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Paper

l5] 380-385 (2001)

Hydrationof
Silicate
ContainingStabilizersDicaicium

PhaseTransformation

and

Choon-Keun PARK
Korea Ihastitute
35-3, Hongchon-Ri, lbjang-toun,Chonan
ofindttstrialfl!cJmolagv'.

v)Trci;-6
?xxtfiil(ldi

{si-rhJLsir)ASi
iF #tc

iJ

330-8215

Korea

b'- ts(7)iegpe..(} zkMNJM

330-825 Jkptftpa JCk"i t,/utfi

ptajthgttrtiff1,eewa,
from reagent grade chemicals
usi]g
temperature and sy]thesized
the most effective stabilizer for dicalcium silicate. Phase transformation from P-to 7-dicalcium silicate depends on the start temperature of quenching. Hydration heat of
shows
that S03 delayed hydration at an early hydration time, but higher heat liberationrate at a later
fi-C2S
hydration time than the other stabilizers. 29Si MAS NMR analysis shows that the h)rdrateof dicalcium silicate
stabilized
by B20g is polymerized more than those of diealcium silicates stabilized by K20 a]d SO:.
of
calcium
silicate hydrate aecordi"g
to stabilizers: dicalcium
Diealeium silicate prese]ts differentshapes
of C-S-H.
foilshape and K20 needle shape
silicate stabilized
by B203 shows crumbled
FReceived
June29, 1999; Accepted Septenibcr20, 2000]
silicate
fi-dicalcium

B!03,K20

Key-words

or

S03 as

was
stabilized
at room
stabilizers.
B20: acts

as

llydrates
Dicalciumsilicate, Slabitixeny
Phase traitstbrmation,Polymeriaation,

1, lntroduction
isone of the main crystalline phases o'f
clinker,
and
has many
advantages:
low
portland cement
during clinkerization,
low heat of Iiberenerg}r
consumption
ation and ]ow absorption
of superplasticjzer
when hydrated,
high flowability
of concrete
of structure etc.
good durability
Although dicalcium silicate has many strong points,ithas a
limitof applications because of itsslow hydrationrate at an
early stage and itsphase transiormation of 6-C2Sto v-C2S
The transformation of fiphase duringthe clinkerization.
C2S to v-C2S cause volume change of clinker, resulting in
them in the kiln which
jnforming dustsand circulating
fluence a sintering process and qualityproblems, The reactivity of 7-C2S is very low and affects low rnechanical
propertiesof cement. Therefore, the transformationhas to
silicate in
be prohibitedin case of rnuch amount of dicalcium
the clinker for better sintering process and quality of
resultant
product,cernent.
For stabilizing or- or 6-C2S
which
isunstable forrnat room
studjesi/''5/' have been conducted
to find
temperature, many
foreignionswhich stabi]ize the 6-C2S
phase at roem tcmperthat thc
ature and increasethe hydrationrate, and reported
foreign ions, such as I3,K, S, Mn, Cr etc., were good
a theostabilizers
for the fi-C2S
phase. Schwiete6)suggested
ry of judgment
to determine ionsstabilizing fi-C2S,
which is
based on ionic radius, Pritts andi Daugherty7)
had also
reported
the judgment
of CfRratio (C:
ionicelectrovalence,
R: Pauling'sionicradius) to determine stabilization of the
dicalciumsilicate crystal at room temperature. They also
reported
that the rate of S-C2S hyclrationwas greatly infiuencedby the type and the amount
ofa
foreignion doped
to the calcium
silicate structure;
the stabilizers incorporated
intothe dicaleium silicated struc:ture may rctard or accelerated by hydration reaction,
In this paper, the characteristics
of fi-C2S
stabilized by
foreignions,such as B, S and K were invest{gatedby XRD,
DTA and SEM, and the phase stability and hydration ol
In addition, the hydration behavior
were
also studied.
fi-C2S
2gSiMASNMR
analysis
ef fi-C2S
was
alse discussed with
and
SEM observation.

