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Cement and Concrete Composites 20 (1998) 163-170

0 1998 Elsevier Science Ltd. All rights reserved

Printed in Great Britain
ELSEVIER PII:SO958-9465(97)00064-4

Expansive admixtures (mainly ettringite)

S. Nagataki,” & H. Gem?
“Department of Civil Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan
“Denki Kagaku Kogyo K. K., Chiyoda-ku, Tokyo 200, Japan

iibstract To cover these faults of concrete structure,

study into the expansive cement has been made
The hydration chemistry of expansive cements is in foreign countries which utilizes the expansi-
described with emphasis on the components for bility of ettringite. Ettringite has been detested
jormation of ettringites. Expansive cement con- as ‘a cement-bacillus’ which causes expansive
c,rete as ‘shrinkage-compensating concrete’ or fracture of concrete. In 1936, Lossier’ began a
‘chemical prestressing concrete ’ is applied to many study to produce chemically prestressed con-
kinds of concrete construction. This paper outlines crete and thereafter Lafuma’ and Klein3 took
the chemical composition of calcium sulfo- over the study to build up a foundation of the
uluminate and lime-based expansive admixtures expansive cement.
und discusses the expanding mechanism, chemical AC1 Standards (proposal)4 show three kinds
prestressing, and typical properties of expansive of expansive cement, that is, ‘K type’, ‘M type’
r,ement concrete. Finally, research and develop- and ‘S type’. In Japan, the beginning of the
ment are introduced with respect to expansive growth of expansive concrete was felt in the
admixtures. Furthermore, these expansive mid-1960s with the development of expansive
udmrjctures are based on cement minerals, except admixtures. Since then for more than 20 years
:qas fomzing admixture’ and ‘admixtures contain- not only the basic research but also the investi-
ing granulated iron filings’. 0 1998 Elsevier gation into practical use has been actively
Science Ltd. All rights reserved. continued. Expansive concretes developed in
Japan, unlike those in America and Europe
Keywords: concrete, expansive admixture, ettrin- which have been made with the use of expan-
gite, shrinkage-compensating concrete, chemical sive cement, are manufactured by mixing
prestressing concrete, expanding mechanism, expansive admixtures with concrete, with the
expansion rate, strength, length change, dura- result that control and management of expan-
bility. sion rate are made easy. Therefore, expansive
concretes of Japanese type are widely used not
only in shrinkage-compensating concrete but
INTRODUCTION also in chemical prestressed concrete which
positively utilizes the expansibility of them, Pro-
Conrete has two inherent properties such as duction of expansive admixtures in Japan is
‘shrinkage due to drying’ and ‘smaller tensile roughly estimated at 70000 metric tons in 1995.
strength compared with compressive strength’. Therefore, about 1700000 rnA3 of expansive
Consequently, it is unavoidable for concrete in concrete was used yearly. Recent tendency
a structure to crack due to drying shrinkage. toward reconsideration of cracks in concrete
These cracks are mentioned as the largest draw- structures from the viewpoint of durability may
back of concrete structure, as they lower the have created a new need for the expansive
durability due to the water entering to hasten admixture as a method of crack prevention.
the corrosion of steel bars, allow the leakage of Moreover, a certain type of expansive
rain, and spoil the beauty. admixture, with a property to control the ‘the
164 S. Nagataki & H. Gomi

thermal cracking due to the heat of hydration of followings are mentioned as expansive; ettrin-
cement’ which has a possibility to be caused gite (C3A*3CaS04+32H20) shown at T-point,
with an increase of larger concrete structures, monosulfate (C3ACaS04*12H20) shown at M-
has also been put to practical use. point and calcium hydroxide (Ca(OH),) shown
In this paper, properties of expansive admix- on CaO.
ture and concrete are expressed and also the Examples of calculation for the volume
present technical problems and the trend of change at the time of hydration of expansive
development are stated. hydrate are shown as follows:
Production of ettringite
ADMIXTURES C4A3S + KaSO,+ 6CaO + 96H20
Expansive admixtures have such as iron powder, Weight 610 1088 336 1728 3762
alumina powder, magnesia, calcium sulfo alumi- Specific gravity 2.61 2.96 3.34
Volume (234 368 101 172:) [2431] ;l::
nate (CaO-A1302-S03) and calcium oxide
(CaO). However, the main groups are the cal- Rate of volume change for hydrates series
cium sulfo aluminate series. 2175-2431/2431 x 100 = - 105%
AC1 STANDARDS (proposal) in the USA4
include three types of expansive cement as fol- Ratio of volume change for C4A3S particle
lows: 21751234 = 9.3 times

