CEMENT and CONCRETE RESEARCH. Vol. 7, pp. 719-730, 1977.

Pergamon Press, Inc

Printed in the United States.
ALKALIES IN CEMENT: A REVI~V
I. Forms of Alkalies and Their Effect on Clinker Formation
Inam Jawed and Jan Skalny
N~rtin ~ r i e t t a Laboratories
Baltimore, Maryland
(Communicated by S. Diamond)
(Received September 15, 1977)
ABSTRACT
Alkalies in portland cement clinker occur as sulfates and,
depending on the amount o f SO3 available, m a y also be present in
calcitun silicate and aluminate phases. Introduction of alkalies
into clinker minerals modifies their crystal structure which, in
turn, can change their hydraulic reactivity. Alkalies affect the
clinkering process b y modifying the physicochemical properties
of the melt formed in the kiln, and m a y have an adverse effect on
the phase composition of clinker.
In Portlandzementklinkern vorkommende Alkalien k~nnen Sulfate
sein oder auch in den Silikat-oder Aluminatanteilen vorkommen, je
n a c h der vorhandenen Menge y o n SO 3. Alkalien in Klinkermineralien
modifizieren deren Struktur und kBnnen dadurch deren hydraulische
Reaktionen ver~ndern. Alkalien beeinflussen den klinkerformenden
Prozess dadurch, (lass sie die physikalisch-chemischen Eigenschaften
der in der Kiln geformten Sc~melze beeinflussen. Die Anwesenheit
y o n Alkalien kann unerw~nschte Folgen for die Phasenkomposition yon
Klinkern haben.
719
720 Vol. 7, No. 6
I . Jawed, J. Skalny
I. I n t r o d u c t i o n
A l k a l i e s a r e u n a v o i d a b l y i n t r o d u c e d in m i n o r q u a n t i t i e s i n t o p o r t l a n d
c e m e n t c l i n k e r . T h e y a r o u s e d p a r t i c u l a r i n t e r e s t w h e n S t a n t o n (I) r e p o r t e d
t h a t a l k a l i n e s o l u t i o n s p r o d u c e d in t h e h a r d e n e d c o n c r e t e s u b s e q u e n t l y
r e a c t e d w i t h s o m e a g g r e g a t e i n g r e d i e n t s c a u s i n g d i s r u p t i v e e x p a n s i o n a n d
d e t e r i o r a t i o n o f c o n c r e t e s t r u c t u r e s . S i n c e t h e n a l k a l i e s h a v e c o m e to b e
r e g a r d e d as p o t e n t i a l l y d e l e t e r i o u s b u t u n a v o i d a b l e s p e c i e s in c l i n k e r .
In fact, t h e a l k a l i - a g g r e g a t e r e a c t i o n h a s b e e n t e r m e d t h e " c a n c e r o f
c o n c r e t e " , a n d t h e a l k a l i e s f r o m t h e c e m e n t c o m p a r e d to v i r u s e s ( 2 ) . S i n c e
S t a n t o n ' s r e p o r t , a v a s t l i t e r a t u r e h a s a c c u m u l a t e d o n the a l k a l i - a g g r e g a t e
r e a c t i o n s . A n a n n o t a t e d b i b l i o g r a p h y o f a l k a l i - a g g r e g a t e r e a c t i o n s , c o v e r i n g
l i t e r a t u r e u p to 1974, w a s c o m p i l e d b y F i g g (3). A r e c e n t r e v i e w b y D i a m o n d
(4,5) s t m m a r i z e s t h e k n o w l e d g e o f t h e m e c h a n i s m o f a l k a l i - s i l i c a r e a c t i o n s .
T h e r e h a s n o w b e e n a r e n e w e d i n t e r e s t in a l k a l i e s in c l i n k e r b e c a u s e
o f c h a n g e s in p y r o p r o c e s s i n g t e c h n o l o g y , c a l l f o r e n e r g y c o n s e r v a t i o n , t h e
l i m i t e d a v a i l a b i l i t y o f l o w - a l k a l i r a w m a t e r i a l s , a n d t i g h t e n e d e n v i r o n -
m e n t a l r e s t r i c t i o n s . I n c r e a s e in fuel p r i c e s h a s a c c e n t u a t e d t h e t r e n d
f r o m w e t t o d r y p r o c e s s e s a n d to t h e u s e o f c o a l as t h e p r i m a r y fuel source.
A l l t h e a b o v e f a c t o r s l e a d to i n c r e a s e s in a l k a l i a n d s u l f a t e c o n c e n t r a t i o n s
in t h e c l i n k e r . A n y m e a n s to r e m o v e a l k a l i e s is a t e c h n i c a l l y d i f f i c u l t a n d
a n e x p e n s i v e p r o p o s i t i o n . T h e w o r l d w i d e t r e n d , t h e r e f o r e , n o w s e e m s to b e
t o w a r d s h i g h e r a l k a l i c o n t e n t s in c e m e n t .
T h e m a x i m u m l i m i t o f a l k a l i e s e x p r e s s e d as N a 2 0 e q u i v a l e n t
(Na20 + 0 . 6 5 8 K20), s p e c i f i e d w h e n t h e c e m e n t is to b e u s e d in c o n c r e t e w i t h
r e a c t i v e a g g r e g a t e s , is 0.6% ( A S T M C 150-74). T h e u s u a l a l k a l i c o n t e n t
(Na20 + K$O) o f p o r t l a n d c e m e n t s , h o w e v e r , r a n g e s f r o m 0.3 t o 1.3%, a n d in
h i g h a l u m z n a c e m e n t s f r o m 0.I to 0.6%.
