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The Effects of Seeding C3S Pastes With Afwillite
The Effects of Seeding C3S Pastes With Afwillite
LafargeHolcim R&D, 95 rue du Montmurier BP15, 38291 Saint Quentin Fallavier, France
Department of Civil and Environmental Engineering, Imperial College, London SW7 2AZ, UK
a r t i c l e
i n f o
Article history:
Received 24 April 2016
Received in revised 28 July 2016
Accepted 22 August 2016
Available online xxxx
Keywords:
Hydration products (B)
Microstructure (B)
Shrinkage (C)
Ca3SiO5 (D)
Seeding
a b s t r a c t
The addition of 14% s/s (dry solids by mass of C3S) of afwillite (C3S2H3) seeds to C3S pastes made with two different commercial polyacrylate-based superplasticizers (SP) allows the pastes to be cast at low water/C3S mass
ratios (w/c) and overcomes the hydration retardation produced by the SPs. SP-free C3S pastes seeded with
afwillite at an initial w/c of 0.50 gave about 30% lower 28-day compressive strengths than the unseeded controls,
due to higher porosities. However, at w/c = 0.35, with the addition of 0.4% s/s SP, the afwillite-seeded pastes gave
similar or higher strengths than the unseeded controls at all ages tested. Hydration rate data obtained by chemical shrinkage measurements suggest that this is because the degrees of hydration of the C3S in the low w/c
afwillite-seeded pastes made with added SP reach higher values than in the unseeded controls, compensating
for the difference in density of the hydrates.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Concrete is the most widely-used manufactured material on Earth.
With the help of hydraulic cements based on Portland cement clinker
(PCC), we can take ordinary stones and sand (aggregates) add water
and mould them into any desired shape, and then let the mix hydrate
to form a hardened concrete mass with high compressive strength, suitable for many types of construction. Most applications of concrete only
really require compressive strength and space-lling. However, concrete is prone to cracking due largely to the brittleness of the cement
paste binding phase. In practice, much of this cracking is due to the signicant shrinkage that occurs within the cement paste as it loses water
by evaporation [13]. This phenomenon, known as drying shrinkage,
is common to many porous materials, including wood. In concrete, the
resultant cracking can sometimes be deleterious to structural durability,
although it is more often simply an aesthetic problem.
Drying shrinkage is often considered to be related to the capillary
tension of the water in the pores of the cement paste [4]. As the porous
paste dries out, a capillary tension (negative pressure) develops in the
liquid phase and increases with decreasing relative humidity (RH). Conversely, the maximum diameter of pores, which remain lled with
water at equilibrium at any given RH, decreases with decreasing RH. It
is the product of the capillary tension and the remaining volume of
water-lled pores that ultimately determines the extent of shrinkage
at any given RH. Based on this hypothesis, it should be possible to reduce shrinkage in at least two different ways: either by adding solutes
that reduce the surface tension of the water, or by reducing the volume
Corresponding author.
E-mail address: matthieu.horgnies@lafargeholcim.com (M. Horgnies).
http://dx.doi.org/10.1016/j.cemconres.2016.08.015
0008-8846/ 2016 Elsevier Ltd. All rights reserved.
of small pores. The former approach has already led to the development
of chemical admixtures (shrinkage-reducing agents, SRAs) which can
reduce drying shrinkage but have quite a high use-cost due to the
need for high dosages of organic compounds. The work presented
here is focused on the latter approach, which involves modifying the hydration products of the cement.
The main binding phase in essentially all construction concretes is a
highly nano-porous amorphous calcium silicate hydrate, of somewhat
variable composition, referred to as CSH gel. The smallest pores
such concretes are always the nano-pores in this gel, which is why it
inherently produces a relatively high drying shrinkage. So one way to
tackle this problem, which is inherent to all PCC-based cements, is to
nd a way to get them to hydrate to form different hydrates with inherently much less ultrane porosity.