(1) K-type: portland cement mixed with Production of monosulfate

anhydrous Hauyne (3Ca0*3Al,03CaS04),
gypsum (CaS04) and quick lime (CaO).
(2) M-type: portland cement mixed with alu-
mina cement and gypsum (CaS04) at a Weight 610 272 336 648 1866
Specific gravity 2.61 2.96 3.34 1.95
reasonable ratio. Volume (234 92 101 64:) [ 10751 957
(3) S-type: normal portland cement mixed with
larger amount of tricalcium aluminate Rate of volume change for hydrates series
(C,A) and gypsum (CaS04). 957-1075/1075 x 100 = - 10.9%
Figure 1 shows a three-component system5 of Ratio of volume change for C4A3S particle
an expansive admixture relating to calcium sulfo 9571234 = 4.1 times
aluminate series. When a component including
Production of Ca(OH),
these minerals hydrates, various kinds of
hydrates are produced. Of these hydrates the CaO+H20-+Ca(OH),
Weight 56 18 74
Specific gravity 3.34 2.24
Volume (17 1:) [35] 33

Rate of volume change for hydrates series

33-35/35 x 100 = -5.7%
Ratio of volume change for CaO particle
33/17 = 1a9 times

Several expansion mechanism of expansive
.. .
cement concrete have been proposed as follows:

(1) volume increase of gel state expansive

ingredients by water adsorption (swelling
CaO C3A C12A 7 CI 4 A1203 (2) spreading out of surroundings by crystal
H : 3Ca0.3A1203.CaS04 growth of crystalline expansive ingredients
T : C3A-3CaS04 eguivaient to ettringite
M : C3A-CaSO 4 euuivdent to mono&fate (crystal growth fheory)8-1’
provfded that C=CaO, A=AI $I 3 S=SO 3 (3) forming coexisting pores by disintegration
Fig. 1. Diagram of expansive admixtures. of expansive ingredients during hydration12
Expansive admixtures 165

In either case, ‘formation of pores in the hard-

ened structure’ or ‘formation of gel state Table 1. Physical properties and chemical composition
hydrates with low density’ is required for the
‘expansion’ to coexist with ‘chemical shrinkage’. Item C-S-A CaO
Further studies are needed to examine quantita- type type
tively the formation of pores and gel state Physical Specific gravity (%) 3.00 3.14
hydrates, and to discuss including the chemical properties Specific surface area 2500 3500
shrinkage and autogenous shrinkageI (or auto- (cm’jg)
Ignition loss (%) 0.8 0.4
genous expansion). In the case of expansion SiO, (%) 4.0 9.6
taking place with formation of ettringite or CH, AI203 (%) 10.0 2.5
topo-chemical reaction at the surface of expan- Chemical FeA (%) 1.0 1.3
composition CaO (%) 51.2 67.3
sive ingredients is widely accepted rather than MgO (%) 0.6 0.4
through-solution reaction. The important factor SO3 (%> 31.9 18.0
in expansion is not merely the hydration of Total (%) 99.5 99.5
expansive ingredients, but the formation of sur-
rounding hydrates which the compressive force
produced from the expansive ingredients are
transmitted to.14 Namely, expansion does not
take place otherwise the hardened matrix struc-
ture is formed by hydration of cement.
Accordingly, it is also importnat that the hydra-
tion of both expansive admixtures and cement
must take place at the opportune moment.
Japanese definition of expansive admixture HsO
explains that ‘Admixtures, when mixed with
cement and water, produce ettringite (3CaO.
A1203CaS04.32H20) or calcium hydroxide SolId Solution
(Ca(OH)*) by hydration reaction to expand the
concrete’. Table 1 shows the physical properties I
(Topochemical Reaction)
and chemical compositions of both ‘ETTRIN-
Ettringite Acicular Crystals
(SITE series’ and ‘LIME series’. Figure 2 shows 3CaO-A/.0,-3CaS0,.32HI0
their chemical reaction formula. Table 2 shows
the quality standards prescribed in JIS A 6202
‘Expansive Admixtures for Concrete’ which are
‘%i?-j + KO -t
now under revision to secure unity with ‘IS0
Standards’. Fig. 2. Schematic representation of the reaction.

