[Cryst. Res. Technol.

I 27 I 1992 I 7 1 K 105 -3
Short Notes

P. B. V. PRASAD, G. SAMBASIVA R A O

S. R. R e s e a r c h L a b o r a t o r y f o r S t u d i e s i n C r y s t a l l i z a t i o n
Phenomena,Hanumakonda, India, and
Department o f M e t a l l u r g y , Regional Engineering College
Warangal, India

P o w d e r XRD S t u d y o n U r e a - B i u r e t (Habit Modifer) System

1. I n t r o d u c t i o n

-
U r e a ( t e t r a g o n a l : 42m) i s an i m p o r t a n t o r g a n i c m a t e r i a l , i n view o f i t s
high non-linear optical properties (CASSIDY e t a l . ) . When c r y s t a l s a r e
grown a t t h e u s u a l g r o w t h r a t e s (>0.3 mm/day), t h e y possess a needle-
l i k e habit. Such h a b i t i s n o t d e s i r a b l e f o r d e v i c e a p p l i c a t i o n s . I t was
r e p o r t e d (DAVEY e t a l . ) , t h a t b i u r e t could modify t h e h a b i t o f urea
growing a t c e r t a i n c r i t i c a l s u p e r s a t u r a t i o n s and i n e f f e c t i v e i n o t h e r
s u p e r s a t u r a t i o n s . T h e s t r u c t u r a l e x p l a n a t i o n s o f f e r e d (DAVEY e t a l . ) in-
dicated incorporation o f b i u r e t molecules i n t o growing urea c r y s t a l s ;
one m o l e c u l e o f b i u r e t c a n r e p l a c e a p a i r o f u r e a m o l e c u l e s . Can s u c h
i n c o r p o r a t i o n l e a d t o an a p p r e c i a b l e a l t e r a t i o n o f t h e c e l l d i m e n s i o n s
o f u r e a ? The p r e s e n t w o r k h a s b e e n t a k e n u p t o p r o b e t h i s p o i n t .

2. Experimental

Crystals o f urea, i n presence o f b i u r e t i n d i f f e r e n t concentrations,

were g r o w n b y s l o w s o l v e n t e v a p o r a t i o n a n d b y s l o w s o l u t i o n c o o l i n g
techniques. Methyl e t h y l ketone, methyl alcohol, isoamyl alcohol ( a l l
o f a n a l y t i c a l grade reagents) and double d i s t i l l e d w a t e r were used as
solvent. Crystal o f u r e a g r o w i n g i n t h e p r e s e n c e o f 10% b i u r e t from
water solutions i s s h o w n i n F i g u r e 1; t h e e x t e n t o f h a b i t c h a n g e s c a n
be n o t i c e d . Attempts t o grow l a r g e s i n g l e c r y s t a l s o f urea ( i n presence
o f biuret)were n o t made. The p o l y c r y s t a l s ( m i l l i m e t e r and s u b m i l l i m e t e r
s i z e s ) w e r e d r i e d a n d p o w d e r XRD a n a l y s e d b y e m p l o y i n g a J e o l X - r a y
diffractometer.
K 106 PRASAO, SAMBASIVA: Study on Urea-Biuret System

Fig. 1. A c r y s t a l o f u r e a g r o w i n g
i n p r e s e n c e of 10% b i u r e t
i n aqueous s o l u t i o n

3. Discussion

The p o w d e r XRO p a t t e r n s w e r e i n d e x e d w i t h t h e h e l p o f s t a n d a r d p o w d e r
XRD i n f o r m a t i o n ( X - r a y card 8-822: I n d i a n I n s t i t u t e o f Chemical Techno-
logy, Hyderabad), and t h e c e l l p a r a m e t e r s ( a , c ) were e v a l u a t e d (Tab. 1).

Table 1
C e l l parameter values, c a l c u l a t e d f r o m XRD d a t a , o f u r e a c r y s t a l s grown
i n presence of b i u r e t

S.No. solvent biuret a C

(% b y w e i g h t )

1 M e t h y l a l c o h o l (MA) 2 5.651 4.717

2 MA 10 5.671 4.715
3 MA 10 5.659 4.707
4 MA 20 5.642 4.717
5 MA 20 5.642 4.709
6 MA t isoamyl alcohol 5 5.659 4.709
7 MA t isoamyl alcohol 10 5.637 4.709
8 water 15 5.648 4.702
9 as r e c e i v e d 0 5.648 4.727
10 WYCKOFF-s v a l u e 0 5.662 4.716
t o . 002
- +o. 002
-

The o b t a i n e d v a l u e s w e r e a l s o compared w i t h t h e c e l l p a r a m e t e r v a l u e s ,
c o m p i l e d b y WYCKOFF. It i s i n t e r e s t i n g t o n o t i c e t h a t there i s no
Cryst. Res. T e c h n o l . 27 (1992) 7 K 107

s p e c i f i c dependence o f t h e v a l u e s o f a and c on t h e p r e s e n c e o f b i u r e t .
It i s estimated that, i n case t h e r e a r e any v a r i a t i o n s i n t h e a- and c
values o f urea c r y s t a l l a t t i c e , due t o t h e i n c o r p o r a t i o n o f b i u r e t , such
v a r i a t i o n s a r e less t h a n 0.1%. P r o b i n g beyond 0.1% r a n g e i s n o t p o s s i b l e
by t h e p r e s e n t t e c h n i q u e , as t h e d a t a a r e overshadowed by t h e f l u c t u -
ations.
An a n a l y s i s , based on t h e m o d e l g i v e n by DAVEY e t a l . o f t h e (001)
face o f urea c r y s t a l s growing under t h e i n f l u e n c e o f b i u r e t , indicates
t h a t s e v e r a l p o i n t d e f e c t s and v o i d s (due t o t h e b u n c h i n g o f p o i n t de-
fects) may o c c u r , leading t o the formation o f defective crystal. T h e PVT
grown urea c r y s t a l s were o f p o o r o p t i c a l q u a l i t y , w h e n b i u r e t was p r e -
s e n t i n t h e m (FEIGELSON e t a l . ) . Bulk c r y s t a l s o f urea, i n t h e presence
o f biuret, a r e being s t u d i e d t o determine t h e i n f l u e n c e o f b i u r e t on t h e
o p t i c a l q u a l i t y o f s o l u t i o n grown c r y s t a l s .

REFERENCES

CASSIDY, C., HALBOUT, J. M., DONALDSON, W . , TANG, C. L.: O p t . Commun.

29 (1979) 243
-
DAVEY, R., FILA, W . , GARSIDE, J.: J. Cryst. Growth 79 ( 1 9 8 6 ) 607
FEIGELSON, R. S., ROUTE, R . K., KAO, T. M.: J. C r y s t . Growth 3 (1985)
585
WYCKOFF, R. W. G.: Crystal Structures, Vol.1; I n t e r s c i e n c e , London 1966,
p. 161

(Received, a c c e p t e d May 1 2 , 1992)

Authors- address:
c/o Dr. P. B. V. PRASAD
S. R. R e s e a r c h L a b o r a t o r y f o r S t u d i e s i n C r y s t a l l i z a t i o n Phenomena
P . 8 . No 2 3
Hanumokonda - 506 0 0 1
India