'Dicalcium

silicate

2. Experimental

The

silicate
6-dicalcium

specimens
of
reagent
grade chemicals

were

synthesized

in Table 1. The
a CaOISi02 rnolecmixtures
of CaO and Si02were
ule ratio of 2.0.The stabilizers,
B, K20 and SO/]were suppliedbychemicalsH3B03,K2C03CaS042HzO,respectively.
For synthesizing
the specimens
the mixtures
were
mixed
in a ballmill and calcined at 10000C for 1 h,After calcination
the mixtures
were
pressed intoa pellet,20 cm in diameter
and
20 cm in height,and then sintered at 1400DC for 3h.
The sintered samples
were coeled down with a cooling rate
ef 300eClh in a furnace to 1400,1200, 1000, and 5000C, and
to investigateefthen finallyquenched by air blow in order
fectsof cooling temperature on the stabilization of dicalciurn
silicatc structure
at room
temperature. (refer
to a cooling
condition
in Table 2)
to invesXRD was performed on the sintered specimens
Free CaO values were measured
tigatephase identification.
sintering
degree of dicalciurnsilicate. To
fordetermining
the fi-C2S,
all the specimens
were
characterize
ground to the
Blaine specific surtace are 3000 cm2fg. The phase stability
obef synthes{zed
6-CzSwas studied using DTA and SEM 2DSi
measurement,
servation.
Micro-conduction calorimeter
MAS NMR analysis and SEM observation were also carried
out for studying
hydrates cured at 200C with selid to liquid
ratio of O.5.Calcium and
silicate ionconcentrations
of solutions filtered
from paste slurries were also measured,
The
paste slurries were prepared and stirred on the magnetic
stirrer
with
WfC=5.
using

as shown
basedon

3, Results and discussion

3.1 Phase stability of dica[cium silicate
Table 2 shows the effects of sintering temperature and
The forejgnions
cooling
condition
on the stability of 6-CzS.
Burnability
act at not only stabilizers
but also mineralizers.
of fi-C2S
is dependent on the foreignion.KzO gradually
decreases ACaO from 1.9% to O.7% as the temperature increases
from 1200 to 14000C. Bz03 shows that the fLCaO
abruptly
decreases frem 12.7to O.2% as the tempcrature increases
from 1200 to 13500C.S03 represents venr lowfCaO
14000C.
at temperatures between 10000C and
(O.5-O.2%)

380

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Table1

381

. Compositionsof MixturesIJsedinthe Study(mass%)

Specimens

CaC03

Si02

H3B03

P-C2S(B)

77.5

22.0

O.7

P-C2S(IC)

74.7

22,3

P-C,S(S)

75.5

21.5

CaS04-2H20

K2CO,

'

3.0

3.0

za

/.

tzadets,1

th
-s

B -C,S (K,O)

B -C,S (SO,)
Fig. 1 . SEM

micrographs

oi

the

stabilized
fi-C2S

B -C,S(B,O,)
by

various

foreign ions.

EXO

:Endo
400

6De

1,OO{]

ueo

1,4oe

1.200

Temperaturec=}
Fig. 2.

Phasa

transformation

of

C2S stubilized by foreign ions (coolimg

rate: 20Cfrnin).

the SO:sisthe bestmincralizer.

The foreignions
the 6-CzSphase as the sintering temperature
increases.At temperatures higher than 14000C, the d-values

As

a result

also

oi

nm

stabilize

(122)of 6-C2Scrystal
regardless

are

of stabilizers

almost

constant

value

of

O.278

used.

When the sintered specimens

were
cooled
down, changes
inlatticeparameters of fi-C2S
occurred.
The B-C2S
stabilized
by K20 shows
that d-value of (122)decreases as the
temperature decreases, while the d-value of 6quenching

C2S stabilized

by SO/sincreases.
The d-valueoE I7-C2S
stabi-

lizedby B203 shows the almost the same value regardless

of
sintering temperature, at temperature higher than 1200"C.
Conversionreaction
from fi-to 7-C2S stabilized by K20
and
S03 isstrongly dependenton the start temperature of

quenching: the phase transformationoccurred much at low

start temperature of quenching, ]owerthan 12000C. Dusting
changes between
phenomena which were caused by volume
two dicalcium
si]icate phases due to the conversion
of S-to
y-C2S

were

observed

when

the quenching

temperature

was

low, lower than 12000C, for the specimens

stabilized
by S03
and
K20. No dusting phenomena were observed
for the
specimen
stabilized
by B203 regardless
of quenching ternat reom
perature. The B203 isa good stabilizer ior the fi-C2S
temperature.
The microtexture
of fi-C2S
stabilized
by various foreign
ionsarc shown in Fig. 1 ,The microtexture
of 6-C2S
crystal
was
influencedby foreignions.On the surfaces of dicalcium
silicates
stabi]ized
with
S03 and K20, there are stripes