Table 2. Specifications of expansive admixtures

Ifems Specified value

Chemical composition Magnesium oxide (%) 5.0 max

Ignition loss (%) 3.0 max

Physical properties Specific surface area (cm2/g) . 2000 min

Residue on 1.2 mm sieve* (%) 0.5 max
Set Initial setting (min) 60 and after
Closing of setting (h) Within 10
Expansivity (rate of length change) 7 days 0.000 30 min
28 days - 0.000 20 min
3 days 6.9 min
Compressive strength (MPa) 7 days 14.7 min
28 days 29.4 min

*The 1.2 mm sieve is 1190 ,um aperture standard sieve specified in JIS Z 8801.
166 S. Nagataki & H. Gomi


When expansive concretes are classified based “E

on size of expansive force, they may be broadly ry)
divided into shrinkage compensating concrete 5
and chemical prestressing concrete. 5 300
Fresh concrete of expansive concrete shows
about the same nature with ordinary concrete in gs 200
which expansive admixtures are absent.15 ‘5
Figure 3 shows the expansion rate of the B
h 100
expansive concrete in the relation between unit E
expansive admixture content and nonrestraint S
expansion rate.16 It shows that the expansive 0 10 20 30 40 50
rate becomes larger with the increase of unit Unit Expansive Admixture Content (kg/m 3,
expansive admixture content having good rela- Fig. 4. Relations among unit expansive admixture con-
tion with unit expansive admixture content. tent, compressive strength and restraint expansion rate.
Figure 4 is an example showing relations among
unit expansive admixture content, compressive
strength and expansion rate.17 It is shown that of steel mold does not show such lowering of
restraint expansion rate becomes larger with the strength and shows about the same strength as
increase of unit expansive admixture content. the ordinary concrete, irrespective of large
However, the compressive strength of expansive expansive rate. It is possible that in the latter
concrete having unit expansive admixture con- case the structure of concrete is kept compact
tent not much exceeding 30 kg/m” and cured by restraining to cause no lowering of strength.
under nonrestraint condition shows about the Under the condition where unit expansive
same value with ordinary concrete. The com- admixture content is not much exceeding 30 kg/
pressive strength decreases when expansive rate m -3, tensile strength, bending strength, bond
increases to some extent. It is possible that strength, Young’s modulus and creep of the
when the expansive concrete is allowed to expansive concrete are about the same as ordi-
expand without restraint the structure of the nary concrete.15
concrete becomes loosened to cause the lower- As for durability, the expansive concrete
ing of strength. However, the expansive given long time water curing does not change
concrete allowed to expand under the restrain the expansive rate after it has reached a settled
value. Though the expansive concrete dry cured
after water curing shows shrinkage due to dry-
ing, it is generally recognized that the shrinkage
rate is smaller than ordinary concrete. One of
I I I I the examples is shown in Fig. 5.” When unit
expansive admixture content not much exceed-

0- 600


10 20 30 40 50 60
Unit Expansive Admixture Content (kg/m 3, 3 5 11 29d. 3 6m. 1 5Y.