II. O r i g i n o f A l k a l i e s i n C l i n k e r
A l k a l i e s i n c l i n k e r o r i g i n a t e f r o m t h e r a w m a t e r i a l s u s e d f o r t h e
m a n u f a c t u r e o f p o r t l a n d c e m e n t -- i . e . clay, l i m e s t o n e , chalk, a n d s h a l e --
a l l o f w h i c h c o n t a i n a l k a l i e s . T y p i c a l a n a l y s e s a r e as f o l l o w s (6):
C l a y L i m e s t o n e S h a l e C h a l k T y p i c a l R a w M i x
K 2 0 (%) 2.61 0.26 4 . 5 6 0 . 0 4 0.52
N a ) O (%) 0.74 0 . i i 0 . 8 2 0 . 0 9 0.13
$ 2 : (%) -- 0.03 0 . 3 0 0 . 0 1 --
S O 3 (%) 0 . 2 1 0.02 -- 0.07 0.07
A l k a l i e s c a n a l s o c o m e f r o m c o a l a s h i f c o a l is u s e d as t h e p r i m a r y fuel.
A s w i l l b e d e s c r i b e d l a t e r , m o s t o f a l k a l i e s i n c l i n k e r e x i s t i n s o m e
c o m b i n a t i o n w i t h sulfur. S u l f u r i n c l i n k e r m a y c o m e f r o m o i l o r c o a l u s e d
as fuel. A d d i t i o n a l l y , it m a y o r i g i n a t e f r o m r a w m a t e r i a l s s u c h as c l a y o r
s h a l e w h e r e it o c c u r s a s p y r i t e s , s u l f a t e s , o r o r g a n i c c o m p o u n d s .
A b o u t 50% o f a l k a l i e s p r e s e n t in t h e r a w f e e d a r e v o l a t i l i z e d in t h e k i l n
b e t w e e n 8 0 0 C to 1000C. T h e s e a l k a l i e s a r e l a t e r p a r t l y c o n d e n s e d i n
c o o l e r p a r t s o f t h e kiln. F o r m a t i o n o f r i n g s a n d c o a t i n g s o n t h e k i l n
l i n i n g h a s b e e n a t t r i b u t e d to t h e c o n d e n s a t i o n o f a l k a l i e s a n d t h e i r r e a c t i o n
w i t h t h e r e f r a c t o r y m a t e r i a l (7-10). T h e e x t e n t o f v o l a t i l i z a t i o n v a r i e s w i t h
r a w m a t e r i a l s , a n d is h i g h e r f o r c l a y s t h a n f o r f e l d s p a r s . U s u a l l y
Vol. 7, No. 6 721
ALKALIES, CEMENT CLINKER, HYDRAULICITY
potassium compounds are more volatile than those of sodium but this is not
universally the case (ii). A direct linear relationship between the
density of the alkali-containing raw materials and the extent of volatilization
has been reported (12). The extent of volatilization is also affected by the
type of kiln. There is a general tendency for the retention of alkalies to
be higher as the energy efficiency of the kiln system increases (6). A
larger amount of alkalies is volatilized when gas or oil is used as fuel as
compared to coal (13).
Sulfur containing compounds from the raw materials and fuel are
oxidized in the kiln to SO 3 and a sulfur cycle f o r m s . The first reaction
of SO5 is to form alkali sulfates, preferentially with potassium, and
later calcium sulfates. At higher temperatures, alkali sulfates are vapor-
ized and calcium sulfate is partly decomposed. More than half of the sulfur
originating from raw materials and fuel appears in the clinker; the rest is
lost in the flue gases and in the kiln d u s t . Besides reacting with alkalies,
SO3 can also combine with silicates and aluminates to form compounds such
as (2 CaO.SiO2)2.Caso 4 or 4 CaO.3 Al203-SO3. These may build up in kiln
rings but decompose again at clinkering temperature.
III. Alkali Compounds in Clinker
Compounds containing alkalies and sulfur may be found in almost all parts
of the cement plant. These compounds occur in the clinker, on the kiln
linings and preheaters, in the kiln dust, in the flue gases, and in the
storage s i l o s . Whereas the presence of fluorides and chlorides in the raw
feed enhances the volatility of alkalies (14-19), the presence of sulfur
leads to reduction of alkali volatility during clinker formation (20-22).
Alkali compounds in clinker can be divided into three main groups (25-26):
(a) Alkali sulfates; (b) Alkali aluminates and aluminoferrites; (c) Alkali
silicates. In some cases, alkali may also occur in the form of carbonates
(2S).
Alkalies as Sulfates
Based on available evidence, it appears that the clinker SO 5 makes
prior demand on the alkalies. The resulting q u a n t i t y of alkali sulfate is
determined by the ratio of total clinker sulfate to total alkali. The
remaining sulfate forms calcium sulfates, either as the soluble double
sulfate or as anhydrite. The alkali sulfates most commonly formed are:
Potassium sulfate (arcanite, K 2 S O 4 )
Sodium potassium sulfate ( a p h t h i t a l i t e , Na2SO4.3~SO4, or a similar
solid solution)
Calcium potassium sulfate (calcium langbeinite, 2Caso4-K2SO4, or
a similar solid solution)
According to Pollitt and Brown (25), potassium sulfate is likely to occur
either alone or in one of the two double sulfate forms depending upon the
available quantities of sodium sulfate and calcium sulfate, the preference
probably being for the double alkali sulfate. Sodium sulfate may occur
alone but, more probably, as the double alkali sulfate. It does not form
a double salt with calcium sulfate. Calcium sulfate occurs either alone or
as 2 CaSO4-K2SO 4 subject to the prior formation of double alkali sulfates.
722 Vol . 7, No. 6
I . Jawed, J. Skal ny
Overall, potassium is twice as likely to produce soluble sulfate as sodium.
The burning zone atmosphere has been reported to influence alkali compound
formation ( 2 7 , 2 8 ) . Calcit~npotassium sulfate, 2 CaSO4.K2SO4, tends to be
produced in an oxidizing flame while sodium p o t a s s i u m sulfate, 3 K2SO 4-
Na2S04 , is produced under reducing burning conditions.
