atoms giving 0-0 distances <. 2.5 A.;^ / 

With two 8-fold positions 8 (A) + 4 (6) + one 8-fold position 8 (g) the fonowuiff 
positions were assumed for oxygen atoms in contact with Nb: . . -*5c 

4 O x in 4 (b) 8 O a in 8 (g) z = 0.324 
8 0 3 in 8(A) z= 0.088 8 0 4 in 8(A) z = -0.088. 

For the remaining 8 oxygen atoms there was only room in the positions 4 (c) 
and 4(5). (0 5) 0 6 ). 
With the above assumptions the distances wouLd be: 



4 Nb 
8 Bil 
8 Bil 



M ei 


-4 Oi = 


2.75 


Me x 


-4 0 8 = 


2.96 


Mea 


-4 0 4 = 


2.96 


o 6 


-4 0 6 = 


2.75 


o 8 


-4 0 4 = 


2.75 



Me, -2 0 6 = 2.29 
Mea -2 0, = 2.29 
Me a -4 0 8 = 2.82 



Nb- Oi = 2.24 
Nb-2 0 8 = 1,94 
Nb-2 0 4 = 1.94 
Nb- O a = 2.24 

0 2 -2 0 8 = 2.96 
O a -2 0 4 = 2.96 



O a -2 O 6 = 2.70 
0 2 -2 O 6 =2.70 
Oj-4 0 3 = 2.96 
Oi-4 0 4 = 2.96 

The above positions might be equally well described by D§ or if a pseudo- 
tetragonal unit cell is assumed (o = 3.89 c — 25.53) by DS. 



470 



The area* 
and the ra 
Ci and C a 
the observe 
were eonsid 

/W/BlNb> fxb, 

calculated £ 
these calcul 
agreement * 




FEB. 22. 2005 10:43AM Mai lgfcOGATE-IE INFO EXPRESS 



NO. 4215 P. 10/19 



ARKiv fob KEfifl. Bd 1 nr 54 

In Figtire 2b sections are made of the unit cell for y = 0 and y = £ showing the posi- 
s possible for the oxygen atoms if the space group C&o is assumed. Possible regions 
denoted by shaded areas. It was found that only with oxygen atoms situated near the 
itions given above, could ootahedra of 0 around all Nb atoms and reasonable distances 
be attained. 

Thus no new arrangements were found when space group CSa was assumed. 
In Table 1 the intensities are calculated from the parameters given above. 

calculated intensities are denoted by Iz. The mode of calculation is the 
me as was used in case 1. It is seen from the Table that both 1 and 2, 
which cases the influence of the oxygen atoms was neglected, account fairly 
»11 for the experimental data. From this follows that the calculated intensities 
en and I2, where regard was taken to the 0 atoms, do pot differ much either. 
^^Sthough the ratio 211:213 (see Table 1 (pseudo-tetragonal indices)) is best 
W$ 'Ascribed by l\ 2' on the whole seemed to satisfy the observed intensities best 
p£for instance the intensity ratios 112 : 114 116 : 118 202 : 204 101 : 103 and 
^^^M?W ' 109)- No definite conclusions- could however be drawn from the study of 
i^gPb^KbO, alone. 

^SSB Just aa for PbBiaNb a 0 9j there was nothing in the Weissenberg photographs 
v'&i?l eto indicate a lover Laue symmetry than D tt -4/mmm. From the powder photo- 
' 'Pfcaphs (Table 6 a) it is however seen that the actual unit cell is ortborhombic 
I:( .^^th axes a = 5.405 6 = 5.442 c == 25.11 A. . 

The intensities of the spots in the Weissenberg photographs indicate tiLat 
tio ^ ^W the metal atoms are probably placed on the lines 00*. The Patterson function 



wing^ 



Tffig. Ib) showed high maxima at 0.20 and 0.40. If the same assumptions 
Yare made as for PbBiisNb 8 0 6 the following arrangements seemed to be possible: 