Fortunately, this possibility appears to exist in the form of the
crystalline phase afwillite (Ca3(SiO3OH)22H2O; or, in oxide notation,
C3S2H3) [5,6]. There are many different ternary phases in the CaO
SiO2H2O system, and their relative stabilities are still not perfectly
well established, partly due to the difculty of establishing true equilibrium. Under the typical conditions of use of Portland cement in ordinary
concretes, X-ray amorphous CSH is the main ternary phase found, although thermodynamic data [7] imply that crystalline tobermorite of
approximate composition C5S6H8 is almost as stable. However, regardless of their relative stability, crystals of tobermorite do not grow rapidly
enough at temperatures below 100 C to be of practical use [8]. The
stability of afwillite relative to CSH in the pure CSH ternary system
is still not completely clear [9]. Lachowski et al. only found afwillite in a
paste of lime and silica after 60 days reaction at 85 C, not at 55 C [10].
However, Glasser and Hong found afwillite (plus some tobermorite)
after hydrothermal treatment of CSH (with C/S = 1.51.6) at 55 C
146
for 730 days, deducing that afwillite was probably more thermodynamically stable than CSH at 55 C [11]. They also presented experimental
results showing that afwillite is stable at 85, 130 and 150 C for 5 months
and that a mixture of jennite and afwillite is stable from 55 to 150 C for
5 months [9], conrming previous studies by Heller and Taylor [12,13].
It has long been known that afwillite can be produced by ball-mill
hydration of C3S slurries at room temperature [14]. Davis and Young
state that the CSH formed along with afwillite in the ball-mill hydration of C3S eventually converts completely to afwillite if kept agitated
for 23 years, which implies that afwillite is stable relative to CSH
in this lime-rich system at room temperature [15]. Saito and co-workers
used the same type of mechanochemical approach to produce
afwillite from a wet paste of portlandite (Ca(OH)2; CH) and silica gel
(SiO2; S) [16]. When the initial CH/S molar ratio was 1.5, and with a
small excess of water (e.g. 2330% by mass of the paste) they formed essentially only afwillite (after 2 h of milling) but when the amount of
water in the paste was increased to 37%, CSH formed instead of
afwillite. The paste temperature in these experiments is unfortunately
not specied, although it rose as high as 70 C in another similar experiment, so the effect of the additional water may have simply been to
modify (probably to reduce) the temperature, rather than to change
the equilibrium at constant temperatures.
Afwillite formation instead of CSH in non-agitated C3S paste hydration at ambient temperatures was rst obtained by Seligmann and
Greening, by seeding the C3S paste with afwillite crystals, which had
themselves been fabricated by ball-mill hydration of C3S. In the same
paper, they also showed that growth of afwillite instead of CSH reduces the drying shrinkage of the hardened paste [17].
We synthesized afwillite (together with portlandite) by ball-mill hydration of C3S slurries, following the procedure proposed by Kantro et al.
[14]. The reaction is shown as Eq. (1). The more usual hydration reaction
of C3S to give CSH plus CH is shown as Eq. (2). Molar masses, volumes
and volume changes (V) are shown below each equation, making use
of data from the references specically given, plus additional data from
[7].
Alite hydration to give afwillite density assumed : 2:63 g=ml18
2
C3S + 5.3H C1.7SH4 + 1.3CH
228.3 + 95.5 227.5 + 96.3 (g)
73.1 + 95.5 113.8 + 43.0 (ml)
V = 11.8 ml/mol = 0.0517 ml/(g C3S) = 7.0% v/v =
16.1% v/v C3S
Thermogravimetric (TGA) and X-ray diffraction (XRD) analyses
were made to quantify the inuence of certain parameters (water/C3S
(w/c) and steel balls/C3S (SB/C) mass ratios; Blaine specic surface
areas, duration of ball-mill hydration, use of superplasticizers, preseeding with germs) and to study the stability of the resulting afwillite
over time. After synthesis and purication, the afwillite germs were introduced into C3S pastes and TGA was used to quantify the rate of
growth of afwillite and also investigate the inuence of the seeding process on the overall hydration rate measured by pycnometry (chemical
shrinkage [20]). Finally, the properties of the hardened seeded C3S
pastes were studied to establish the inuence of afwillite seeding on:
(i) the nal paste microstructure studied by mercury intrusion
porosimetry (MIP) and scanning electron microscopy (SEM), (ii) paste
compressive strengths, and (iii) paste drying shrinkage.