Alkalies in Aluminates and Silicates
After allocating alkalies to sulfate, the remainder appears to be
distributed between the silicates, aluminates and aluminoferrites. The
rules governing the quantitative division of alkalies b e t w e e n silicates,
aluminates and ferrites are not yet clear but, it is known, that aluminates
and ferrites accomodate about h a l f or more of the available alkalies. The
quantity of alkalies in the aluminate and ferrite phases, respectively, is
found to be related to the alumina contents of these phases ( 2 5 ) . Lea (6)
has given the following typical ranges of solid solutions in the four m a i n
clinker components:
Na20 (%) K20 (%)
C3S 0.I - 0.3 0.i - 0.3
C2S 0.2 ~ 1.0 0.3 - 1.0
C3A 0.3 ~ 1.7 0.4 - I.I
C4AF 0. 0 - 0, 5 0. 0 - 0 . I
The characteristic sodi~n containing compound is NC8A3 and has been the
subject o f extensive investigations (24,25,29-41). The exact stoichiometry
of N C s A 3 and its potassium containing analog is, however, v e r y difficult to
confirm. Free alkali reacts w i t h C 3 A to form N C s A 3 and free l i m e ; this CaO
could theoretically react w i t h C2S to form C3S but the reaction is sluggish
and often incomplete. A l k a l i contents may, therefore, influence the degree
of lime saturation and cause latent unsoundness.
According to Suzukawa (33), N C 8 A 3 is a d a r k prismatic interstitial
phase w i t h slight silica content, having refractive indices o f 1.702 and
1.711, birefringence o f 0.010, and negative elongation. The x-ray pattern
is similar to that of C3 A but w i t h the following difference: the strong
C 3 A lines are split - the 23045 ' 28 lSne w i t h d = 1.91 N i~to 1.89 and 1.92 ~i
and the 2936 ' 2@-line w i t h d = 1.56 ~ into 1.55 and 1.56 ~ C39].
If clinker contains anhydrite (CaS04), it can react w i t h N C 8 A 3 to give
thenardite (Na2SO 4) and C3A. A value of 2576 kcal/mole for the heat of
formation of N C 8 A 3 and 4850 kcal/mole for its heat of reaction w i t h CaSO 4 to
form Na2S04 and C 3 A h a s been reported (42).
The existence of compound KC23S12, as discussed by Taylor (43-4~), is
difficult to identify b y optical microscopy. Nurse (46,47) and Suzukawa
(48,49) have concluded that this product is not a distinct compound but a
p o t a s s i u m stabilized form o f e'-C2S. Petrographic examination shows that
KC23S12 consists m a i n l y of irregular or r o u n d e d particles w i t h relatively
low blrefringence ( 5 9 ) . Its refractive indices are 1.702 and 1.695, and
the x-ray pattern differs from the 8-C2S p a t t e r n o n l y in the intensity of
some lines (46). It reacts easily w i t ~ a n h y d r i t e (CaSO4) to give arcanite
(K2SO4) and C2S. If N C 8 A 3 is present simultaneously, formation of solid
solutions of the type (Na,K)zSO 4 is observed. The composition of these m i x e d
sulfates as a function of clLnker composition has b e e n discussed b y Newkirk
(23,24), who also developed equations to indicate the effect of alkalies on
Vol. 7, No. 6 723
ALKALIES, CEMENT CLINKER, HYDRAULICITY
the potential phase composition of clinkers. V e r y small changes in sodi~n,
potassium, and SO 3 contents m a y cause relatively large changes in the amount
of C3S and C 3 A . The heat o f formation of KC23S12 from elements has been
calculated as 6420 kcal/mole (50), t h i s ; however, cannot be used to decide
whether a real compound or a crystalline solution exists. The heat of
reaction of KC23S]2 w i t h anhydrite to form 8-C2S and orthorhombic K2SO 4 has
been given as 36.3 kcal/mole. Heats of solution of 8-C2S preparations con-
taining increasing amounts of K20 show a maximum near the composition of
KC23S12.
Besides NC8A3 and KC $IS 2, the existence, of sodium, substituted, belite,
NC23S12, and an orthorhom~Ic phase of potasslum substituted alumznate,
KCsA3, has been suggested [ 2 6 , 4 9 ) . Suzukawa (49) noted that KC8A3 formed
only in the presence of SiO 2 which indicated that Si ions replaced A1 ions
in this product. The formation of K20-4SiO 2 and Na20.2SiO 2 at 6 0 0 C , and
Na2Ca(C03) 2 and K3Na(SO4) 2 at 7 0 0 C , is also reported (51,52).
Other Alkali Compounds in Cement ~ n u f a c t u r i n g
The kiln dust contains alkali halides in addition to sulfates, the most
common being sylvite (KCl) ( 2 6 , 5 3 ) . The most common sulfates in kiln dust
are arcanite [K2SO4) , aphthitalite [Na2SO4-3K2SO4) , and calcium langbeinite
(2CaSO4.K2SO4). Formation of lumps in cement during storage has been
attributed to another alkali calcium sulfate, syngenite (K2SO4.CaSO4.H2 O)
[54-56). Increased syngenite formation was noticed w h e n cement contained
more than 12% by weight of C3A and had a total potassium content of about 1%
(57-59). Syngenite is also formed during grinding of clinker in the mill if
the temperature is lowered by water ( 6 0 ) . Compounds of alkali and sulfur w i t h
or without silicates are major contributors to the formation of rings and
coatings in the inner wall of k i l n , suspension preheater, Lepol grate
chambers, e t c . These coatings result from the m o l t e n matter and contain
alkali sulfates and chlorides,often together with spurrite ( 2 C 2 S . C A C 0 3 ) ,
sulfo-spurrite (2C2S.CASO4) , calcium sulfoaluminate (C3A.CaSO4) and calcium
langbeinite [2CaSO~.K2SO4) ( 6 1 - 6 7 ) . The formation of spurrite is known to be
promoted by such fluxes as CaF 2 . Gutt and Smith (68) found that Na2SO 4 and
K2SO 4 acted similarly to CaF 2. Simultaneous presence of alumina and K2SO4,
however, discouraged spurrite formation.
IV. Effect of Alkalies on Clinker
The formation of clinker grains and their macro-and microstructure
depend on the amount and the physico-chemical properties o f the melt formed
in the clinkering process. These properties of the melt a r e , in turn,
dependent on the variation in the chemical composition of the raw mix, on
introduction of ki.lndust and various additives into the r a w mix, and on
other factors influencing the composition of the liquid phase of the clinker.