4 Nb in 000 B. 
8 BiTi in ± 0 0% 
8 BiTi in ± 0 02a 

C a 4 Bi in 00 0 
8 NbTi in ± 0 02 2 
8 Bi in + 00% 



4 Ti in 000 

8 BiNb in± 00% 

8 BiNb in ± 00% 

% - 0.20 



d 4 Bi in 0 0 0 
8 NbTi in + 0 0% 
8 Bi in + 0 0 % 

3,-0.40 



The areas under the peaks at 0.20 and 0.40 were calculated as for PbBi a Nb a 0» 
and the ratio 0.20/0.40 was found to be 1.4. The calculated ratios for A, B, 
Cx and Ca were 1.0, 1.0, 0.84 and 1.2. The area ratio for Cb agreed best with 
the observed one. The differences are however small, so that all alternatives 
were considered. The intensities were calculated as for PbBi a Nb i 0 9 . The ratios 
hlfmm, /W/am and f^U were assumed to be 0.26, 0.57 and 0.34 The 
,. calculated and observed intensities for A and B are compared in lable 4. in 
; || these calculations the influence of the oxygen atoms was neglected. The best 
Agreement was found for 



mdo- 



A 
B 



0.198 
0.196 



*2 

0.400 
0.400 



471 



t' . 



Si 



I 



8:t 



f 

% 

■ri 
li 

I 

1 :li 



FEB. 22. 2005 10:43AM Ma ij^lFOGATE-IE INFO EXPRESS 



N0.4215». 11/19 



b. auhivhjjtts, Mixed bismut oxides urith layer lattices 



TaUe 2 

Weissenberg photographs of BigNbTiOe. 



1 


*A 






I obs. 
hit 


*20Z 


2 i 

8 

10 


4.0 
7.3 
2.3 
7.3 
510 


i 

12 
22 
5.3 
22 
440 


m 
w 
m 
st 


WW 

8t 
8t 
W 
St 


vw 
m+ 
m 
m 

St / 


12 
14 
16 
18 
20 
22 
24 
26 
28 
30 


1.4 
15 

0.2 
11 
500 

0.1 
27 

0.6 
14 
490 


2.6 
52 

o.o i 

• 30 ! 
400 
0.4 
94 
' 2.0 
31 
350 


w 

m+ 
w 
m+ 
st 

in 
w 
m 
m 


vw 
vw 
w 

Bt 
XXX 

m 

m+ 

m + 


vw 
w 

vw 
m+ 

m 
m+ 


I 












1 

3 
* 

o 

7 
9 


4.4 
6.8 
520 

- 2.6 

11 


12 
17 
450 
6.3 
35 


st 
m 
vst 

m 


m + 
vw 
vst 

ZX1 




11 


0.8 


1.4 


w 


w 




13 
16 
17 
19 
21 
23 
26 
27 
29 

1 31 


9.0 
510 

0.6 
20 

0.0 
12 
600 

0.0 
34 

1.4 


27 
420 
0.3 
70 
0.6 
31 
380 

3.2 
120 
4.4 


vw 

6t 

w 
w 
m 
m+ 

m 
m 


w 

w 

w 
w 
m 
m+ 


i 

i 



One half 
notes the 



From Table 2 it is seen that A and B account quite well for the observed 
intensities. . .! 

With A and B, Bi and Ti or Bi and Nb would occupy the Mn^PJJ™ 
position. This seemed a priori unlikely and if it was assumed that Bi 3 NbTi09 
and PbBi 3 Nb a 0 9 were built up in the same way, arrangements A and B would: 
imply that Pb, Bi and Nb were distributed over one point position, in 
PbBi 2 Nb a 0 9 . Therefore, although arrangements A and B cannot be 
from intensity discussions alone, they seem very improbable and will not be 
dealt with in the following. 



I 

•3 



v 



The £< 
8 NbTi i 
following 

4 ( 
8 ( 
8 ( 

In Tal 



4 Bi i 
la case : 
4 Oj in 



472 



■FEB. 22. 2005 10:43AM fail pGATE-IE 1KFO EXPIESS 



arkiv t6b kemi. Bd 1 nr 54 



NO. 4215 P. 12/19 



m 




Dserved >| 



# Bi •NbTf O 0 

Li Figure 3. ^ 



. - Case Ci 

'■j j >< "Ri in 000 8 Bi in + 00 0.396, 

1 8 S&W? SX^ JEtUi - -i *- 

L folkwing positions we arrived at: 

4**00* 8O 8 in±0O 0.092 8 0, m x 00 0.268 

In Table 3 the intensities are calculated from these parameters. 