2. Experimental
2.1. Raw materials
The principal raw material used was pure triclinic tricalcium silicate
prepared in the Lafarge research laboratories. X-ray uorescence analysis showed this C3S to contain 25.6% SiO2, 71.1% CaO and small amounts
of Al2O3 (0.13%) and MgO (0.34%). The C3S was ground in a planetary
agate Ball Mill (PM 400 from Retsch Technology GmbH) to three different Blaine specic surface area (BSS) values (380, 460 and 660 m2/kg),
before analysis. It was stored under vacuum to minimise hydration
and carbonation. Two samples of commercial polyoxyalkyenepolycarboxylate (PCP) superplasticizers (SP) were obtained from
Chryso, France, for use in selected experiments. All of the water used
was demineralized, and, when necessary, also decarbonated by boiling
and cooling just before use.
2.2. Preparation of the specimens
2.2.1. Synthesis of afwillite
Samples of afwillite were made by hydration of C3S slurries continuously agitated using 1 cm diameter stainless steel balls in a 0.18 kW
Turbula T2F mixer (WAB, Muttenz, Switzerland) under the various
sets of conditions listed in Table 1. The speed of the mixer was xed at
23 rpm. In most cases the water/C3S mass ratio (w/c) used was 9, but
some tests were done at w/c = 4. Steel ball/C3S (SB/C) mass ratios
from 0.4 to 23.5 were used. Slurry samples were taken after various periods of ball-mill hydration, dried at 20 C for 48 h using a rotary vane
pump (with an ultimate vacuum of 2 103 mbar) and then ground
by hand to pass a 63 m sieve before being analysed by TGA and XRD.
2.2.2. Use of chemical admixtures
Two
different
high-range
water-reducing
admixtures
(superplasticizers; SP), Chrysouid Optima 203 and Premia 190,
with dry solids contents of 21.8% and 20.0% respectively, were used in
certain tests. SPs were added to the suspension in the Turbula at a
mass ratio of dry SP/C3S of 3.5%, while a mass ratio of 0.4% SP/C3S was
used to uidify the C3S pastes made at w/c = 0.35 to study hardened
paste properties.
2.2.3. Pre-seeding of C3S-based slurries and pastes with afwillite
Many of the C3S pastes and slurries were seeded with afwillite. The
relatively pure afwillite used as seeds in the paste experiments was
manufactured by rst applying 48 h of Turbula ball-milling to slurries
of C3S plus an SP and impure afwillite seeds obtained from earlier experiments. These slurries, comprising principally afwillite and portlandite,
were then puried by leaching with decarbonated demineralized
water to remove the portlandite. Leaching was continued until the pH
of the slurry fell below the pH of 12.7 typical of a saturated portlandite
solution at 20 C. They were then dried and re-ground by hand (as in
2.2.1.) in order to be dry-mixed with C3S before paste mixing.
2.2.4. Preparation of specimens for hardened paste tests
Table 2 details the experimental conditions and the methods of characterization used to study the growth of afwillite in C3S pastes. Most of
the C3S pastes were cast into 5 ml sealed polyethylene tubes, except
those to be used in drying shrinkage experiments, which were cast
into cylindrical Teon-based mould (160 20 mm). All samples were
cured at 20 2 C in small containers with a few drops of water (i.e.
at close to 100% relative humidity) for either 7 or 28 days before testing.
For MIP or SEM analyses 5 ml hardened paste samples were broken into
pieces of about 1 ml which were immersed in 20 ml of isopropanol, (the
solution being renewed after 2 days and then left for a further 7 days,) in
order to stop the hydration; and then nally dried in high vacuum. For
TGA and XRD analysis, the procedure was similar but the dried samples
were ground by hand to pass a 63 m sieve and stored under vacuum
147
Table 1
Conditions tested for synthesis of afwillite by milling C3S slurries.
C3S BSS (m2/kg); particle size
distribution (D10/D50/D90, m)
w/c
SB/C
Pre-seeding with
afwillite (s/s C3S)
Ball-mill hydration
time (hours)
4 or 9
0.34 to 23.5
- None
- Optima 203 (0.035)
- Premia 190 (0.035)
None
0.03
24
48
72
96
264
2.3.4. Pycnometry
5 g C3S paste samples were mixed by hand for 1 min before being
cast into 20 ml glass pycnometers and immersed in decarbonated
demineralized water. Chemical shrinkage at ages from 1 to 91 days
was measured by weighing them under water [20].