Changes in the melt composition affect the surface tension and viscosity of
the melt ( 6 9 ) . The surface tension leads to aggregation while the forces of
gravity and viscosity offer resistance. Timashev et al. ( 7 0 ) noted that the
size of the clinker grains increased w i t h increasing surface tension of the
m e l t . Single oxides or oxide mixtures ~ O , Na$O, M g O + Na20 , M g O + K20),
which have little influence on the surface tenszon but do lower the viscosity
of the melts, favored a g g r e g a t i o n ~ d t h formation of uniform grain size c l i n k e r s
Introduction of SO jointly w i t h K~O or Na20 into the melt modified the
surface tension and led to phase separation. The less dense melt w i t h lower
surface tension is displaced onto particle surfaces. This slows down the
aggregation and dust-like clinker grains are f o r m e d . The density of
724 Vol. 7, No. 6
I . Jawed, J. Skalny
Na2SO 4 melt ( 3 . 0 g / c o ) is very close to that of clinker liquid phase
(3702 g / c c ) whereas that of K2SO 4 is lower ( 2 . 8 g / c c ) . Hence, Na2SO 4
droplets are dispersed into the parent melt whereas K2SO 4 droplets rise to
the surface and phase separation occurs. The high surface activity of K20
in comparison w i t h Na20 is also important; it facilitates separation of
K2SO 4 as an independent liquid phase.
The rate of formation of C3S has been found to be proportional to the
amount of liquid phase in the kiln at a given temperature ( 7 1 ) . Because
alkalies decrease the temperature of melt formation, an effect on C35
formation is expected. However, the results of Johansen (72) showed that
clinkers w i t h or without alkalies had the same amount of free CaO after
burning at 1400-1500C. Vulkov et al. ( 7 3 ) showed that optim~n raw feed
grain size led to an increase of liquid phase resulting in dissolution of
greater amount of alkali oxides. This had an adverse effect on the
crystallization conditions of C3S and decreased its content. Luginina et al.
(74) also noted formation of highly fluid liquid phase at about 800C due to
presence of alkalies which affected the clinker formation. Results of
Azelitskaya et al. ( 7 5 ) showed that a significant amount of free CaO
appeared sooner than normal in alkali containing raw mixes. Increased
amount of liquid phase formed but its alkali content prevented CaO from
dissolving. The amount of C3 S decreased and formation of N C 8 A 3 type solid
solution was observed.
Kr~mer and zur Strassen (76) have shown t h a t , whereas K2SO 4 does not
influence the formation of clinker minerals, Na2SO 4 has a significant effect.
In the presence of Na2SO 4, the XRD intensities of alite peaks decreased
whereas peaks of CaO appeared. This is the same effect as shown by K20.
T h e y conclude that Na. 2S04 is taken up by C2S in solid solution, w h i c h
prevents the formatzon of alite in the same w a y as KC23S12 d o e s . Woermann
(77) observed the decomposition of alite by high concentrations of K20.
He concluded that K + m a y be contained in alite crystals at high temperatures
but, at lower temperatures, the equilibrium alite ~ belite + CaO is shifted
to the right causing decomposition of alite. Hive~ (78) also noted that K20
promoted decomposition of C3S to C2S plus C a O , and that it resulted in the
formation of solid solution KC23S12. Yamaguchi and U c h i k a w a (79) showed the
influence of Na~O on the formation of alite. Their high temperature .XPd9
studies revealed a strong tendency towards disintegration of alite and
appearance of free C a O . C3S changes from triclinic to monoclinic symmetry as
soon as 0.33% Na20 is taken up. The structure of this monoclinic phase is
identical with that reported by Yamaguchi and Miyabe (80) w i t h two Na + ions
replacing one Ca 2+. Volatilization of Na20 brings about a retrograde
conversion of the monoclinic symmetry of the crystals to triclinic.
Ono et al. (81,82) found that w i t h increasing alkali and decreasing
M g O contents the free CaO first increased and then decreased considerably
w i t h increase in K 2 0 . ~-C2S increased w i t h increasing N a 2 0 + K 2 0 . The
decrease of specific gravity of clinkers is attributed to the occurrence of
~ - C 2 S , which has low specific gravity. ~-C2S is stabilized by N a 2 0 or K20
whereas ~'-C2S is stabilized by K20 or K20 + MgO. However, on increasing
K20 content, ~'-phase transforms into s-phase. Luginina et a l . (83) have
discussed the microstructure of clinkers containing alkalies and MgO.
Presence of K2SO 4 imparted an equigranular texture to clinker w i t h high
porosity and contributed to development of coarse crystals of belite.
Presence of M g O prevented the low temperature interaction of alkali w i t h
CaCO 3 (i.e., spurrite e t c . , are not formed). Clinkers containing alkalies
Vo]. 7, No. 6 725
ALKALIES, CEMENT CLINKER, HYDRAULICITY
in the presence of M g O form CaO.ZAI2Os.FeO 5 as a stable compound. In high
alkali r a w mixes, addition o f M g C O 5 impeded the formation o f spurrite.
Suzukawa and Sasaki (84,85) n o t e d that increase in Na20 content decreased
the amount of FeO required to cause dusting of clinkers; they attributed
this to the lowering of 8-~y inversion temperature of C2S (86) and to the
change in the chemical composition of clinkers ( 4 5 ) . Chin et al. ( 8 7 ) have
found that a decreasing FeO/CaO ratio in the raw m i x significantly decreases
the alkali content in the clinker.
Pollitt and Brown (25) have shown that introduction of alkalies into
C 3 A m o d i f i e s its normal cubic fol~n to orthorhombic. This orthorhombic form
of C S A is formed w i t h a minimum alkali content of 2.8% equivalent Na20 or
1.8% equivalent K 2 0 . Works of Moore (88,89), Day (90), and Fletcher et al.