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382

Phase Transformationand Hydration of Dicalcium

Silicate
Containing
Stabilizers

Effectsof Sintering
Temperature

Table2,

on

the Formationef

fi-C2Sand Effectsof Cooling Condition

on

the

Phase

Stability
of fi-C2S

(Sintering)Specimens
SinteringTemp.(OC)

dof(122>*"
Oo'iom)

f-CaO(O/,)

P-C7S.(K)S

1,2001,2501.3001,3SOI,4002.79402.793S2.79202,79422.7861
1.91.71.61.5O.7

P-c2s-(s)

1,2001,2501,3001,3501,400
2.78232.78172.78252.78212.7805
O,5O.2O.202O,2

P-C2S-(B)

1,2oo1,2501,3oe1,3501,4002.77792.77712.77982.78132.7811
l2.76.52.3O.2O.2

(Cooling)Specimens
StartTemperatureof

dof(122)

Quenching(OC)

P-C2S-(K)

3-C2S-(S)

p-c,s-e)

S;S03,

*K:K20,
""

d value

***

ef

1400,l,2001,OOO500

2.78482.78472.78402.7gll

l,4001,2001,OOO500

2.78112.78152.78172.7827xooo

1,4001,2001,OOO500

2.78132.78172,78112,7811xxxx

sion,

silicate
B diealgfufn

i occurred,

: not

occurred.

seem

but the

xooo

BIB20s

tobe larnella-like
waves
related
to of }fi converspecimens
stabilized
by B203 was not observed.
The grain sizes of fi-C2Sstabilized by Bz03 and S03 are
smaller
than thatof K20. The crystal size isclosely related
with
the burnabilityas shown
in Table Z. The low "CaO
shows
larger
crystal
size of the dicalcium silicate.
The results of DTA of dicalcium silicates are shown
in
Fig. 2. All specimens
were
heated to 15000C with heating
rate 10[C!min and then cool down with
20C!min. All specimens
show
exothermic
peaks of phase transiormation of
from cr to hightemperature forrn(cbi')
from low temperature iorrn (eq.")
to fi-C2S
around
at 1400 and 7000C, respectively. In the specimen
stabilized by B203 S- to y-C2S phase
transiormation around
not
at 500"C was
occurred.
But in the
which

Dustingphenornena**th

(10'i"m)

stabilized
by S03 and K20, and the controlled
the exotherrnic peak of fito y-C2S were detected
around
at 5000C. Especiallythe controlled
at the specimen
stabilized
by SO:ishow high exotherrnic
much
peak meaning
phase transformation of fi-to y-phase. The exothermic
were
shown
differentshapes and ocpeaks of the specimens
curred
at slightly
differenttemperatures because of different influencesoi foreignions to crystallization
of dicalcium
silicate. The foreign ions incorporated
into the dicalcium
silicate structure
is locally
distortedits latticeand causes
crystal
imperfections.i),2),6)7)
The degree of crystal imperfection by a foreign ion is strongly dependent on ionic
radius,
mode
polarizationability related with substitution
and
binding force between metal ions and (SiOD.O2>
B3'/
specimens
specimen

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383

AoruocobL"ties9Nte2

10

otobuMinutes

.c-.rv9di.-,

30

20

Heurs

Time
Fig.3.

Heat

of

liberationrates

for the

as a
6-C2S's

function of hydration

time

cured

at

different
temperatures.

ISOO
?v='l

fiEaeE:atcsxb:28
1500

1000

1ooO

:.

;E,soo

soo

:/

a1

o1
10Time

100

leoo

10Time

1OO

1000

{hr)

(hr)(A)

(B)
20DO

AegEws':ee'g:e:eL-:.":e"

1500

1000

soo

o1
10Time

1OOO

{hr)1OO

(C)
Fig. 4.B203,
Solublecalcium

and

(B)fi-C2Sstubilized

silicate

by KzO,

ion concentrations

stabilized
(C)fi-C2S

in the solution
by S03.

for Si4',and K' for Ca2" inthe formula

crystal
by
foreign ion is closely related with thermodynamic equation,
E= UL71S, where E isfreeenergy for the transformationof
dicalciurmsilicate, [J is internalenergy and S is entropy.
When a foreignion isincorporatedintoa dicalcium silicate
and

S6'

oi

(Ca2

substitute
.M.)