3 point V$ 
N0)Ti0 9 |C. 

ion, i^ : .>^ 

not 



Case C2 



4 Bi in 000, 8 Bi in ± 00 0.200 and 18 ^J^^^Ti 

im. In case 2' (see PbBi 2 Nb 2 0 9 ) the Pf^^.ff tlie ^ 

^.#4 (Till 001, 8 0 a in+ 0 0 0.324, 4 0 5 in Hi. 

notbe.^ ■ 1 8 . ... „ n ■ ....in-, z = 0.088 



=4 ' 



4 0, in ui. 8 2»i n ii ,; ; 

8 0,in 1*2; it* 2 



z = 0.088 
a = -0.088 



473 



I 



i 

Si- 

Hi": 

% 

''J 



1 



ill* 



Ms 



Si 



■'.I. 



fir? 1 ?-* 



FEB. 22. 2005 10:43AM 



IGATE-IE INFO EXPRESS 



N0.4215^P. 13/19 



b. ATWvnxiTis, Mixed bismuth oxides with layer lattices 

Table 3 

Weissenbeig photographs of Bi 8 NbTiQ 9 



4 
6 

8 

10 

12 

14 

16 
18 
20 
22 
24 
26 
28 
30 



100 
190 



1 


i : 
2.0 


Bt 


17 II 


3 


29 


in 


6.3 j 


5 ! 


270 


vst 


300 




17 




1.2 ' 


5 1 


29 


m 


56 |i 


11 


5.8 


w 


15 !; 


13 


49 


vw 


28 j 


16 


270 


Bt 


270 


17 


5.3 




0.6 


19 


44 


w 


92 


21 
23 


16 


w 


38 


110 


m 


46 | 


25 


200 




200 


27 
29 


4.4 




. 1.2 


65 


m 


110 


31 


41 


m 


76 j 


202 


J c, 


I obs. 


1 

\ 


2 


18 


vw 


2.9 


4 


12 


m* 


37 


6 


0.1 


m 


16 


8 


48 


m 


17 


10 


300 


St 


320 


12 


33 


vw 


5.8 


14 


37 


w 


68 


16 


2.6 




31 


18 


100 


vw 


45 


20 


240 


m + 


240 


22 


12 




0.6 


24 


42 


m 


140 


26 


29 


m 


45 


28 


100 


m+ 


35 




«£■ In T» 
tjroni tl 
^08:204 

"'■6.396 ai 
fliscrepa 
be • 
£bertainl: 
isto be * 
£■ Thus 
^.consider 
e. r 2' seenu 
r With 

(00 0; 



With 
(00 0; 



Vah 



•v|FEB. 22. 2005 10:43AM Mai j^piFOGATE-IE INFO EXPRESS 



NO. 4215 P. 14/19 



AHKIV FOR KEMI. Bd 1 HT 54 



4m 



\ In Table 3 the intensities are calculated with these assumptions.. It is seen 
\ m the Table that with & the order of the reflections 101 : 103, 211 : 213, 
j2 : 204 and 107 : 109 are reversed. The same result was obtained if the in- 
fluence of the oxygen atoms was neglected. If z m and 2HbTi were varied around 
^'396 and 0.192 so as to give correct- ratios for some of these reflections, large 
xepancies occurred for other reflections. With Cg the intensities turned out 
, be of the right order. There are however a few discrepancies. 00 20 is 
rtainly stronger than 0018 and 00 30 > 0028, but the calculated ratios seem 
jpto be too large. On the whole the agreement is however good. 
I^Thus if the X ray data for only one of PbB^NbgOj or Bi 3 NbTi0 9 were 
Considered, different atomic arrangements appeared to be possible, whereas only 
seems to explain the observed data both f or . PbBi 8 Nb 2 0 9 and Bi^NbTiOg. 
r With orthorhombic description the positions will be: 
; 3)g— mmm 

" (000; OH; i<>i; H<>) + 

4 Bix (MeO in 4 (a) 000 
8 Bi a (Mej) in 8 (») ± 00 0.200 (0.202) 
8 NbTi (Nb) in 8 (i) ± 00 0.412 (0.412) 
4 Oi in 4 (6) 0 0* 

8 O a in 8 (i) 0 0 0.324 (0.324) 

8 0 3 in 8 (/) Hi; HI 

16 0 4 in 16 (j) \\z; Hi; iM 

i = 0.088. 