(34) have also shown t h a t small amounts of Na20 or K20 could replace CaO
in the cubic C 3 A and that greater replacement of CaO gave rise to orthorhombic
structures of N C s A 5. Boikova et al. ( 9 1 ) have also sho~n that presence of
Na20 results in four polymorphic modifications of C ~ . The hydraulic activity
of these modifications is a function of their Na20 content and is lower than
t h a t of pure C 3 A . Maki (37,92), on the other hand, claims t h a t orthorhombic
CsA exists in two forms, the low form containing 3.7% and the high form 5.9%
N a 2 0 . These forms also take small amounts of SiO 2 into solid solution. From
microscopic study of synthetic clinkers w i t h varied contents o f Na20 ,
Suzukawa (49) noted t h a t N C s A 3 causes shirtings in the aluminoferr[te phase
composition towards the higher ferrite contents, i . e . , from C4AF to C6AF 2.
Data of Butt et al. ( 9 5 ) show that the presence of alkalies in the r a w
material decreases the rate of the clinkering reactions. Similar effects
of alkalies on clinker formation have also been reported by Benyei (94),
Volkonskii and Shteiert [95), and Lokot et al. (96).
V. Effect of SO 5 on Clinker in Presence of Alkalies
At this point, a brief discussion of the effect of SO 3 on clinkers seems
very relevant. G u t t and Smith (97) studied the role of SO 3 on clinker
minerals and showed tha~, in the absence of alkalies and ~ O , the combined
presence of A15+ and SO~-ions prevents the formation of C3S and favors solid
solution of C2S w i t h these i o n s . The presence of M g O counteracts this effect.
In a later study, they noted a v e r y complex effect o f combined presence of
alkalies and CaSO 4 ( 6 8 ) . Whe D CaSO 4 w~s present in e x c e s s , neither Na20 nor
K20 modified the effect of A1 ~+ and SO~-ions on C 3 S formation noted previously.
Whereas in the absence of alumina both-sodium and potassium have mineralizing
effects, in the presence of alumina their effects differ. At low concentra-
tions of K2SO4, CxS is formed rather easily b u t , at higher c o n c e n t r a t i o n s of
K2SO4, substantial liquid formation occurs at 1400C and quenching results in
pr.oduct containing only glass and 8-C2S w i t h traces of K2SO 4. In contrast,
in mLxes containing Na2SO 4 and alumina, the liquid formation Is not so great
and C3S is formed e a s i l y . Examination of portland cement clinkers showed
that K2SO 4 in no w a y modified the effect of A13+ and SO~-ions in forming
C 3 S . However, Na2SO 4 proved to be deleterious and prevented the formation
of C 5 S . This contrasted w i t h the behavior of Na2SO 4 in C3S mixes where no
adverse effects were found.
Tsuboi et al. (98-100) found that the addition o f SO X m a d e burning and
sintering v e r y difficult as a result of increased viscosity o f the melt.
The alite crystals became larger and assumed "amoeba-like" shapes, whereas
belite crystals did not have lamellae. The C 3 A content of clinkers decreased
726 Vol. 7, No. 6
I . Jawed, J. Skalny
a n d the c l i n k e r p o r e s b e c a m e larger. F u k u d a ( i 0 1 ) n o t e d that a n a d d i t i o n o f
3.5% C a S O 4 to r a w m a t e r i a l s d e c r e a s e d s h a r p l y the C 3 A f o r m a t i o n ; at the
s a m e t i m e f o r m a t i o n o f C 3 A . C ~ w a s o b s e r v e d . A b o v e a c e r t a i n C a S O 4 level
(5.3%), t h e C 3 S f o r m a t i o n d e c r e a s e d a n d a s i g n i f i c a n t i n c r e a s e in f r e e C a O
w a s n o t i c e d . F o r m a t i o n o f C 3 A . C g , w h e n g T p s u m is p r e s e n t in the r a w meal,
has a l s o b e e n r e p o r t e d b y Li (102).
~ r t y n s t e v et al. ( 1 0 3 ) f o u n d t h a t the a d d i t i o n o f 0.5% S O 3 i m p a r t e d
a c o a r s e c D ' s t a l l i n e s t r u c t u r e to c l i n k e r s w i t h w e l l d e f i n e d a l z t e c ~ s t a l s .
A n i n c r e a s e to 1% S O 3 r e s u l t e d in fine g r a i n e d s t r u c t u r e . SO~ a l s o
d e c r e a s e d t h e c l i n k e r i n g t e m p e r a t u r e b y a b o u t 200C. A d e c r e a s e o f c l i n k e r i n g
t e m p e r a t u r e w i t h i n c r e a s e in SO~. (added as g y p s u m to r a w meal) h a s a l s o b e e n
r e p o r t e d b y ~ h r a k a m i et al. ( I 0 ~ ) . O v e r b u r n e d c l i n k e r s w i t h h i g h s u l f u r
s h o w e d l a r g e a l i t e c r y s t a l s . C l i n k e r s b u r n e d at 1300C, h o w e v e r , h a d b a d l y
f o r m e d a l i t e c r y s t a l s . B u t t et al. ( 1 0 5 ) h a v e f o u n d t h a t i n c r e a s e o f S O 3
(1.2 to 4.7%) in t h e r a w f e e d d e c r e a s e d t h e K 2 0 c o n t e n t in the c l i n k e r f r o m
't~,r " 7
2.4 to 2.03%. C l i n k e r s c o n t a i n i n g 2.1% S O 3 e r e c h a r a c t e n _ e d b y
h e t e r o g e n e o u s s t r u c t u r e s a n d i n d i s t i n c t c r y s t a l l i z a t i o n o f m i n e r a l s . :in
i n c r e a s e in S O 3 f r o m 1.55 to 7.7% s i g n i f i c a n t l y c h a n g e d the s p e c i f i c surface.
I n c r e a s e in S O 3 f r o m 3.97 to 4 . 2 4 % i n c r e a s e d t h e a m o u n t o f b e l i t e a n d
d e c r e a s e d t h a t o f alite.