The imperfection of
(Sii-,N,)04.

filteredfrom the paste

slurries

of

(A)S-C2Sstabilizedi
fi-C2S's.

by

the entropy
increases, and the free energy
decreases.At temperature lower than the phase transiormation temperature of rs-to y- of C2S, the increase
of free
energy
ismore significant than thatof entropy, and the distributionof foreignion in a crystal causes the latticeenerg}r
to increase,resulting in unstable dicalcium silicate.i) From
structure,

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Phase Transformationand Hydration of Dic;]lciumSi]icHte

CcmtuiningStnbilizers

the results B/i'substitutes for Sid' easier than Si6',resulting in stabilizing high temperature fiform of dicalcium siljcate at room
temperature. ,K- substitutes
for Ca2 , different mode
from those of B and S and shows differentshape of
exothermic pcak, lo"rerexothermic
peaks at lower temperatures,compared Lo B and S.
3.2 Hydration of fi-C2Sstabilized by foreign ions

isnot
fi-C2S

reactive

with

water

cornpared

with

other

QO
L

ce-

tricalcium silicatc, calcium

aluminate
etc. Fierens and TirlocaS']
reported
that the types
of foreignions greatlyaffected
the degree of hydration of
speci6-C2S.Figure 3 shows the heat ef liberationof fi-C2S
were
mens
stabj]ized by various stabilizers. The specimens
liberation
heat
cured at 20 and 400C for 36 h, and mcasured
rate as a function
of hydration
time, The specimens
containing S03 liberates
highliberation
heatrate immediately
after
contact
oi the spceimen
with water,
compared
to the other
specimcns
which
are very
similar
each
other,
But the environmental
temperature docs not infiuencethe very early
liberliberation
heatrate, Aftercontact water the specimens
trends according
ated heat continuously, and show diflerent
SO/t liberates
to the stabilizers. The specimen containing
heatlittle
at an early hydration
time and much until/ 36 h,but
the environmental
temperature infiuences
hydrationrate;
high temperature accelerates
hydration resulting in ealy
maximum
peak from at 2-3h at 200C to 9 at 40MC. The
spccimen
containing
S03 also shows the hydration isretarded, especially
at 200C, and hydrated centinuously
and
very
containing
actively at a laterhydrationtime. The specimens
KuO and B203 represent similar hydration except that B203
higher heat liberatjon
rate than K20. The environmental
temperature affects to accelerate
hydration,
butthe effects
of temperature
on the liberationheat rate are not so significant,
compared
to the S03.
The results measured
the concentrations
of Ca2' and Si4in the solution tiltered
from the paste slurries are shown in
Fig. 4. Three specimens
represent
that the ca]cium
ion conhigher than the silicate ion concentration
centration ismuch
in the solution. The trends of soluble cation concentrations
are inagreement
with
the results of Trettin
et al.9) that calcium
ion concentration
ishigher than silicate ions,resulting
in increasingCIS ratio in thc liquidphase with hydration
time. In the specimens
of BzO/sand
K20 the distinguished
maximum
concentrations
of silicatc are occurred
within
20
min.
The specimen
containing
KzO shows higher concentration of calcium
and higher maximum
concentration
of silicate than the other
specimens.
This specimons also shows
soluble
K ionwhich increases
concentration
with time. The
at
K ion isconsidered
to accelerated
hydration of the fi-C2S
an early hydration time and forming high calcium and maxistabimum
silicatc ion concentration.
For the of specimcn
lizedby SO/s,the calcium ien concentration
increases
linearly and represents
high silicate ion concentration
at all over
hydration time. This result means the hydration isoccurred
ment

rninerals,

such

as

continously more actively than two other specimens.

