CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 933-938, 1993. Printed in the USA.

0008-8846D3. $6.00+00. Copyright © 1993 Pergamon Press Ltd.

E F F E C T O F B U R N I N G C O N D I T I O N S A N D MINOR C O M P O N E N T S
ON THE C O L O R O F P O R T L A N D C E M E N T C L I N K E R

M.ICHIKAWA and Y.KOMUKAI

Cement&Concrete Research Dept.

Central Research Laboratory
Chichibu C e m e n t Co.,Ltd.
2-1 - 1, T s u k i m i - C h o , K u m a g a y a - S h i
S a i t a m a , 360 J a p a n

(Communicatedby H.F.W. Taylor)

(ReceivedAug. 20, 1992)

ABSTRACT
The s u b s t i t u t i o n of Me 2 ~(Mg,Zn) for AI a ~ and F e a ~ in the c a l c i u m
a l u m i n o - f e r r i t e phase, which i n t r o d u c e s e x t r i n s i c o x y g e n v a c a n c i e s in t h e
s t r u c t u r e , is e s s e n t i a l to t h e c h a n g e in c o l o r f r o m yellowish brown to
dark g r e y . H o w e v e r , an i n c r e a s e of t h e r a t i o Me 4 ~(Si,Ti)/Me z ~ in t h e
ferrite phase, which, for e x a m p l e , is e n c o u r a g e d by slow c o o l i n g in
n i t r o g e n , r e d u c e s t h e n u m b e r of e x t r i n s i c o x y g e n v a c a n c i e s and p r e v e n t s
the above color change. With C 6 A 2 F solid solutions t h e c o l o r c h a n g e is
a c c o m p a n i e d by a d e f i n i t e i n c r e a s e in e l e c t r i c c o n d u c t i v i t y , i n d i c a t i n g
the significance of electrons released by the oxidation of FeO in
a d d i t i o n to t h e o c c u r r e n c e of o x y g e n v a c a n c i e s .

Introduction

Previous studies l) 2) showed that w i t h MgO in c l i n k e r the f e r r i t e phase is

dark grey w h i l e i t is yellowish brown w i t h o u t MgO. However, w i t h o u t oxygen in
the atmosphere the f e r r i t e phase remains yellowish brown even in the presence
of MgO.
In the present study laboratory clinkers and C 6 A z F solid solutions of
different colors were prepared by systematically changing those factors
relevant to the color and subjected to FeO analysis, EPMA and e l e c t r i c
c o n d u c t i v i t y measurement. Discussions have been made concerning the mechanism
of the color change.

Materials

1. C l i n k e r s
The c l i n k e r s w i t h and w i t h o u t m i n o r c o m p o n e n t s w e r e p r e p a r e d under d i f f e r e n t
burning a t m o s p h e r e s and c o o li n g c o n d i t i o n s . The b asi c c l i n k e r was of t h e
q u a r t e r n a r y s y s t e m : SiO2 23.396, Al2Oa 5.196, F e 2 0 3 3.tt96 and C a O 68.0% by
w e i g h t . The r a w m i x e s , a f t e r being p e l l e t i z e d , w e r e h e a t e d a t 50Wmin up to
10001~ and t h e n at 30Wmin up to t h e m a x i m u m t e m p e r a t u r e l tt901~ with r e t e n t i o n
for 20 and 5 min a t 1000 and 14901~, r e s p e c t i v e l y . Tab l e 1 shows t h e

933
934 M. Ichikawa and Y. Komukai Vol. 23, No. 4

a t m o s p h e r e s , coo l in g r a t e s and q u e n c h i n g t e m p e r a t u r e s employed. Q u en ch i n g was

m a d e in air r e g a r d l e s s of t h e burning a t m o s p h e r e s .

