CEMENTand CONCRETERESEARCH. Vol. 6, pp. 707-710, 1976. Pergamon Press, Inc Printed in the United States.
STUDIES
ON E X P A N S I V E
I- V O L U M E H.
E6-Didamony,
N.
CEMENT
CHANGES
Mostafa
and M o Z o
Mostafa
Chemistry Department,Faculty of S c i e n c e , Z a g a z i g U n i v e r s i t y and Refractories and Building Materials Department, National Research Centre, Bokki, Cairo, Egypt.
(Communicated by H. F. W. Taylor) (Received May 25, 1976)
ABSTRACT K a o l i n w a s u s e d as an a l u m i n o u s r a w m a t e r i a l i n s t e a d of b a u x i t e f o r the m a n u f a c t u r e of e x p a n s i v e c e m e n t clinker. The linear expansions and compressive s t r e n g t h s of the d i f f e r e n t e x p a n s i v e c e m e n t p a s t e s were investigated. T h e e x p a n s i b i l i t y of the p a s t e w a s h i g h e s t at a m o l a r r a t i o G a S 0 L , : CaO : C4A3~ of 8 : 6 : I.
In e i n e r L a b o r u n t e r s u c h u n g wird Kaolin aber kein B a u x i t als R o h s t o f f e d e r A 6 p 0 3 f ~ r d i e Q u e l l z e m e n t h e r stellun~ verwendet. Die L~ngen~nderungen sowie die Druckfestigkeiten der verschiedenen Mischungen werden bestimmt. Es w i r d f e s t g e s t e l l t , d a s s das Molverhaltnis yon CaSO 4 : Ca0 : C4A3~ = 8:6 : I die besten Quelleigenschaften und Festigkeiten besitzt.
707
708
Vol. 6, No. 5 H. EI-Didamony, N. Mostafa, M. Z. Mostafa Introduction
Concrete made from normal portland cement suffers from shrinkage, which can cause major problems. S h r i n k a g e c a n be e l i m i n a t e d , or at l e a s t r e d u c e d , b y u s i n g an e x p a n s i v e c e m e n t , and for s o m e a p p l i c a t i o n s it m a y be d e s i r a b l e to d e v e l o p a p o s i t i v e e x p a n s i o n , as for i n s t a n c e to i n d u c e t e n s i l e s t r e s s e s in the r e i n f o r c i n g steel. The most successful expansive c e m e n t s h a v e b e e n o n e s in w h i c h e x p a n s i o n is c a u s e d b y the f o r m a t i o n of e t t r i n g i t e , C ~ A . 3 C ~ . 3 2 H 2 0 . One w a y of p r o d u c i n g this p h a s e is b y u s i n g a m l x t u r e of P o r t l a n d c e m e n t w i t h an e x p a n s i v e c l i n k e r c o n t a i n i n g the c o m p o u n d C 4 A 3 S . F o r the f o r m a t i o n of e t t r i n g i t e , it is n e c e s s a r y that the e x p a n s i v e c l i n k e r s h o u l d a l s o c o n t a i n free C a S 0 4 and Ca0. Expansive c l i n k e r s c o n t a i n i n g t h e s e two c o m p o n e n t s h a v e u s u a l l y b e e n m a d e u s i n g b a u x i t e as a r a w m a t e r i a l , b u t N a k a m u r a et al. (I) and E6-Didamony and H e n n i n g (2) h a v e e x a m i n e d the p o s s i b i l i t y of r e p l a c i n g this w i t h k a o l i n . In the p r e s e n t p a p e r , we i n v e s t i g a t e the p o s s i b i l i t y of m a k i n g an e x p a n s i v e c l i n k e r u s i n g g y p s u m , l i m e s t o n e and k a o l i n f r o m E g y p t i a n s o u r c e s , and the s t r e n g t h and e x p a n s i v e c h a r a c t e r i s t i c s of the e x p a n s i v e c e m e n t s prepared using varying proportions of e x p a n s i v e c l i n k e r and portland cement.