Table 2
Summary of the experimental conditions tested and methods of characterization used to study the growth of afwillite in C3S pastes.
C3S neness (BSS, m2/kg)
w/c
Methods of characterization
380
0.50
None
None
0.02
380
0.35
None
0.02
460
460
460
460
0.70
0.50
0.50
0.50
None
Premia 190 (0.004)
Optima 203 (0.004)
None
0.02
0.02
0.02
None
0.01
0.02
0.04
460
0.35
None
0.02
460
0.35
None
0.02
460
0.35
None
0.02
- TGA
- Pycnometry
- MIP
- Compressive strength
- TGA
- Pycnometry
- MIP
- Compressive strength
- TGA
- TGA
- TGA
- TGA/XRD
- Pycnometry
- SEM
- MIP
- Drying shrinkage
- Compressive strength
- TGA
- MIP
- Compressive strength
- TGA
- MIP
- Compressive strength
- TGA
148
Table 3
Inuence of SP (at 3.5% s/s C3S) and/or afwillite (at 3% s/s C3S) additions on the rate of formation of afwillite during Turbula milling of C3S slurries (460 m2/kg BSS) at SB/C = 23.5,
w/c = 9.
Use of SP
(3.5% s/s C3S)
Afwillite seeds
(3% s/s C3S)
None
No
Yes
No
Yes
No
Yes
Optima 203
Premia 190
48 h
72 h
96 h
38
48
18
38
37
53
41
47
33
51
45
54
47
34
56
-
41
38
-
Key: (s/s) dosage on a dry solids/dry solids mass basis; () not measured.
149
Carbonates
C-S-H
Afwillite
Portlandite
Afwillite
Fig. 2. TGA analyses of afwillite prepared by Turbula milling of a slurry of 460 m2/kg BSS C3S at SB/C = 23.5, w/c = 9, for 48 h. (a) Before leaching; (b) after leaching.
from these results whether the SPs simply retard overall C3S hydration
or whether they favour formation of CSH over afwillite.
3.2.2. Rate of hydration
We used pycnometry to follow the rate of hydration of C3S pastes
under water at 20 C for several weeks. Fig. 4a compares the reference
150
2400
2300
2200
2100
2000
1900
1800
1700
d=6.56447
1600
Lin (Counts)
1500
1400
1300
1200
200
d=1.45634
d=1.52682
d=1.51404
d=1.50340
d=1.60397
d=1.59178
d=1.56032
d=1.63498
d=1.77541
d=1.80616
d=1.86271
d=1.72679
d=1.70410
d=1.68645
300
d=2.15338
d=2.13887
d=2.12110
d=2.09775
d=2.07492
d=2.05698
d=2.01987
d=1.99019
d=1.95817
d=1.94700
d=1.92431
d=1.91780
d=2.18538
d=2.34897
d=2.31700
d=2.28206
d=2.44027
d=2.58821
400
d=2.50546
500
d=2.67032
600
d=3.27856
700
d=4.15159
d=5.77938
800
d=4.69929
900
d=3.98168
d=3.88927
d=3.74606
d=5.08078
1000
d=3.13595
d=3.05134
d=3.01458
1100
100
0
6
10
20
30
40
50
60
2-Theta - Scale
purified afwillite - File: afw7 mathieu.raw - Type: 2Th/Th locked - Start: 5.172 - End: 65.140 - Step: 0.017 - Step time: 59.7 s - Temp.: 25 C (Room) - Time Started: 0 s - 2-Theta: 5.172 - Theta: 2.503 - Chi: 0.00
Operations: Displacement -0.250 | Import
01-073-2105 (C) - Afwillite - Ca3Si2O6(OH)2(H2O)2 - Y: 121.50 % - d x by: 1. - WL: 1.54056 - Monoclinic - a 16.27000 - b 5.63200 - c 13.23000 - alpha 90.000 - beta 134.800 - gamma 90.000 - Base-centered - Cc (9)
Fig. 3. XRD pattern of the puried afwillite used for seeding in paste tests.
