Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
TheCeramicSociety
Society of
of
Japan
Japan
Journaiofthe
CeramicSocietvofJapan
leY
Paper
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!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
380
NII-Electronic
NII-Electronic
Library Service
The Ceramic
TheCeramicSociety
Society of
of
Japan
Japan
Jbuntag
oft'heCeramic SocielyoffoPanle9 [5] 2001
Choon-Keun PARK
Table1
381
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
As
a result
also
oi
nm
stabilize
(122)of 6-C2Scrystal
regardless
are
of stabilizers
almost
constant
value
of
O.278
used.
C2S stabilized
by SO/sincreases.
The d-valueoE I7-C2S
stabi-
were
observed
when
the quenching
temperature
was
NII-Electronic
NII-Electronic
Library Service
The Ceramic
TheCeramicSociety
Society of
ofJapanJapan
382
Effectsof Sintering
Temperature
Table2,
on
the Formationef
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
NII-Electronic
NII-Electronic
Library Service
The Ceramic
TheCeramicSociety
Society of
ofJapanJapan
jburnai
ofthe Cememic SocielyofjuPan 109 [5]2001
Choon-Keun PARK
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.
S6'
oi
(Ca2
substitute
.M.)
The imperfection of
(Sii-,N,)04.
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,
NII-Electronic
NII-Electronic
Library Service
The Ceramic
TheCeramicSociety
Society of
of
Japan
Japan
384
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-
rninerals,
such
as
Q",
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
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
The Ceramic
TheCeramicSociety
Society of
ofJapanJapan
'5] 2001
Choon-Keun I]ARK
385
6-CzSwas
stability
of
stabilized
fi-CzS
by KL,Oand
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)
5)
Menetrier, D.
3)
(1979).
{1980).
and
C, H., .1.
Am, Ceium
J.Am.
Svc,,62,
Jawed,I.,CEm. Concr.
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).
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-
NII-Electronic
NII-Electronic
Library Service