CEMENT and CONCRETE RESEARCH. Vol. 16, pp. 67-73, 1986.

Printed in the USA

0008-8846/86 $3.00+00. Copyright (c) 1986 Pergamon Press, Ltd.

REACTION P R O D U C T OF LIME A N D SILICA FROM RICE HUSK ASH

3ose 3ames and M.Subba Rao

D e p a r t m e n t of Inorganic and Physical C h e m i s t r y
Indian I n s t i t u t e of S c i e n c e
Bangalore - 560 012
India

(Communicated by D.M. Roy)

(Received Sept. 17, 1985)

ABSTRACT

Rice husk ash (about 95% silica) with known physical and c h e m i c a l
c h a r a c t e r i s t i c s has b e e n r e a c t e d with lime and w a t e r . The s e t t i n g
process for a l i m e - e x c e s s and a l i m e - d e f i c i e n t m i x t u r e has been
investigated. The p r o d u c t of the r e a c t i o n has been shown to be
a c a l c i u m s i l i c a t e h y d r a t e , C-S-H(I) + by a c o m b i n a t i o n of t h e r m a l
analysis, XRD and e l e c t r o n m i c r o s c o p y . F o r m a t i o n of C-S-H(I) a c c o u n t s
for the s t r e n g t h of l i m e - r i c e husk ash c e m e n t .

Introduction

Rice husk ash (RHA) is an i m p o r t a n t source of silica. By c o n t r o l l e d t h e r m a l

d e c o m p o s i t i o n of rice husk (l), it is possible to produce an ash which c o n t a i n s
r e a c t i v e silica. The ash is largely composed of silica with minor a m o u n t s of a l k a -
lis and other e l e m e n t s . Silica from rice husk is finding use as a c o n s t i t u e n t of
low-cost c e m e n t s . Though the use of rice husk a s h - l i m e m i x t u r e as a c e m e n t i -
tious m a t e r i a l has been known for a long t i m e , the r e a c t i o n of silica in RHA with
lime is l i t t l e studied (2). It has been r e p o r t e d t h a t the R H A - l i m e c e m e n t has
v a r y i n g s t r e n g t h , depending on the r e a c t i v i t y of ash. Even with r e a c t i v e ash, the
s t r e n g t h i n c r e a s e s upto 28 days and l a t e r a g r a d u a l d e c r e a s e is noTticed (3). The
n a t u r e of the r e a c t i o n p r o d u c t b e t w e e n RHA and lime is not well u n d e r s t o o d .
Here an a t t e m p t has been made to u n d e r s t a n d the c h e m i s t r y involved in the
r e a c t i o n b e t w e e n RHA and l i m e in the p r e s e n c e of w a t e r and to suggest possible
causes for the long t e r m d e c r e a s e in the s t r e n g t h of R H A - l i m e c e m e n t .

Experimental

Rice husk ash

Rice husk used for the p r e p a r a t i o n of ash is from the E x t e n s i o n C e n t r e

+ Symbols used : C=CaO S=SiO 2 H=H20

67
68 Vol. 16, No. I
J. James and M. Subba Rao

of ASTRA (Centre for A p p l i c a t i o n of Science and Technology to Rural Areas).

Husk is washed w i t h water to free it from adhering soil and clay and dried in air
at ambient temperature. The dried husk is heated in a m u f f l e furnace at 500C
for 12 hours to obtain ash.

Lime

BDH l a b o r a t o r y r e a g e n t grade c a l c i u m hydroxide powder from fresh unopened

bottles.

RHA-lime mixtures

Mixtures in two r a t i o s of a s h : l i m e were p r e p a r e d - l;3(lime excess) and 2:1

(lime d e f i c i e n t ) mole ratios. These m i x t u r e s were mixed with m i n i m u m q u a n t i t y
of w a t e r to p r e p a r e p a s t e s . Blocks of 1.0 cm size were prepared from these
pastes and the blocks were kept in d e s i c c a t o r s to avoid c o n t a c t with c a r b o n -
dioxide from air. The blocks were kept moist by wrapping wet c o t t o n wool
around t h e m . A few blocks were kept i m m e r s e d in w a t e r and a few were kept
moist and exposed to a t m o s p h e r i c c a r b o n dioxide. At known i n t e r v a l s ranging
from one day to 2g days, the blocks were t a k e n out, powdered and i m m e r s e d in
a c e t o n e , washed with e t h e r and thoroughly dried in a v a c u u m and were analysed
for the products.

C-S-H(1)

A c o m p a r i s o n s a m p l e of C-S-H(I) was p r e p a r e d by a known p r o c e d u r e (4)

from sodium s i l i c a t e and c a l c i u m hydroxide.