paste (C3S; BSS = 460 m2/kg; w/c = 0.5) with equivalent pastes seeded
with 4% afwillite; results of two repeats are shown. In both cases the
chemical shrinkage tends ultimately towards a similar asymptotic
value of about 1819% by volume (v/v) of initial C3S, but the seeded
sample reaches the asymptote much more quickly than the control
(for example, it reached 85% of its nal value in only about one day, as
compared to 7 days for the control paste). Similar results are obtained
on changing the C3S BSS to 380 m2/kg and the seed dosage to 2%,
while reducing the initial w/c to 0.35 by adding 0.25% s/s of PCP (Optima 203) as shown in Fig. 4b. The absolute chemical shrinkage values
measured in our experiments diverged signicantly from the values
we calculated for complete hydration following Eq. (1) for CSH formation (16.1% v/v C3S) or Eq. (2) for afwillite formation (17.1% v/v
C3S). However, it is important to note that the calculated values depend
Table 4
Chemical and physical results for C3S paste tests.
460
w/c
SP
(0.4% s/s C3S)
Afwillite seeds
(2% s/s C3S)
0.50
0.50
0.35
0.35
0.70
0.50
0.50
0.50
0.50
0.35
0.35
0.35
0.35
0.35
None
None
Optima 203
Optima 203
None
Optima 203
Premia 190
None
None
Optima 203
Optima 203
Premia 190
Premia 190
None
No
Yes
No
Yes
Yes
Yes
Yes
No
Yes
No
Yes
No
Yes
Yes
Key: (s/s) dosage on a dry solids/dry solids mass basis; (-) not measured.
Amount of afwillite
detected by TGA (%)
Amount of CH
detected by TGA (%)
Amount of
afwillite/theoretical
maximum (%)
Total porosity
measured
by MIP (%)
7 days
28 days
7 days
28 days
7 days
28 days
28 days
0
27
0
14
22
12
13
0
23
0
16
0
17
14
0
25
0
15
0
18
0
18
0
17
-
21
17
21
21
33
23
25
14
25
19
25
20
21
23
23
25
23
24
30
29
20
27
23
25
-
0
45 (3)
0
24 (3)
36 (2)
20 (2)
22 (2)
0
38 (3)
0
27 (3)
0
29 (5)
24 (3)
0
41 (3)
0
25 (2)
0
41 (2)
0
30 (5)
0
29 (5)
-
23.6
25.7
11.1
11.2
27.1
32.5
6.0
8.8
-
151
Fig. 4. Chemical shrinkage of C3S pastes expressed as volume fraction of initial C3S (e.g. ml/ml): (a) C3S BSS 460 m2/kg; initial w/c = 0.46; with or without 4% s/s afwillite; (b) C3S BSS
380 m2/kg; initial w/c = 0.35; Optima 203 @ 0.25% s/s; with or without 2% s/s afwillite.
white and the hydrated phases become darker with increasing porosity.
As expected, at 7 days the seeded pastes contain many fewer anhydrous
grains than the reference pastes.
The Ca/Si ratios measured by point analysis of the hydration products around the anhydrous grains in the reference C3S pastes is highly
variable, which is typical of CSH gels containing microcrystalline
portlandite (CH). Large light grey masses in the interstitial areas are
also portlandite. Large portlandite crystals apparently only grow
where there are large empty pore spaces [25]. In afwillite-seeded C3S
pastes, small crystals of afwillite are scattered on a background of
large continuous masses of portlandite. Afwillite has a similar grey
shade to portlandite, implying that it is also not internally porous, although voids are observed inside some afwillite crystals.
Fig. 6a shows the microstructure of the fracture surfaces of the seeded paste after 7 days of hydration, using secondary electron imaging.
152
Afwillite
C-S-H
C-S-H
CH
CH
Anhydrous C3S
Anhydrous C3S
CH
Afwillite
C-S-H
CH
Fig. 5. BSE SEM images of polished sections of C3S pastes after 7 and 28 days of hydration: (a,c) reference pastes; (b,d) afwillite-seeded pastes.
32.5%, about 20% higher than that of the equivalent unseeded paste. Fig.
7 compares the full MIP curves of this pair of pastes down to an estimated diameter of 3 nm. The seeded paste contains much more porosity in
the 0.05-1 m range than the reference paste, while the reference paste
contains much more porosity with diameters below 10 nm. Thus,
seeding with afwillite substantially coarsens the pore structure of hydrated C3S pastes.