A p o s i t i v e e f f e c t o f g~/psum a d d i t i o n to a l k a l i c o n t a i n i n g r a w m a t e r i a l s
o n t h e f o r m a t i o n o f c l i n k e r m i n e r a l s h a s b e e n r e p o r t e d b y A z e l i t s k a y a et al.
(106,107). T h e c l i n k e r i n g t e m p e r a t u r e d e c r e a s e d . T h e a m o u n t o f C - S
i n c r e a s e d a n d a p o s i t i v e e f f e c t o n the b i n d i n g o f C a O w a s noted. P r e s e n c e
o f a l k a l i s u l f a t e s r e s u l t e d in w e l l d e v e l o p e d a l i t e a n d b e l i t e c r y s t a l s .
D i f f e r e n t a l k a l i c o n t a i n i n g r m m a t e r i a l s r e q u i r e d d i f f e r e n t a m o u n t s o f
gypsum. It is c l a i m e d t h a t u s e o f p r o p e r a m o l m t o f g y p s u m r e s u l t e d in
h i g h e r k i l n o u t p u t a n d r e d u c t i o n o f fuel c o n s u m p t i o n .
VI. R e f e r e n c e s
(i) T.E. S t a n t o n , Proc. Am. Soc. Civ. E n g r . , 66, 1781 (1940).
(2) G.M. Idorn, Proc. Symp. E f f e c t o f A l k a l i e s o n the P r o p e r t i e s o f C o n c r e t e ,
Sept. 1 9 7 6 C & CA. L o n d o n , p. 3 (1977).
(3) J.W. Figg, A l k a l i - A g g r e g a t e ( A l k a l i - S i l i c a a n d A l k a l i S i l i c a t e % R e a c t i v i t y ,
C ~ U R E A U , P a r i s (19/7).
(4) S. D i a m o n d , Cem. Concr. Res., 5, 329 (1975).
(5) S. D i a m o n d , ibid., 6, 549 (1976).
(6) F.M. Lea, T h e C h e m i s t r y o f C e m e n t a n d C o n c r e t e , Chem. Publ. Co.,
2nd Ed. N.Y. (1971).
(7) E. V o g e l , S i l i k a t t e c h . , 9, 361, 449, 502 (1958).
(8) H.E. S c h w i e t e , Z e m e n t - K a l k - G i p s , 9, 351 (1956).
(9) R. A l ~ g r e a n d P. T e r r i e r , Rev. N ~ t e r i a u x Constr. et. tray. publ.
523, 89 (1959).
( I 0 ) H.M. G a r r e t t , P i t & Q u a r r y , ( 3 ) , 84 (1976).
(ii) M. R u s t o m , S c h w e i z e r . Arch. Angew. Wiss. T e c h . , 22, 197 (1956).
( 1 2 ) I . P . Y a n e v et al., Trans. Mosk. Khim, T e c h n o l . Inst., 76, 125 (1973)
C. A. no. 8 2 : 1 4 4 2 4 I V .
Vol. 7, No. 6 727
ALKALIES, CEMENT CLINKER, HYDRAULICITY
( 1 3 ) R . A . L o v e l a n d , q u o t e d b y W . J . ~ C o y a n d O . L . E s h e n o u r , P r o c . 5 t h
I n t l . S y r u p . C h e m i s t r y o f C e m e n t , T o k y o , I / o l . I I , p . 4 3 7 C 1 9 6 8 ) .
( 1 4 ) H . W o o d , R o c k P r o d . , 4 5 , 6 6 ( 1 9 4 2 ) .
( 1 5 ) E . R . H o l d e n , I n d . E n g g . C h e m . , 4 2 , 3 3 7 ( 1 9 5 0 ) .
( 1 6 ) A . D . A z e l i t s k a y a , S i l i k a t t e c h ) 5 , 1 2 0 ( 1 9 5 4 ) .
( 1 7 ) A . D . A z e l i t s k a y a , T s e m e n t ( 3 ) , 1 3 ( 1 9 5 4 ) .
( 1 8 ) V . L . P a n k r a t o v a n d L . Y . L o p o t n i k o v a , T s e m e n t , ( S ) , 1 9 ( 1 9 7 0 ) .
( 1 9 ) V . M . B l o n a k a y a a n d V . M . S t e p a n o v , T s e m e n t , ( 4 ) , 1 2 ( 1 9 6 9 ) .
( 2 0 ) W . C . T a y l o r , J . R e s . N B S , 2 9 , 1 4 2 ( 1 9 4 2 ) .
( 2 1 ) T . F . N e w k i r k , i b i d , 4 6 , ( 1 9 5 0 ) .
( 2 2 ) J . P . D r a p e r , q u o t e d i n T h e C h e m i s t r y o f P o r t l a n d C e m e n t b y R . H . B o g u e ,
p . 1 2 9 , R e i n h o l d P u b l . C o r p . N . Y . ( 1 9 5 5 ) .
( 2 3 ) T . F . N e w k i r k , J . R e s . N B S , 4 7 , 3 4 9 ( 1 9 5 1 ) .
{ 2 4 ) T . F . N e w k i r k , P r o c . 4 t h I n t ' l S y m p . C h e m i s t r y o f C e m e n t , L o n d o n ,
p. 151 (1952).
( 2 5 ) H . W . P o l l i t t a n d A . B r o w n , P r o c . 5 t h I n t ' l . S y m p . C h e m i s t r y o f C e m e n t
T o k y o , V o l . I , p . 3 2 2 ( 1 9 6 8 ) .
( 2 6 ) L . D . A d a m s , P a p e r p r e s e n t e d a t 75th A n n u a l C e r a m i c S o c i e t y M e e t i n g
a t C i n c i n n a t i , A p r i l 1 9 7 5 .
( 2 7 ) J . E . M a n d e r , P r o c . S y m p . E f f e c t o f A l k a l i e s o n P r o p e r t i e s o f C o n c r e t e
S e p t . 1 9 7 6 C & C A . L o n d o n , p . 2 7 ( 1 9 7 7 ) .