With' pseudo-tetragonal description the positions will be: 
KdU-I i/mmm 
(000; Hi) + 

2 Bij (Me x ) in 2 (a) 000 
4 Bi a (Mea) in 4 (e) ± 0 0 0.200 (0.202) 
4 NbTi (Nb) in 4 (e) ± 00 0.412 (0.412) 
2 O x in 2 (6) 00} 

4 0 2 in 4 (e) ± 0 0 0.324 (0.324) 

4 0 3 m 4 (d) OH; *0£ 

' 8 0 4 in 8 (?) ± (0}z; *0s) z = 0.088. 

Tabh 4 

Yalues of the tolerance factor, t, for different compounds having the 

CaBijNb 8 0 9 structure. 



Compound 


t. 100 ! 




91 




91 




91 




99 




99 




106 




101 




91 




97 



475 



FEB. 22. 2005 10:43AM Mail I0GATE-IE INFO EXPRESS 



N0.4215W- 15/19 



B . Atrarvrwius, Mixed bismuth oxides with layer lattices 

. Table 5 

Powder photographs of CaBi^O, and SrBiaNbA- 

tetragonal indices. 

CaBiaNbgO,, 



g^able 5 (co 



Cr K radiation. PsendoCtt 

.*S2 



hkl 

006 
008 
114+0 0 10 


I 6bs. 

m 

(m) 


la 

8.4 
61 
230 


0.8 
9.6 
230 


h 
0.01 
0.6 


00 12 
0 0 14 
00 16 
00 18 


vw 
w 


0.6 
29 
2.6 
. 100 


19 
46 

. 0.6 
34 


47 
56 
4.0 
13 


101 
103 
105 
107 
109 


St 

vst 
w 

WW 


1.2 

36 
200 
21 
18 


0.5 
1.4 
200 
0.3 
32 


2.9 
1.4 
200 
7.8 
43 


— 10 11 
. 10 13 
20 1 0+10 1 5 
oil 1-4-T 017 


m+ 
(st) 
(w) 


7.0 
79 
160 
22 


0.2 
19 
160 
0.2 


0,5 
4.4 
160 
9.0 


112 

00 10+114 


(m) 


26 
4.4 


0.04 
14 


4.8 

22 


116 
118 
204+11 10 
11 12 
11 14 


w 

m 

(Bt) 
W 


4.4 
69 
200 
22 
41 


17 
13 
200 
0.1 
61 


26 

1.7 
200 
8.4 

/Z 


202 

11 10+204 
206 

9 1 K-l- 9 A ft' 

10 16+20 10 
20 12 • 


w 
(st)_ 

w 
(St) 
(8t) 
VW 


27 
3,6 
3.2 

69 

220 
1.4 


13 
0.04 
9.0 
220 
15 


4.4 
20 
1.4 
0.5 
220 
41 


9 11 

it X X 

2 13 
208 + 216 
2 17 
2 19 
10 17+2 1 11 


w~ 
w 
(at) 

WW 

(w) 


0.1 
38 
210 
21 
18 
4.4 


2.3 
2.0 
210 
0.3 
33 
0.01 


6.3 
1.0 

ZrXV/ 

7.8 
43 
1.4 




SrBi,Nb a 0 9 






006 
008 
] 14+00 14 


VW 

(m) 


3.2 
45 
260 


0.1 

11 

260 


0.2 
2.6 
260 


00 12 
00 14 
00 16 
00 18 


VW 

m 
w 


0.2 
42 

0.3 
83 


18 
68 

1.4 
35 


35 
64 
4.4 
18 


00 20 


St 


160 


160 


160 



jSOC 



One half 
tioned in 
detennine 
00 0.202. 
f Ca, Sr, Ba 

■| do not diff 
valid for tl 
Ca, Sr, Ba 

a Only 1 
P Kando: 
y Only 1 



476 



•■?FEB 22 2005 10:43AM Mail HMATE-IE INF0 EXPRESS 



NO. 4215 P. 16/19 



ARKXV FOR KEMI. Bd 1 IIT 54 



4** 



.4 



1.2 
S.6 
) 

) 

L4 

) 



hkl 


^obs. 