3.3. Properties of hardened C3S paste seeded with afwillite
3.3.1. Drying shrinkage
The same pair of pastes shown in Fig. 7 was compared for drying
shrinkage. Results are shown in Fig. 8a. During the rst two days,
both pastes shrink by about 500 ppm (microstrains). After that
they both shrink roughly in proportion to log(time), but the seeded
153
(a)
Afwillite
C-S-H
Afwillite
C-S-H
(b)
Fig. 6. SEM images of (a) the fracture surfaces of afwillite-seeded C3S paste after 7 days of hydration; (b) the puried afwillite seeds used in making the seeded pastes.
4. Discussion
4.1. Hydration kinetics
The seeding of C3S pastes with micron-sized afwillite seeds strongly
accelerates their hydration. A paste of 460 m2/kg BSS C3S seeded at
with a dry afwillite dosage of 4% reached about 85% hydration in 1 day
at 20 C, as opposed to about 7 days for the equivalent unseeded paste.
Seeding of C3S pastes with similar dosages of freshly-prepared wet C
SH seeds is also known to accelerate strongly [26,27]. Details are
given in Fig. 2. of ref. [26] in terms of cumulative heat of hydration vs.
time. If one uses the literature value of 123.5 kJ/mol for the enthalpy
of hydration of C3S to give CSH plus portlandite, one can easily convert
the ordinate of that gure into a degree of hydration, from which we can
see that the addition of 4% CSH seeds allows this C3S (which was fairly
similar to the one used in the present work) to reach about 66% hydration after 24 h when hydrated at w/c = 0.5 and at 20 C. However, it appears that the rate of hydration decreased considerably after this point.
Note also that the unseeded C3S paste only reached about 36% hydration
after 24 h, which implies that it was slightly less reactive than the C3S
used in the present paper, perhaps due to a lower Blaine specic surface
area (unfortunately, this value was not provided in the reference).
Based on the above arguments, it appears that dry afwillite seeds are
at least as effective, on a mass per pass basis, as wet CSH seeds for accelerating early C3S hydration. Moreover, (and, apparently, unlike CS
154
Fig. 7. MIP pore-size distributions (and total porosity down to 3 nm) on C3S (460 m2/kg BSS; w/c = 0.50) pastes after 28 days of hydration, with or without 2% s/s afwillite seeds.
H seeding,) the use of afwillite seeds also seems to accelerate the later
stages of C3S hydration, such that essentially complete hydration can
be obtained in only about one week at 20 C with the 460 m2/kg BSS
C3S used here (at 0.5 w/c) as opposed to well over a month for the
equivalent unseeded paste. It seems that the more open porosity obtained with afwillite seeding allows the nal stages of C3S hydration,
(which are probably diffusion-controlled, at least in unseeded and C
SH-seeded pastes,) to progress signicantly more rapidly because
less CSH is present.
One more point of practical importance must be stressed here. In our
experience, in order to obtain a strong accelerating effect with pure C
SH seeds, the CSH preparation used must be wet. Drying it rst,
even if followed by regrinding in an attempt to get good re-dispersion,
generally leads to poor results. However, no such constraint seems to
exist with afwillite seeds, which could be a great advantage in practice
for example, if they were to be added into cement in powder form.
155
Fig. 8. Drying of C3S (460 m2/kg BSS; w/c = 0.50) pastes after 28 days of hydration with or without afwillite seeding. Length changes vs. (a) time; (b) mass.
Table 5
Compressive strengths of C3S pastes.
Fineness of C3S used
(BSS, m2/kg)
380
460
w/c
Afwillite seeds
(2% s/s C3S)
0.50
0.50
0.35
0.35
0.50
0.50
0.35
0.35
0.35
0.35
None
None
Optima 203
Optima 203
None
None
Optima 203
Optima 203
Premia 190
Premia 190
No
Yes
No
Yes
No
Yes
No
Yes
No
Yes
Key: (s/s) dosage on a dry solids/dry solids mass basis; (-) not measured.