X - r a y d i f f r a c t o g r a m s were recorded w i t h a Philips PWI050/70 diffracto-

meter w i t h Cu K~ radiation at a scan rate of 2/min. Thermal analyses were
carried out on a co~nbined TG, DTG, D T A u n i t - U L V A C 1 5 0 0 . Infrared spectra
in the 200-4000 cm region were recorded in alkali halide pellets on a Perkin
Elmer 597 Spectrometer. Electron micrographs were recorded w i t h a Cambridge
Stereoscan 150 scanning electron microscope. Transmission micrographs were
taken w i t h a Philips EM 301 microscope.

Results and Discussion

The c h a r a c t e r i s t i c s of the rice husk ash are as follows: analysis-SiO2-95%;

CaO -0.441%; MgO -0.425%; Fe20 3 -0.713%; K20 -1.048%; N a 2 0 -0.415%; and
o
carbon less than 1%. The average c r ~ s t ~ l l i t e size of silica was around 25 A and
the surface area of the ash was 150 m g

Thermograms of R H A : l i m e mixtures before and a f t e r setting are shown

in figure I. The w e i g h t loss step in the temperature region 490-550C (figure la)
represents the decomposition of calcium hydroxide to calcium oxide. This step
is absent in lb, i n d i c a t i n g the absence of free lime in the f i n a l product. Even in
the lime excess m i x t u r e , the mass of free lime and calcium carbonate present
in the final p r o d u c t is much less than the i n i t i a l mass of lime. The set lime.-
d e f i c i e n t m i x t u r e e x h i b i t s an e x o t h e r m i c peak around g40C in DTA. The X-ray
d i f f r a c t o g r a m s show i n i t i a l l y p r o m i n e n t r e f l e c t i o n s of c a l c i u m hydroxide, while
the final p r o d u c t s show only broad r e f l e c t i o n s around 29.4 and 32 two t h e t a
for a l i m e - d e f i c i e n t m i x t u r e . Even in l i m e - e x c e s s m i x t u r e s in addition to the
r e f l e c t i o n s from u n r e a c t e d lime, these a d d i t i o n a l r e f l e c t i o n s are n o t i c e d . How-
e v e r , the X-ray r e f l e c t i o n s of u n r e a c t e d lime and c a l c i u m c a r b o n a t e (formed
Vol. 16, No. I 69
RICE HUSK ASH, C-S-H(1), XRD, SEM, TG

by reaction with atmospheric carbondioxide) overlap the principal reflections of

the C-S-H(I) phase. (Figs. 2-4)
The absence of unreacted lime in a lime deficient mixture
is further corroborated by the i n f r a r e d l s p e c t r a of the samples. In the final
product OH-absorption around 3600 cm Ls absent (figure 5b), confirming the
absence of free lime (5) after setting.
0

(a)
Figure 1 (b)
TG of RHA:lime mixtures f,
(a) 2:1 mixture before setting (d)
(b) 2:1 mixture after setting
(c) TG ol synthetic C-S-H(I)
()
(d) TG of 1:3 mixture alter 28 days
of setting.
(e) DTA of 2:1 mixture before
setting.
(f) DTA of 2:1 mixture a!ter
setting.
(g) DTA of syntheticC-S-H(I)
(h) DTA of 1:3 mixture a l t e r
28 days of setting.

o ~oo ~;o ~o ~ ~o
Temperature, oC

The thermal behaviour (6), XRD of the set product and that of the residue
obtained by heating to 900C, are identical to those ol the synthetic sample of
C-S-H(I). Hence there is conclusive evidence for the formation of calcium sili-
cate hydrate in the setting of rice husk ash-lime pastes. The reaction appears
to be complete in less than four days (figure 2) for a lime-deficient mixture.
Alkalis act as catalysts in the formation of calcium silicate hydrate from lime
and silica. This might be due to the formation of sodium silicate which further
reacts with calcium hydroxide to form C-S-H(I). Presumably the NaOH released

(c)

Figure 2
XRD of
(a) 2:1 RHA:lime mixture before
setting.
(b) 2:1 RHA:lime mixture after
setting.
(c) synthetic C-S-H.

,o----- 2 B
70 Vol. 16, No. ]
J. James and M. Subba Rao

: 11: : i f : i ~ :2:L~:~__ ZZZZI:~__: -- -

Figure 3
X R D of
(a) h3 mixture before setting
(b) 1:3 mixture after setting for 2g
days exposed to air.
~__ i J (c) 1:3 mixture after setting exposed
31 30 29 2B 31 30 29 28 31 30 29 28 I
to air.
(d) 1:3 mixture after setting immersed
in water.
(e) 1"3 mixture after setting in a desi-
ccator free from atmospheric
carbondioxide.
(b) _ _

3-
J
3~,
U2 32 30 28 26
2e
24 22 20 18

in this reaction would react again with silica and thus continue the cycle. The
presence of alkalis in RHA could explain its rapid reaction with lime.