T a b l e 1 Burning c o n d i t i o n s o f c l i n k e r s
Atmosphere C o o li n g r a t e (~/min) Q u en ch i n g temp.(~)
Air, N2(O2<10 4atm) 20 1350, 1200, 300
Air, N2(O~<10 4atm) 10, 100, 500 300

2. C6A2F solid solutions

For s i m p l i c i t y , C6A~z x / 2 ) M x F and CoA~2 x~MxSxF with X=0~0.#5 w e r e p r e p a r e d
on a s s u m p t i o n t h a t MgO and SiO~ s u b s t i t u t e for A1203, though part of MgO m ay
s u b s t i t u t e for F e 2 0 ~ .
The raw m i x e s w e r e burnt in n i t r o g e n on the s a m e h e a t i n g p r o g r a m as in t h e
c l i n k e r burning e x c e p t t h a t t h e m a x i m u m t e m p e r a t u r e and t h e r e t e n t i o n t i m e
w e r e 1#50~ and 20rain. The fired p r o d u c t s w e r e c o o l e d at 10~/min down to 300~7
in t h e f u r n a c e and then q u e n c h e d in air. C a l c i u m a l u m i n a t e , c a l c i u m s i l i c a t e
and p e r i c l a s e w e r e found to c o e x i s t in small q u a n t i t i e s by XRD.

Experimental

The c o l o r s w e r e m e a s u r e d using a c o l o r d i f f e r e n c e m e t e r for the p r o d u c t s

ground to t h e Blaine s p e c i f i c s u r f a c e a r e a of 2 9 0 0 i 1 0 0 c m 2 / g . The r e s u l t s w e r e
giv en a c c o r d i n g to t h e H u n t e r ' s e q u a t i o n . F e O was a n a l y z e d by t h e c o l o r m e t r i c
method with a - a' d i p y r i d y l as an i n d i c a t o r 3 ~. In slowly cooled clinkers
(10~/min) the f e r r i t e c r y s t a l s have been d e v e l o p e d large. Point analysis of
the f e r r i t e phase was made using an e l e c t r o n probe m i c r o a n a l y z e r ( J E O L - 8 6 0 0 M )
with a c c e l e r a t i o n v o l t a g e of 15KV and probe c u r r e n t of 2×10 8A. The number of
points measured was 10 or m o r e f o r each c l i n k e r sample and the c o r r e c t i o n f o r
i n t e n s i t i e s was made by Z A F . The f e r r i t e crystals in r a p i d l y cooled c l i n k e r s
(500~/min) w e r e not l a r g e enough f o r EPMA, so that w e t c h e m i c a l analyses w e r e
made a f t e r e x t r a c t i n g the f e r r i t e phase 4~
The C o A 2 F solid solutions w e r e pressed i n t o disks at 1000kg/cm ~, s i n t e r e d at
1200~ in a i r or in n i t r o g e n and s u b m i t t e d to e l e c t r i c c o n d u c t i v i t y m e a s u r e m e n t
b e t w e e n 50 and 250~.
R e s u l t s and discussion
1. C l i n k e r s
Fig. 1 shows the i n f l u e n c e of o MgO 0% ( ): FeO(ppm)
MgO, burning atmospheres and 19 • MgO 1.5%
quenching t e m p e r a t u r e s on t h e b (850) (810) (860) (3200)
va l u e in t h e H u n t e r ' s e q u a t i o n . 17
In a c c o r d a n c e with th e previous 15
studies i ~ 2~ the b value was
remarkably lowered in the >~ 13
p r e s e n c e of MgO in c l i n k e r . The (2160)
c o n c e n t r a t i o n of F e O was also 11
g r e a t l y decreased w i t h the fail 9 Air Nitrogen
in b v a l u e .
7
The effect of q u e n c h in g
t e m p e r a t u r e on the b v a l u e was 5 (1 ) (14o) (120)
n o t i c e a b l e f o r the c l i n k e r s w i t h I I I ! | I

MgO and burnt in n i t r o g e n . The 135o 1200 30(1 1350 1200 3(X)
clinker quenched in air from Quenching Temp. ( 0(3 )
13 50~, which is apparently
higher than the crystallization Fig. 1
temperature of the ferrite Co l o r variation of clinkers
Vol. 23, No. 4 BURNINGCONDITIONS,COLOR,FERRITEPHASE 935

phase, was dark g r e y in c o l o r and g a v e t h e s a m e b v a l u e as those burnt in air.