7 days
28 days
6 (1)
6 (1)
5 (1)
6 (1)
42 (10)
57 (11)
15 (4)
17 (3)
54 (1)
45 (3)
15 (2)
14 (2)
90 (22)
91 (16)
77 (14)
85 (31)
27 (3)
19 (1)
91 (4)
79 (5)
23 (4)
17 (1)
99 (14)
111 (41)
110 (14)
135 (33)
156
since portlandite forms in both systems, these results also imply that the
SP-retarding effect is probably not primarily due to inhibition of
portlandite growth.
In a related observation, the data in Table 3 show that the addition of
one of these SPs, Premia 190, to the agitated C3S slurries used to make
afwillite seeds actually led to enhanced afwillite formation, (which is
why it was used to make the seeds). This suggests that this polymer retards the growth of CSH more than the growth of afwillite, and it is
also consistent with the observation (see Table 4) that this SP gave
higher one-day paste strengths than did the other SP (Optima 203).
4.3. Mechanical strengths
Despite the high level of variation in the results of paste strength
tests in this work, probably mainly due to the small samples used, a signicant loss in ultimate strength was observed to occur in afwilliteseeded C3S pastes made at w/c = 0.5, (compared to the equivalent unseeded pastes), consistent with the signicantly higher porosity of such
pastes. However, when pastes were mixed at w/c = 0.35 (using SPs to
overcome the reduced uidity), there was little signicant difference
in strengths at 7 days, and apparently even an increase in 28-day
strengths for the afwillite-seeded pastes. This is probably because the
higher degree of C3S hydration obtained with afwillite offsets the reduced volume of hydrates formed.
something else, presumably CSH; but these results could also have
been affected by carbonation. The co-existence of CSH and afwillite
in the presence of excess portlandite and water might, however, be
due to the presence of limited quantities of impurities, which dissolve
in one phase and not the other. Note also that, while we often observed
mixtures of the two phases, or of CSH alone, during the hydration of
C3S pastes, we never observed afwillite forming without any CSH.
This does tend to suggest that CSH is slightly more stable, at least at
room temperature.
The stability of afwillite in the more complex phase assemblage of
hydrated Portland cements is even less clear. Previous study from
Seligmann and Greening [29] and preliminary work from our team suggest that the presence of calcium aluminate phases tends to destabilize
afwillite relative to CSH, presumably due to the well-known ability of
CSH to take up signicant quantities of aluminium in solid solution
[30]; and this may well be the reason why afwillite is never seen in ordinary Portland cement pastes. On this basis, the use of afwillite additions either to accelerate hydration or to reduce the drying shrinkage
of ordinary Portland cement based concretes currently appears unrealistic. But, on the positive side, it appears that the risk of catastrophic
strength loss of hardened concrete structures due to conversion of C
SH to afwillite can, fortunately, be restricted to the realm of science
ction!
5. Conclusions
It is not easy to calculate the extent of the reduction in drying shrinkage that one would expect from the differences in pore structure caused
by the growth of relatively large afwillite crystals instead of nano-porous CSH using the capillary tension hypothesis proposed in the introduction. However, the disjoining pressure approach used by
Gartner to explain the expansive behaviour of certain gypsum pastes
seems somewhat easier to apply [28]. If we assume that the origin of
drying shrinkage at 50% RH is simply due the collapse of inter-particle
water lms, then the observed paste shrinkage of about 10 3 for
afwillite-rich pastes implies loss of a wet lm thickness of about
1 nm for the closest contact point between two 1 m-diameter particles.
This is not totally unreasonable it is of the order of thickness observed
for adsorbed water layers on at mineral surfaces over this RH range.
However, this does not represent a true model for the origin of drying
shrinkage in these pastes, as it ignores the true microstructure and the
ratio of bonded to unbonded interfaces, (assuming that shrinkage
occurs mainly at unbonded interfaces, which will reduce the shrinkage signicantly if one assumes a high degree of bonding) [28]. Moreover, it is clear that the hydration products in the seeded C3S pastes
used in the drying shrinkage experiments are not at all free of CSH;
quite a lot of CSH is visible in the micrographs, and this, no doubt,
contributes quite a lot to the observed drying shrinkage of the seeded
pastes. Thus, it seems likely that signicantly less drying shrinkage
could be obtained if the formation of CSH could be completely
avoided.
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