Experimental The m a t e r i a l s u s e d w e r e p o r t l a n d c e m e n t , k a o l i n (fro m Kalabsha, Aswan, Egypt), limestone (from Sammalout, Minia, E g y p t ) and g y p s u m (from A l e x a n d r i a , Egypt). Table 1 gives a n a l y s e s of the k a o l i n , g y p s u m and c e m e n t ; the l i m e s t o n e c o n t a i n e d o v e r 9 8 % C a C O 3. The calculated phase composition of the g y p s u m w a s C a S O 4 . 2 H 2 0 , 88%; C a C O 3, 9%; other phases ( i n c l u d i n g SiO 2 and N a C g ) , 3%. T h e w e i g h t s of k a o l i n , l i m e s t o n e and g y p s u m n e e d e d to m a k e an e x p a n s i v e c l i n k e r of g i v e n p h a s e c o m p o s i t i o n , r e f e r r e d to the i g n i t e d w e i g h t , w e r e c a l c u l a t e d by N a k a m u r a ' s e q u a t i o n s (I). 100 1 . 7 8 ( ( 0 . 5 5 + 0 . 1 8 3 n ) P + 1 . 1 7 F + 1.875) 1.13 ( 0 . 4 4 5 ( I + m ) P + I. 13S ) , w h e r e 5% Ag203 - 0.426 %Fe203) in k a o l i n ; Fe203 in k a o l i n ; % Si02 in k a o l i n ; desired molar ratio OaS04/C4A3S in c l i n k e r , desired molar ratio CaO /C4A3S in c l i n k e r .
Kaolin Limestone Gypsum P F S
= = = = = =
m
=
n
=
Four each case porcelain then mixed and b u r n e d g r o u n d to
c l i n k e r s w e r e m a d e w i t h d i f f e r e n t r a t i o s m : n. In the t h r e e c o n s t i t u e n t s w e r e g r o u n d s e p a r a t e l y in a b a l l m i l l to p a s s c o m p l e t e l y t h r o u g h a 2 0 0 - m e s h sieve, in a s l u r r y w i t h w a t e r in the b a l l m i l l for one h o u r , as p e l l e t s for one h o u r at 1150°C. The p r o d u c t w a s b e l o w 63 wm. Table 2 gives analyses.
and
P a s t e s w e r e m a d e u s i n g m i x t u r e s of one or o t h e r of t h e s e e x p a n s i v e c l i n k e r s w i t h the p o r t l a n d c e m e n t in v a r i o u s p r o p o r t ions, at a w a t e r / t o t a l c e m e n t r a t i o of 0.25. The expansive c e m e n t c l i n k e r and p o r t l a n d c e m e n t w e r e m i x e d t o g e t h e r for one
Vol. 6, No. 5
709
EXPANSIVE CEMENT, VOLUMECHANGES, RAW MATERIALS TABLE
I
Chemical Analyses of Kaolin, Gypsum and Portland Cement
Kaolin Gypsum Portland
Cement
SiO 2
A6203
Fe203
46.02
39.44
0.45
0.38
--
5.40
3.45
64.03
-21.06
CaO
MgO
0.30
0.26
34.06
0.03
41.03
3.31
0.80
2.40
--
TABLE
S03
C02
. . . .
I.L.