( 2 8 ) J . E . M a n d e r a n d J . S k a l n y , C e r a m . B u l l . , 5 6 , ( 1 9 7 7 ) ( t o b e p u b l i s h e d ) .
( 2 9 ) L . T . B r o w n m i l l e r a n d R . H . B o g u e , A m , J . S c i . , 2 3 , 5 0 1 C 1 9 3 2 ) .
( 3 0 ) K . T . G r e e n e a n d R . H . B o g u e , J . R e s . N B S , 3 6 , 1 8 7 ( 1 9 4 6 ) .
( 3 1 ) D . L . H e a t h , J . A m e r . C e r a m . S o c . 4 0 , 5 0 ( 1 9 5 7 ) .
( 3 2 ) J . A . C o n w i c k a n d D . E . D a y , J . A m . C e r a m . S o c . 4 7 , 6 5 4 ( 1 9 6 4 ) .
( 3 3 ) Y . S u z u k a w a , Z e m e n t - K a l k - G i p s , 9 , 3 4 5 ( 1 9 5 6 ) .
( 3 4 ) K . F . F l e t c h e r e t a l . , M a g . C o n c r . R e s . , 1 7 , 1 7 1 ( 1 9 6 5 ) .
( 3 5 ) A . G u i n i e r a n d M . R e g o u r d , P r o c . 5 t h I n t ' l . S y m p . C h e m i s t r y o f C e m e n t ,
T o k y o , V o l . I , p . 1 C 1 9 6 8 ) .
( 3 6 ) S . C h r o m y a n d M . G r e g o r , Z e m e n t - K a l k - G i p s , 2 1 , 4 5 1 ( 1 9 6 8 ) .
( 3 7 ) I. M a k i , R e v . 2 4 t h G e n . M t g . C e m . A s s c n . J a p a n , T o k y o , p . 5 ( 1 9 7 0 ) .
( 3 8 ) L . A . D o b r o n r a v o v a e t a l . , T r . ~ b s k . K h i m - T e c h n o l . I n s t . , 8 7 , 4 4
( 1 9 7 5 ) C . A . n o . 8 6 : 1 6 0 0 8 0 E .
(39) I.A. Kryzhanovskaya et al . , Cem. and Lime Mfg. 65), 45 (1966).
(40) I. Maki, Cem. Concr. Res., 3, 295 (1973).
( 4 1 ) M . R e g o u r d e t a l . , J . A p p l . C r y s t . , 6 , 3 5 5 ( 1 9 7 3 ) .
( 4 2 ) E . S . N e w m a n , J . R e s . N B S , 6 1 , 7 5 ( 1 9 5 8 ) .
( 4 3 ) W . C . T a y l o r , i b i d , 2 1 , 3 1 5 ( 1 9 3 8 ) .
( 4 4 ) W . C . T a y l o r , i b i d , 2 7 , 2 1 1 ( 1 9 4 1 ) .
728 Vol . 7, No. 6
I . Jawed, J. Skalny
( 4 5 ) W.C. T a y l o r , ibid, 2 9 , 4 3 7 ( 1 9 4 2 ) .
( 4 6 ) R.W. N u r s e , Proc. 3 r d Int'l. S ~ . C h e m i s t ~ " o f C e m e n t , L o n d o n , p. 56,
169 (1952).
(47) R.W. N~rse, Proc. 4th I n t ' l . Symp. Chemist~" of Cement, Washington
Vol . I , p. 9 (1960).
(48) Y. Suzukawa, Zement-Kalk-Gips, 9, 390 (1956).
(49) i". Suzukawa, Zement-Kalk-Gips, i , 433 (1956).
(50) E.S. Newman, J. Res. NBS, 62, 207 (1954).
(51) I . G. Luni ni na and M. A. Shaposhnikova, Tsement, ( 8) , 18 (1970).
(52) I . G. Luni ni na et a l . , Si l i k a t t e c h . , 24, 374 (1973).
(53) W. Danowski and W. St r ubel , Zement-Kalk-Gips, 29, 458 (1976).
(54) J. Forest , Rev. des b~t er i a~x Const r . , 557, 35 (1962).
(55) F. ~t ouschek, Zement-Kalk-Gips, 25, 395 (1976).
(56) H.A.C. Ni el sen, Rock Prod. 7~? (2), 72 (1974).
(57) W. Ri char t z, Zement-Kalk-Gips, 26, 1, 67 (1973).
(58) S. Sprung, i b i d 27, 259 (1974).
(59) Z.T. Jugovi c and J . l . Gi l l i am, J. b~t er . , 3, 517 (1968).
(60) K. F u j i i et a l . , Yogyo Kyokai Shi , 76, 50 (1968). Ceram. Abs. 53,
(i0) 240 i (1970).
(61) A. T s u m a g a r i a n d T. H i t a , Rev. 2 4 t h Gen. Mtg. Cem. A s s c n . J a p a n ,
p. 68 (1970).
(62) bl. A m a f u j i a n d A. T s u m a g a r i , Proc. 5 t h Int'l. Symp. C h e m i s t ~ ' o f
C e m e n t , T o k y o V o l . I, p. 1 3 6 (1968).
( 6 3 ) I . G . L u n i n i n a , T s e m e n t , ( 7 ) , 17 (1969).
(64) F. B e c k e r a n d W. S c h r ~ m l i , Cem. & L i m e M f g . , ( 9 ) , 91 (1969).
( 6 5 ) H.bl. Sylla, Z e m e n t - K a l k - G i p s , 2 7 , ( I 0 ) , 4 9 9 (1974).
( 6 6 ) F.W. L o c h e r e t al., ibid, 2_~5 (i), 1 (1972).
(67) F. T r o j e r , C e m e n t - W a p n o - G i p s , 2 5 ( 1 2 , 3 6 4 ( 1 9 7 0 ) .
(68) W. G u t t a n d M . A . S m i t h , Cem. T e c h . , 2, 143 ( 1 9 7 1 ) .
( 6 9 ) Yu. M. B u t t e t al., Proc. 6 t h Int'l. Congr. C h e m i s t r y o f C e m e n t ,
M o s c o w , P r i n c i p a l P a p e r (1974).