By c o n t r a s t , th e c l i n k e r s q u e n c h e d a f t e r t h e c r y s t a l l i z a t i o n of t h e f e r r i t e
phase w e r e yellowish brown with t h e b v a l u e s as high as t h o se of t h e c l i n k e r s
w i t h o u t MgO.
Fig.2 g i v e s t h e e f f e c t of c o o l in g r a t e s on the c o l o r of c l i n k e r s w i t h MgO.
The c l i n k e r s w e r e all q u e n c h e d in a ir at 300~. The b v a l u e s r e m a i n e d v i r t u a l l y
un ch an g ed with c o o l i n g r a t e s for e a c h burning a t m o s p h e r e . A f t e r r e h e a t i n g in
air a t 950g for 15 m i n u t e s , the F e O c o n c e n t r a t i o n in t h e c l i n k e r s burnt in
nitrogen decreased to the same l e v e l as in the clinkers burnt in air
i r r e s p e c t i v e of th e c o o l i n g r a t e s w h il e t he b v a l u e s did not with slow co o l i n g
(100g/rain and 10g/rain).
Fig.3 shows t h e e f f e c t of minor a d d i t i o n of TiOz(1.0%) and ZnO(1.0%) on t h e b
value. The q u e n c h in g t e m p e r a t u r e and c o o l i n g r a t e w e r e f i x ed at 300g and
10~/min, respectively. TiO2 and ZnO are opposite in effect; i.e., TiO2
i n c r e a s e d t h e b v a l u e while ZnO d e c r e a s e d it. A f t e r r e h e a t i n g in ai r a t 950~,
the c l i n k e r s burnt in n i t r o g e n showed t h e s a m e c h a n g e in t h e b v a l u e as t h e
slowly c o o l e d c l i n k e r s in Fig.2 and t h e r e v e r s i o n r e m a i n e d i n c o m p l e t e .

MgO 1.5% I MgO 1.5%

21 ( ): FeO(ppm) I 21 Cooling rate 10 °C/min
19 I
(2600) (2740) I 19 A" ~ A Nitrogen
i
17 ~°)Nitrogen 17
15 15
~> 13 13
> i ,,,~Affer reheating
" 11 (190). .o II
9 , reh ating 9
• O

7 7
Air
0 ~ 0 Air
5

500 100 10 ZnO I ~ No TiO2 1

Cooling rate (°C/rain) Additive
Fig.2 Fig.3
Effect of cooling rates on Effecl of minor components
clinker color on clinker color

Fig.4 g i v e s t h e r e l a t i o n b e t w e e n t h e m o l a r r a t i o Me 4*(Si,Ti)/Me 2 ~(Mg,Zn) in

t he f e r r i t e phase and t h e b v a l u e . The b values of t h e c l i n k e r s burnt in
nitrogen are those a f t e r reheating. The b v a l u e rises in p r o p o r t i o n to
Me 4 ~ / Me 2 . , which was i n c r e a s e d by slow co o l i n g in n i t r o g e n or in t h e p r e s e n c e
of TiO2.
E x t r i n s i c o x y g e n v a c a n c i e s a r e f o r m e d with t h e s u b s t i t u t i o n of Me z~ for AI 3+
and F e 3. to c o m p e n s a t e for t h e d e f i c i e n c y of p o s i t i v e c h a r g e . This p r o c e s s is
e x p r e s s e d as follows using t h e KrOger-Vink n o t a t i o n 5> .

gMe O=2Me ( A , , F o ' +200 +Vo

( V o : Oxygen vacancy)

The c o u p l e d s u b s t i t u t i o n Me 2 ++Me 4 ~ 2 ( A I 3 ~,Fe a ,)6) 7) is e x p e c t e d to d e c r e a s e

the n u m b e r of o x y g e n v a c a n c i e s with i n c r e a s i n g Me 4 +/Me ~ ~ r a t i o . Thus, t h e
M e4 ~ / Me 2~ r a t i o e x e r t s i n f l u e n c e on t h e b v a l u e through o x y g e n v a c a n c i e s in
the f e r r i t e phase.
936 M. Ichikawa mad Y. Komukai Vol. 23, No. 4

1.4

.0

1.2

'6
E
+ 1.0 m

/ No Additive Burning Cooling

+ atmosphere rate(*C/min)
~o 0.8 -- / 1 TiO21o/, Nitrogen 10
4 / 2 TiO'21"/, Air 10
C~/ O 3 No Nitrogen 10
g(~ 5 4 No Air 10
0.6 - /'~ 5 Zn01:~ Nitrogen 10
/O 6 ZnO1'/o Air 10
/ " 7 NO. Nitrogen 500
8 No. Air 500
, i I
5 I0 15
b value
Fig.4
Me4+/M~ + molar ratio and b value