Fig. 3. Relation between unit expansive admixture con- Age

tent and nonrestraint expansion rate. Fig. 5. Rate of length change.
Expansive admixtures 167

ing 30 kg/mm3 are air entraining agent is used,

freezing and thawing resistance shows about the
same value as the ordinary concrete. However,
when unit expansive admixture content not
much exceeding 50 kg/me3 is used and concrete
is allowed to expand with unsatisfactory
restraining, it is reported that frost damage
resistance is sometimes lowered.15 The element
which exerts the greatest influence on durability
factor is the kind of supplementary AE agent.
Therefore, it is shown that the durability can be
improved by increasing the air volume and
restraining with reinforcing bars, even if unit 7d 28d
expansive admixture content is not less than
35 kg/m-3.‘9 Fig. 7. Compressive strength of concrete.
Figure 619 shows the relation between dura-
bility factor and boid distance factor in
expansive concrete. It shows that durability specimens applied with phenolphthale in which
factor of steel fiber reinforced expansive con- had been exposed for 8 and 22 years respec-
crete gives little change with the variation of tively. Results of measurement of carbonation
hoid distance factor. As for the expansive con- depth by phenolphthale in method gave about
crete without steel fiber durability factor shows the same value.
great fall when the boid distance factor takes Though it is reported that sulfate resistance
not less than 300 ,um, with the result that the and wear resistance of expansive concrete show
same relation as ordinary concrete between about the same values as ordinary concrete, it is
durability factor and boid distance factor is recognized that water tightness of expansive
formed. concrete cured under restrained condition
With regard to comparison of samples of shows a tendency to give smaller value than
expansive concrete and ordinary concrete taken ordinary concrete.2’ This may be due to the
from actual concrete structures of 22 years old, compact structure of the expansive concrete
expansive concrete and ordinary concrete resulted from compressed air void in the con-
showed 28 day compressive strength of 18.6 and crete by press effect owing to the restraining of
18-l MPa respectively, that is, almost the same concrete during curing (Fig. 9).
strength; after 8 years, 56.3 MPa of compressive Expansive concrete has a chemical prestress
strength; after 22 years, 59-O MPa of compres- effect which introduces compressive stress into
sive strength; after 22 years of exposure, concrete by restraining the expansive energy
samples taken from the actual concrete struc-
tures showed satisfactory compressive strength
(Fig. 7).20 Figure 820 shows the carbonation
depth measured on the cut surface of core test 0 CSA concrete
0 Plain concrete

t l odecif-m
Subhon add ,*kMk&
5 20
ORegin lym UFKberM.?xed
cl 10

150 200 250 300 350 400 450

Boid Distance Factor ( I.Lm> 0 2 4 6 8 10 12 14 16 18 20 22 24
Fig. 6. Relation between boid distance factor and dura- Ape W
bility factor. Carbonation depth of concrete.
168 S. Nagataki & H. Gomi

2 loo amount of work U calculated from following

c equation, chemical prestress cCpXin the above-
‘I 80 mentioned eqn 1 can be computed.
.g 60 (2)
5 where:
PS restraining steel ratio of uniaxially
a” restrained standard specimen ( = 0.96%)
s 20
E, Young’s modulus of restraining steel
‘S However, in the actual concrete structure it is
CT! O unusual to have a restrainer only in one direc-
0 10 20 30 40 50
tion. For example, reinforcing bars in slab are
Unit Expansive Admixture Content (kg/m 3> arranged in two directions and in beam and
Fig. 9. Result of permeability test. column members it is arranged in three direc-
tions. Generally the expansive concrete has
multiaxial restraint such as biaxial or triaxial
produced from hydration reaction. However, restraint. There are some reports discussing the
the chemical prestress varies greatly in accord- expansive properties, compressive strength, test
ance with such factors concerning mix method of expansive amount and assuming
proportion of concrete as unit expansive method of expansive amount, of expansive con-
admixture content, kind of cement and unit crete which has multiaxial restraint.23,24 As for
binder content, water-binder ratio, and curing the expansive concrete writers proposed that it
method and is also highly influenced by the is a question to consider the expansive proper-
amount of restrained and restraining method. ties of concrete under multiaxial restraint
As for the restrained, reinforcing bar, structural simply and easily as an amplification of uni-
steel, steel pipe, ground and existing concrete axially restrained expansion and also offered
structure are thinkable. Therefore, it is neces- that the expansive properties with annular
sary to assume the chemical prestress for the restraint can be assumed by multiaxially amplify
arrangement of these restrainers and their ‘the notion concerning amount of work’ in uni-
amount. After all, to utilize the expansive axial restraint.25
energy it is the most important point to estab-
lish the estimating method for it. As for the EXAMPLES OF USE AND FUTURE VIEW
chemical prestress under unit-axial restraining OF EXPANSIVE CONCRETE
condition, the method of test is prescribed in
JIS A 6202. And according to the method bas- As for the records of performance of expansive
ing on ‘the notion concerning amount of concrete, the following may be mentioned,
work,22 the assuming method of chemical pres-
tress can be calculated by the following (1) Application to shrinkage-compensating con-
equation. crete26 for cast-in-place concrete.
(2) Application to shrinkage-compensating con-
u = &X’C7’cPX (1) crete of factory products and to chemical
where: prestressing concrete.26
(3) Application to filling concrete for place-
u amount of work done to a restrainer by ment in inner space formed by existing
unit volume of expansive concrete concrete, steel pipe and rock.
F‘X expansion rate
As stated before yearly production of expan-
d CPX chemical prestress
sive concrete in Japan was 70000 metric tons in
Generally the amount of work U can be 1995. And the share of application was 30% for
assumed as constant within the limits of practi- cast-in-place concrete and 70% for precast con-
cal restraint. crete.
Using expansive coefficient E,, obtained from As for the use of cast-in-place concrete, water
a restrained specimen according to A-method utilizing structures such as water tank, under-
or B-method prescribed in JIS A 6202, and ground pit and pool, and structures such as
Expansive admixtures 169