Morphologies of C-S-H(I) produced during the setting of R H A - l i m e cements

are depicted in figure 6. Figure 6(a) shows dense fibrilar structure radiating
in a 'porcupine' fashion from silica grains, while 6(b) shows gel coatings around
the silica deposits. Closer scrutiny reveals fine surface protuberances on the gel
coatings. Figures 6(c) and (d) show the transmission electron micrographs.
Bundles of interlocking acicular fibres can be seen. A l t e r n a t e light and dark
patches along the length of the fibre might indicate, hollow tubular cross-
sections /or these fibres. Similar features have been reported in the electron
micrographs of set portland cement, where C-S-H is known to be one of the
major products of hydration (7).

Figure 4
XRD of
(a) set cement and (b) synthetic
C-S-H, after heating at 900C
I for 12 hours.
J

~ 2 e
Vol. 16, No. l 71
RICE HUSK ASH, C-S-H(1), XRD, SEM, TG

Figure 5
IR spectra of
(a) 1:3 m i x t u r e after
setting exposed
to air.
(b) 2:1 mixture before i

setting.
(c) 2:1 mixture after 3~ 36o0 ~0o 3~ 3000 , ~ 1200 10~ O~O
setting. Wavenumber (cm-1)

It is reported (2) that the strength of portland cement increases when mixed
with 10-20% of rice husk ash. In the setting of portland cement C-S-H gel and
CH comprise over 75% of the hydrated cement paste and it has been postulated
(g) that CH represents the weaker o5 the two phases. Primarily the strength of
cement is attributable to the C-S-H component (9). The conversion of liberated
lime also into C-S-H, confers enhanced strength to the mixture of portland

Figure 6a
Scanning electron micro-
graph of 2:1 RHA:lime
paste after setting.

Figure 6b
Scanning electron micrograph
of 2:1 RHA:lime paste after
setting.
72 Vol. 16, No. 1
J. James and M. Subba Rao

Figure 6c
Transmission electron
micrograph of 2:1 RHA:lime
paste a f t e r setting.

0.1 um

Figure 6d
Transmission electron
micrograph of 2:1 RHA:lime
paste a f t e r setting.

c e m e n t and RHA. The f o r m a t i o n of C-S-H(I) during the setting of a paste of

lime and rice husk ash accounts for the strength of the set mass.

The following r e a c t i o n sequence might explain the setting process leading to

e i t h e r d e v e l o p m e n t of strength or its e n h a n c e m e n t .

SiO2(RHA) + H20 > C-S-H + u n r e a c t e d silica (1)

C S (portland cement) + H20 > C-S-H + Ca(OH) 2 (2)

c32s
Portland c e m e n t + RHA + H20 > C-S-H + u n r e a c t e d silica (3)

The long-term decrease in strength of R H A - l i m e cement might be due to

changes in m o r p h o l o g y / c r y s t a l l i n i t y of C-S-H and unreacted silica,
Vol. 16, No. l 73
RICE HUSK ASH, C-S-H(1), XRD, SEM, TG

Acknowledgements

We wish to thank our colleague, Professor A.K.N. Reddy, for his keen
interest and e n c o u r a g e m e n t during this investigation.

References

1. 3ose 3ames and Mo Subba Rao, Thermochim. Acta (in press).

2. P.K. Mehta, Proc. Workshop on Rice Husk Ash Cement, UNIDO/ESCAP/RCTT,

pp. 113-122, Peshawar, Pakistan (1979).

3. M.R. Yogananda, K.S. 3agadish and R. Kumar, Alternative Building Series 9,

Studies on Surki and Rice Husk Ash Pozzolana, pp. g5-90 (1983).

4. H. Funk, Silikatechnik l__l_l,375 (1960).

5. D.S. Snell, J. Amer. Ceram. Soc. 5_gg, 292 (1975).

6. S.A. Greenberg, 3. Phys. Chem. 58, 362 (1954).

7. F.M. Lea, The Chemistry of C e m e n t and Concrete, 3rd Ed., Ch.9, pp. 177-249,
Edward Arnold Ltd., London (1970).

8. R.W. Williams, Electron Microscopy and Structure of Materials, (eds.)

G. Thomas, R.M. Fulrath and R.M. Fisher, Univ. California Press, Berkeley,
(1972).
9. S.O. Oyefesobi and D.M. Roy, Cem. Concr. Res., 7, 95 (1977).