2. C 6 A ~ F solid s o l u t io n s
Fig.5 shows the influence of 20 Formula of
c o e x i s t i n g MgO and SiO2 on t h e b raw materials
values for the C6A2F solid solutions. Ig A CsA(2-x)MxSxF
The specimens were burnt in nitrogen 16 ~ ~ ~I'i C6A(2-xt2)MxF
k
and subsequently reheated in air at C6A.2F
950~. The b value was lowered w i t h the ® 14
increase in MgO content. But the
coexistence of SiO2 considerably > 12
depressed this change due probably to I0 SiO2
the decrease in the number of oxygen
vacancies. The C~A~F solid solutions, 8
when unreheated in air, gave almost
the same b value as C6A2F.
6

4
~ SJO2

E l e c t r i c c o n d u c t i v i t y measurement was
i • I i i f
made f o r the C6A2F solid solutions
burnt in nitrogen. The specimens 0 0.1 0.2 0.3 0.4 0.5
sintered in a i r at 1200~ also gave the X
same b values as those reheated in a i r Fig.5
at 950~, while those sintered in Effect of MgO and coexistent of Si02_
nitrogen showed almost as high b
v a l u e s as C 6 A 2 F . It is c o n s i d e r e d t h a t
this d i f f e r e n c e in color comes f r o m the degree of FeO o x i d a t i o n during
sintering as in the clinkers. Fig.6 shows the l o g a r i t h m i c plot o f the specific
c o n d u c t i v i t y at 200~ against the b value. The specific c o n d u c t i v i t y f or the
specimens sintered in air increases w i t h decreasing b value along a straight
line, Whereas the specific c o n d u c t i v i t y f o r the specimens sintered in nitrogen
lies widely o f f below the line as that of C6A2F. Between 50 and 250~ the
logarithmic plots of the specific conductivity against reciprocal absolute
Vol. 23, No. 4 BURNINGCONDITIONS,COLOR,FERRITEPHASE 937

temperatures gave a straight line fo r each specimen, indicating that the

t yp i c a l semi-conduction prevails at these temperatures. Furthermore, the
specific c o n d u c t i v i t y rapidly became constant in spite of the d i r e c t i o n of
current f l o w, meaning that the c a r r i e r w i l l be electron.

10_3
- 1 2

10 4

-~ 10-5
No. Formula of Sintering
raw materials atmosphere x,
~0 10_6 1 CeA1rtsMo,~F
0 2 C,sA~5sMo4sSo4d=
O 3 C,~ 9sM0~F
0
10-7 4 CsAIeMolSolF
Air
70 8 (339
5 C~1 ~7~MoosF
6 C~I~Mo o'~Soo~
¢,0
10 -8 7 CoAl77sMI0,~F
Nitrogen
8 C~1~sMo~.qo
9 C~F Air
I I I
5 l0 15
b value
Fig.6
Relation between specific conductivity and b value

These results suggest that the presence of electrons released by the

o x i d a t i o n of FeO, in association w i t h the occurrence of ex t r in s ic oxygen
vacancies, is essential to the darkening of the color of the f e r r i t e phase.

Conclusions

I) The f o r m a t i o n of extrinsic oxygen vacancies w i t h the substitution of

Me2~(Mg,Zn) f or AI a+ and Fe 3., when coupled w i t h the o x i d a t i o n of FeO during
cooling, produces the color change of the f e r r i t e phase from yellowish blown
to dark grey.
2) The ferrite phase w i t h a high Me 4 +(Si,Ti)/Me 2 +(Mg,Zn) ratio remains
yellowish brown even i f FeO is oxidized. This indicates that the Me 4 ÷/Me 2
r a t i o influences the number of e x tr i ns ic oxygen vacancies in the f e r r i t e
phase.
3) With Co A2 F solid solutions the electric conductivity has a close
relationship w i t h the number of oxygen vacancies and electrons released by the
o x i d a t i o n o f FeO.
938 M. Ichikawa and Y. Komukai Vol. 23, No. 4

Acknowledgments

The authors thank Professor h Maki of the Nagoya Institute of Technology for
his helpful discussions.

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