bridge slab and pavement slab, and watertight external pressure. With these efforts, concrete
concrete may be mentioned. In recent years, product having chemical prestress or expansive
with a tendency of concrete structure to grow admixture presents ever-increasing demand.
larger, also the expansive admixture of hydra- In recent years with the object of (1) labor
tion heat reducing type27 which has an addition saving of concreting works, (2) complete filling
of hydration heat reducing admixture is used. of concrete to the structure with complex sec-
Concrete structures with comparatively large tional shape or high density re-bar arrangement,
section (mass concrete) in such facilities as (3) arresting of vibration and noise to the
water treatment installation tend to cause ther- neighborhood, (4) improving of high strength
mal cracks due to the hydration heat of cement concrete execution, high fluidity concrete”573”
instead of shrinkage cracks in smaller struc- has been applied to the actual works on a job
tures. The object of the use of expansive site to increase performance records. Though
admixture of hydration heat reducing type is to sometimes cracks appear in a high fluidity con-
reduce the hydration heat of cement and to crete applied to a large-scale project, it may be
decrease the thermal stress by relaxing the due to the mix proportion of the high fluidity
restraining stress during the drop of tempera- concrete in which the proportion of powders
ture with expansive energy maintaining. Results such as cement, iron-blast-furnace slag, fly ash
of execution test by actual structures on a job and powdered lime stone increase, with the
site show that with the use of expansive result that thermal shrinkage due to the hydra-
admixture of hydration heat reducing type it is tion heat of cement, drying shrinkage and
recognized that width and number of crack is ‘Autogeneous-shrinkage’“7 of cement paste due
diminished and also a part of crack disappear to the hydration reaction become large. With
with the lapse of time showing the recovering the object of compensating the shrinkage of
effect of expansive action,28 though the com- high fluidity concrete, a high fluidity concrete
plete prevention of thermal cracks is not yet with expansive admixture is used in a wall con-
achieved. crete of installation such as water treatment
It was also considered that the use of expan- facilities where the members have a thickness of
sive concrete in place of reinforced concrete over 1 m. Result of comparison between the
slab of highway steel bridge may have effect on high fluidity concrete with expansive admixture
diminishing of crack due to the introduction of and the high fluidity concrete without expansive
chemical prestress and shrinkage decreasing admixture shows that the former presents a
effect.29 They made a trial execution on actual, slower rate of increase in the initial tensile
bridge and recognized that the results of investi- strength with the lapse of age than the latter,
gation and measurement proved the decrease of with the result that the former has low inci-
crack to improve durability.30-34 dence of crack. This also proves the shrinkage
As for the use of precast concrete, Hume compensating effect of expansive admixture in a
pipe, box culvert, precast slab and steel pipe high fluidity concrete.
lining are mentioned. These are the products
which positively use the expansive admixture to
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