BeU et al.iO)studied hydrates using ZUSi MAS NMR and
reported
that the total range of 2YSi shifts in silicates was
related
to the degree of pelymerizationo[ the Si04 tetrahedra
where
O" represcnts the Si04 tetrahedron while
of other tetrahedra to
the superscript refers to the number

Q",

islinked by sharing of O and OII. It can be divided

'formonosilicated
into separate
ranges
(QO;-66--74
-75--82
disilicate
and
chain
end
ppm),
groups (Q';
-85
-89 ppm), chain
ppm), chain middle groups ((}2; to
branching site (Q3;-95--100ppm)
and
three-dimensional frame work
(Q`;-10S--115 pprn). 20Si MAS NMR
spectra
of hydrates of 6-C2Scured
at room
temperature for
7 d are shown in Fig. 5. The hydrate of fi-CzS
stabilized
by
B203 show Qi and OZ spectra at 7 d, The other hydrates of

S03

tspmvWww

K20

Ql

bu,.NwhNN

rr--7"-rr

-60

-so

---"-T----T
-100

PPM
Fig, 5, 29Si MAS NMR
foreign ions (Thespecimens

spectra

hydrates of fi-C2Sstabilized by
bydratad fer 7 d at room
temper-

of

were

ature),

which

by S03 and' K20 do not show Q2. The

hydration of 6-C2Sstabilized by
stabilized
by
polyrnerized tban thosc of fi-C2S

stabilized
fi-C2S's
results

suggest

that the

Bz03 ismore
K20 and S03,

The rnicrestructures
the types of stabilizers,
6) The morphology
(Fig.

of

6-C2Shydrate

dependcnt on
C-S-H gel,
hydrate o'i fi-C2S
stabilized
by

especially
of

the

are

shapes

of

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385

B203 and S03 in crumbled

foils,
while
the morphology
of hydrate of fi-C2S
stabilized
by KzO isneedle shape. The specimen
stabilized
by S03 shows very short calcium si]icate hydrate, compared
with
K20 and B203. SEM micrographs
show
that the crystallinity of C-S-H forthe fi-C2S's
stabilizedwith Bz03 and K20 are higherthan that of S03.
4. Conclusions
prepared at 14000C ior 3h in order to investigate phase stability and the hydrationreaction. The results
obtained
from the study are as follows
stabilized
by B203 shows a very stable phase
(1) fi-C2S
regardless
of the start temperature of quenching,

6-CzSwas

(2) The phase

stability

of

stabilized
fi-CzS

by KL,Oand

S03 is dependent on a quenching condition: fi-C2S

is stabilizedby K20 and S03 when the quenehing temperature is
greater than 12000C.
(3) Heat of hydration of the 6-C2Salso depends on the
stabilizers:
S03 delayed hydration at an early hydration
time, but showed
high liberationheat rate at a laterhydrationtime,compared
to two other stabilizers. The B203similarto KzO except a couple of hoursdelayedhydrationand
high liberationheat.
(4) 6-C2Sstabilized by various foreign ions shows
differentcrystallinity and morphology
of calcium
silicate hydrate: the specimens
stabilized
by B203 and S03 present
crumbled
foiland K20 presents neeclle shape. The crystallinityof C-S-I{ prepared by S03 islower than by B203 and

K20,

References
16, 587-601 <1986).
X. and Long, S.,Cem. Concr'.
Res'.,
2) Puertas,F, and Glasser,
F. P.,Cem. Concr.Res.,18, 783-88
1)

Feng,

(1988).

4)

Kantro,D. L. and Weise,

621-26 (1979),
Fujii, K. and Kondo, W.,

5)

Menetrier, D.

3)

(1979).
{1980).

and

C, H., .1.
Am, Ceium

J.Am.

Svc,,62,

Ceratn. Soc., 62, 161-67

Jawed,I.,CEm. Concr.

Res., 1O, 425-32

6) Schwiete,H, E.,Zentent-Kalk-GiPs,
21, 350-72 (1968).
7) Pritts,I.M. and Daugherty,K. E., Cem. Concr.Res.,6,
8)

783-96 (1976),
Fierens, P. and Tirloca, J.,Cem

{1983).

Concr.Res., 13, 267-76

9) Trettin,
R,, Satava,V. and Wieker, W.,
and SetLing o'iCement,"Ed. by Nonat,A. and Mutin, J.C,,E & FN
Spon, London (1992)
pp, 289-97,
10) Bell,G, M, M,, Benstend,J.and Glasser, F. P., Adv. Cem.
Res,, 3, 23-37

Fig.eignture)6,ionsSEM
micrographs

{Thespecimens

of
were

hydratesof fi-C2S
stabilized
hydrated for 7d

at

room

"Hydratien

(1990.

by fortemparu-

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