T - 




101 
103 
105 
107 
1 09 


vw 

St 

w 


0.0 
24 
230 
12 
28 


2.0 

2.0 
240 
0.01 
42 


4.0 
v. x 
230 
3.6 
49 


10 11 
10 13 
20 10+10 15 


m 

(Bt) 


2.3 
61 
190 


0.01 
20 
200 


0.8 
8.4 
200 


500 20+220+10 1 7 
V 10 19 


m 


13 
88 


0.01 
110 


4.0 
120 


112 

00 10+114 
116 


(m) 
vw 


16 
10 
10 


0.3 
20 
22 


26 
29 


118 
11 10. 
11 1 I 
1114 


w 

St 

w 


52 
230 
13 
56 


14 
240 
0.0 
74 


4.4 
230 
3.6 
81 


11 16 
11 18 


m 


0.1 
40 


4.0 
10 


8.4 
2.3 


202 
. 204 
206 

011 14+2 0 8 
10 16+2 0 10 


(w) 

{St} 


17 
9.0 
0.5 

43 
250 


0.4 
19 
0.6 
10 
260 


1.4 
24 
2.3 
2.3 
250 


521 13+20 iz 
20 14 
2 0 16 


(VW) 

w 


0.01 
42 
0.2 


12 
68 
1.7 


29 
64 
4.8 


211 
213 
215 
217 
219 


w 
w 

St 

vw 


0.6 
26 
240 
12 
27 


4.8 
2.6 
240 
0.01 
42 


7.8 
0.01 
240 
3.6 
49 


21 11 
2 1 13 
2 0 10+2 1 15 


m 

(Bt) 


1.2 
59 
190 


0.4 
19 
190 


2.0 
7.8 
190 



_ On. ha., of *e ^-^^^^St^"ff«i ptT» 
■ ; m tioned in the discussion on » positions 000 and 

m: determine How Pb and Bi ^. d ^^ 0 °^ r £ VKE*. positions of 
. 00 0.202. It therefore seemed of n^*** fcBuNbaO,, BaBi^O, and 
l l Ca, Sr, Ba and K in M ^^^qTbI and K compounds 

KBi^O^. As the cell dimensions of ^^U^ 3 PbBi 2 Nb 2 0, are also 
do & 'differ much it ^^^S^S^ °of 'disUuting 
valid for the other compounds. * nCT ® a ~TX 0 0 202- 
Ca, Sr, Ba and K over the positions 000 and 00 U.atc. 

Only Bi in 00 202 
Random distribution 
Only Bi in 000. 

477 



i 



a 

p 

y 



FEB. 22. 2005 



IFOGATE-IE INFO EXPRESS 



B. AxramuJUS, Mixed bismuth oxides wiili layer lattices 

Table 6 a 



Powder photographs of BiaNbTiCV Cr K radiation. 
' Orthorhombic indices. 




17/19 



The intensities were calculated for these possibilities by calculataons i si milar 
ix> those for PbBiaNbA, and compared with tie observe^ ones. T *™ t 
It was found that in no case did y explain the observed intensities. For tte 
Sr Ba and K compounds the observed intenaitiiea did not permit any decision 
between a and 0. For CaBi 2 Nb a 0 9 , however only a seemed to give > correct 
intensities. It was therefore concluded that the compounds discussed have tue 
a arrangement. 

478 



J — 




lie I 


It 


1 U 1 








A AO 

0 U o 




1 A £ 




t 1 A 

110 








114 




tfl 09 




|Tl6 




109 




0200 




00 12 




118 




10 11 




200 




11 10 




00 14 




10 13 




211 




208 




215 




10 15 




20 10 





The strac 
BiNbTiOf 1 
akite struct 
view was £ 
was observe 
would allow 
t is calculate 
between the 
(see Table 
to be stable 

* was calcul 



In the calo 
ionic radii we 
L33, Kb 64 
distributed ove 

47 t 



22.2005 10:43AM Mat I ^OGATE-IE INFO EXPRESS 



Table 6b 

Powder photographs of PbBi 2 Nb 2 O fi . Or K radiation. 
P66udo-tetragonal indices. 




NO. 4215 



ABKTV FOB ICE Ml. Bd 1 I1T 54 



11 14 
219 
00 18 
00 20 
10 17 
1116 
0306 

220 



10* Bin 1 6^ 



XXL 

m 

8t 

vst. 
m 

ro 



6682 

5974 

6520 

6663\ 

6685/ 

6889 \ 

6903/ 

6950 

7419 

7744 

7839 

8049 

8133 

8238\ 

8268/ 

8332 

8688 

8872 
8962\ 
9010/ 
9449 



lOW0 obsu 




5699 


m 


6990 


m 


6529 


w 


6664 


WW 


6924 


m 


6934\ 


m 


6976/ 


zn 


743$ 


m 


7749 


m 


7846 


vw 


8052 


m 


8131 


m+ 


8268 


vw 


8339 


mi- 


8673\ 


m + 


8690/ 


m 1 - 


8874 


st 


8980 


m 


9450 


WW 



dcailar' v 
,ble 5, 

jciaion 
jorrect 
re the 



the. 