( 7 0 ) V.V. T i m a s h e v et al., Zh. Prikl. K h i m . , 4 9 , 1 9 1 9 ( 1 9 7 6 ) .
( 7 1 ) F.W. L o c h e r , Z e m e n t - K a l k - G i p s , 2 8 , 265 (1975).
(72) V. J o h a n s e n , ~ n u s c r i p t o f p r e s e n t a t i o n i n ~ d r i d , ( N o v . 1976).
(73) V. V u l k o v e t al., S t r o i t . ~ t e r . S i l i k a t . , 1 2 3 (1971), C. A. no.
7 5 : 1 1 2 5 0 5 Y.
( 7 4 ) I . G . L u g i n i n a e t al., N a u c h . S o o b s h c h . V s e s N a u c h Issled. I n s t . Tsem.
P r o m . , 2 3 , 26 (1968), C. A. no. 7 2 : 1 3 5 9 9 5 K .
( 7 5 ) A . D . A z e l i t s k a y a e t al., I z v . A k a d . N a u k S S R N e o r g . ~ t e r ~, 9 3 9 (1969),
C. A. no. 7 6 : 3 3 1 0 8 K .
Vol. 7, No. 6 729
ALKALIES, CEMENT CLINKER, HYDRAULICITY
(76) H. K r ~ m e r a n d H. z u r S t r a s s e n , Proc. 4 t h Int'l. Symp. C h e m i s t r y o f
C e m e n t , W a s h i n g t o n , p. 32 ( 1 9 6 0 ) .
(77) E. W o e r m a n n , ibid, p. 1 1 9 (1960).

(78) L. H i v e s , S i l i k a t y , I, 42 ( 1 9 7 1 ) .
(79) G. Y a m a g u c h i a n d H. U c h i k a w a , Z e m e n t - K a l k - G i p s , 1 4 , 497 (1961).
(80) G. Y a m a g u c h i a n d H. M i y a b e , J. A m e r . C e r a m . S o c . , 4 3 , 2 1 9 (1960).
(81) Y. O n o e t al., Rev. 2 3 r d Gen. Mtg. Cem. A s s c n . J a p a n , p. 61 (1969).
(82) K. T a k e m o t o a n d Y. O n o , ibid, p. 4 5 (1962).
( 8 3 ) I . G . L u g i n i n a e t el., T s e m e n t , [ i i ) , 13 (1974).
(84) V. S u z u k a w a a n d T. S a s a k i , Proc. 4 t h Int'l. Symp. C h e m i s t r y o f C e m e n t ,
W a s h i n g t o n , Vol. I, p. 83 ( 1 9 6 0 ) .
(85) Y. S u z u k a w a a n d T. S a s a k i , Rev. 1 3 t h Gen. M t g . o f Cem. A s s c n . J a p a n ,
p. i, (1959).
( 8 6 ) E.S. N e w m a n a n d L.S. W e l l s , J. Res. N B S 3 6 , 1 3 7 (1946).
(87) C. Chin, e t al., T ' a i N i C h i Shu, 7., 1 6 9 ( 1 9 7 2 ) C.A. no. 7 9 : 1 1 8 0 4 8 F .
( 8 8 ) A.E. M o o r e , N a t u r e , 199, 4 8 0 (1963).
( 8 9 ) A.E. M o o r e , Meg. Concr. R e s . , 18, 59 (1966).
( 9 0 ) D.E. Day, A S T M Publ. no. 395, 48 (1965).
( 9 1 ) A.I. B o i k o v a e t el., T s e m e n t , ( 8 ) , 2 0 (1976).
(92) I. ~ k i , Rev. 2 S t h Gen. M t g . Cem. A s s c n . J a p a n , p. 23 (1971).
( 9 3 ) Yu. M. B u t t e t al., T s e m e n t , ( 5 ) , 9 (1957).
(94) K. B e n y e i , E p i t o a n y a g , 2 4 , 71 (1972).
( 9 5 ) B.V. V o l k o n s k i i a n d N.P. S h t e i e r t , T s e m e n t , ( I 0 ) , 6 ( 1 9 7 0 ) .
( 9 6 ) A.A. L o k o t e t el., Vyzh. ~ t e r . Sib. V o s t o k a , 1 2 3 (1970), C.A.
no. 7 5 : 7 9 9 9 0 9 H .
(97) W. G u t t a n d M.A. S m i t h , T r a n s . Brit. C e r a m . S o c . , 6 7 , 4 8 7 (1968).
(98) T. T s u b o i e t al. Rev. 2 4 t h G e n . M t g . Cem. A s s c n . J a p a n , p. 1 3 (1970).
(99) T. T s u b o i e t al., Z e m e n t - K a l k - G i p s , 2 5 , 292 (1972).
(100) T. T s u b o i e t al., ibid, 25, 4 2 9 (1972).
(i01) M. F u k u d a , Rev. i S t h Gen. Mtg. Cem. A s s c n . J a p a n , p. 3 6 (1961).
(102) C.H. Li, H w a h a k K w a K o n n g o p , ( 6 ) , 3 2 6 (1972), C.A. no. 7 9 : 1 1 8 0 1 3 R .
(103) P.P. M a r t y n s t e v e t al., T r a n s . N b s k . K h i m - T e c h n o l . Inst., 7 6 , 1 1 6
(1973). C.A. no. 8 2 : 1 4 4 2 4 0 U .
(104) K. M u r a k a m i e t al., S e k k o t o S e k k a i , 109, 2 4 1 (1970).
(105) Yu. M. Butt e t al., T s e m e n t , ( 4 ) , 1 4 (1971).
(106) A.D. A z e l i t s k a y a , e t al., ibid, ( 2 ) , 6 [1969).
(107) A.A. L o k o t a n d A . D . A z e l i t s k a y a , T r a n s . N o v o c h e r k a s s k . P o l i t e c h .
Inst., 189, I 0 3 (1969). C.A. no. 7 2 : 5 8 7 6 6 .