Total
13.50
99.97
21.32
100.17
2.42
99.55
2
Chemical Analyses of the Clinkers SiO 2
A6203
Fe203
Ca0
SO 3
Total
m
n
m/n
I 2
10.74 9.70
9.00 7.75
0.70 0.65
48.30 52.00
31.72 30.10
100.46 100.20
8 8
6 8
1.33 1.00
3
9.40
7.60
0.60
51.80
31.25
100.65
9
7
1.29
4
9.15
7.30
0.50
52.92
30.02
99.89
10
8
1.25
h o u r in a p o r c e l a i n b a l l m i l l u s i n g one b a l l . Mixing was d o n e u s i n g o r d i n a r y g a u g i n g t r o w e l s on a s t e e l p l a t e c o n t i n uously and vigorously for 4 minutes. The pastes were moulded i n t o I x I × 6 cm p r i s m s f o r e x p a n s i o n t e s t s and i n t o one i n c h ( 2 . 5 4 cm) c u b e s f o r the c o m p r e s s i v e s t r e n g t h t e s t s . I m m e d i a t e l y a f t e r m o u l d i n g , the s p e c i m e n s f o r e x p a n s i o n t e s t s w e r e c u r e d in a moist c a b i n e t f o r 6 h o u r s ; they were then r e m o v e d f r o m t h e i r m o u l d s a n d c u r e d c o n t i n u o u s l y at r o o m temperature (23 ~ I°C) in w a t e r f o r 28 days. Length measurem e n t s w e r e m a d e a f t e r 6 h o u r s and 3, 7, 14, a n d 28 d a y s , u s i n g a p r o c e d u r e s i m i l a r to t h a t d e s i g a t e d C 1 5 1 - 6 0 in the A S T M s t a n d a r d s f o r c e m e n t , l i n e a r e x p a n s i o n s in m m / m b e i n g c a l c u l a t e d f r o m a v e r a g e l e n g t h c h a n g e s b a s e d on the i n i t i a l measurements at 6 h o u r s . Results
and
Discussion
Fig. I s h o w s the v a r i a t i o n w i t h c u r i n g t i m e a n d p r o p o r t i o n of e x p a n s i v e c l i n k e r in c o m p r e s s i v e s t r e n g t h a n d l i n e a r e x p a n s i o n f o r p a s t e s m a d e u s i n g e a c h of the f o u r d i f f e r e n t expansive clinkers. I n Fig. r e p l o t t e d to clinkers.
2 the allow
results for 20% expansive clinker a direct comparison between these
are four
I n all c a s e s the e x p a n s i o n i n c r e a s e s w i t h the a m o u n t of expansive clinker. The highest expansions were obtained with e x p a n s i v e c l i n k e r 1, w h i c h a l s o g a v e r e a s o n a b l e c o m p r e s s i v e strengths. In t h i s c l i n k e r , the m o l a r r a t i o s C a S O 4 : C a O : C 4 A 3 S are 8 : 6 : 1 ; t h i s c o r r e s p o n d s to the c o m p o s i t i o n of e t t r i n g i t e ,
710
Vol. 6, No. 5 H. EI-Didamony, N. Mostafa, M. Z. Mostafa
w h e r e a s m i x t u r e s c o n t a i n i n g l o w e r p r o p o r t i o n s of s u l p h a t e m i g h t be e x p e c t e d to y i e l d m o n o s u l p h a t e : H20 3 (C3A. 3CS. 32H20) C4A3S + 8CaSO 4 + 6CaO
ion
H20 04A3S
> 3 ( C 3 A . C S . 12H20)
+ 2CaSO 4 + 6CaO
r ,
I
uJ
S 10
15
j_gJ- J
20
Tame(days) EC% Expansive Chnker 2
Dine (days)
EC% Expansive Clinker 1
13 7 Dine (days)
%
28
10
Dme (days)
f C Z
15 20 EC %
Expansive Chnker 4
Expansive Clinker3
FIG. 1 Linear expansions (E,mm/m) and compressive strengths (R,ibxinxll0-3) for pastes made with four different expansive clinkers, plotted against curing time and the percentage of expansive clinker in the cement (E.C.). In plots against time, percentages of expansive clinker are shown thus: o 0%, o 10%, • 15%, and A 20%. In plots against percentage of expansive clinker, curing times are shown thus: o 1 day, • 3 days, A 7 days, ; 14days, and i 28 days. 14
12
#0
R8 6 4 2 I
I
I
I
20
E
FIG. 2 Linear expansion (E,mm/m) and compressive strengths (R, ib/in2xl0 -3) for pastes made with 20% of four different expansive clinkers.
~6
o Clinker 1
• Clinker 2
~2
A Clinker 3
i Clinker 4
~0 8
m Portland cement
6 &
2 3
1 .
2.
7
~ rime ( d ~ s }
N. Nal~amura,
G.
References S u d o h and S . A k a i w a ,
Cement, Tokyo,
1968, ~,
H.
and O. H e n n i n g ,
Eg-Didamony
5th
Int.
Symp.
Chem.
351 ( 1 9 6 9 ) . S i l i k a t t e c h ~ 2__44 279
(1973).