The Btructuie of BijNbTiOs is thus built up of BiaOS* layers between which. 
BiNbTiOf" layers are inserted. The structure may be looked upon as a perow- 
akite structure where perowskite layers are separated by BiiOS* layers. This 
view was supported by the fact that in all cases where the above structure 
was observed the radii of the ions in the layers lying between the Bi a OT kyers 
would allow for the formation of a perowskite structure. If the tolerance factor 
t is calculated from the ionio radii of the elements constituting the layers 
between the Bi a 0|* layers, it is found to He between the limits 0.9 and 1.1 
(see Table 4), the same limits within which perowskite structures are found 
to be stable. 

t was calculated from the formula: 1.06 (R A + Ro) = 0.95 t V% (Rb + Ro). (See (3).) 
A = (K + Bi)/2 Ca, Sr, Ba etc. 
B = (Nb + Ti)/2 (Ta + Ti)/2 Nb. Ta. 

In the calculations oase a was assumed. For calculating t the following values for the 
ionio radii were used: Bi*+ 1.00, Ba?+ 159. Sr 3+ 1.20, 0a»+ 1-02, Pb 2 * 1.26, Na + 0.97, 
K + 1.33, Nb 8+ 0.69, Ta 5+ 0.69, Ti t+ 0.66 and 0 ,_ 1.36. If, for instance, 1 K + 1 Bi are 
distributed over one 2-fold position the radius of (K, Bi) was taken as (r K + r B t)/2. 



FEB. 22. 2005 10:43AM Mai 



F06ATE-IE INFO EXPRESS 



NO. 4215 : :P. 19/191 



m 



p..' 



It''; 



5^' 
Si*'- 



b. axtbiyhxitjs, Mixed Ksmu* oxides wiifc layer lattices 

beyerite l^M™*^ ?w tetragonal with a == 3.767 andc = 21.690 1 Th^W 
cell of beyerite is WW*™} .^3^ b rite ^ Ca 0 0 0 and Bi±00 0.19». 
^4^™a^ a = L60 c = 24.87, Ca in 000 and Bg|, 

in 4 00 «WW ?a W^ in beyerite correspond to octahedral Mjgfc 
m in r^BUtt oY Swing the notations given by Lagekckaktz 
i^SKc&I^above might also be denoted by X u . ^ 



SUMMARY 



8 Bi in 
8 NbTi in 
4 0 in 
8 0 in 
8 0 in 



A series of tetragonal or paendo-tetragonal phases of general composition^ 
(Bi, Me),B 4 0i8 nave been investigated. 
Me: Na, K, Ca, Sr,' Ba, Pb. 

siderations. # 

The following structure is proposed: 

(000; OH; 40* i; H0) + 
4 Bi in 4 (a) 000 

8 (») ± 0 0 0.200 
8 (») ± 00 0.412 
4 (6) 00i 

8 (») ± 0 0 0.324 ^ 

ten intend ca!— it ™Jri^l^S^*^t ,: 
andKtatta correwontog <^P<¥»*> ^ B S?KXnating wHh single -3 

I wish to thank Pressor L. 8. SiuJbr for valuabte discussions concern* 

^ota HS^ola. Institute d lao^c and PhysW Chancy, ' 

1949. 

BEFERENCES. L Internationale . 
Berlin 1936. - 2. Wells A. F. Z ^ 96 1937^ A ^ Sillen , L. G. 

mistry, New York and London, 1938, p. 27/. *. 
Arkiv Kemi etc. 25, N:o 20, 1948. 

Tryckt den 31 december 19*9 
TJppsaU 1949. Almqvist * Wiksells Boktryckeri AB 

480 



Ix 
in t 
forn 



has 
alco- 
witb 
httl< 
wat< 
tinu 
M 
kno"< 
not 
Ana 
solv* 
is n 
watc 
(Fig 
inne 
In 
cap£ 

met! 
ben: 
T 
also 
witl 
are 
As 
thai 
qua; 
be 
per 

48 



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