EARLY VOLUME CHANGES OF HIGH PERFORMANCE SELFCOMPACTING CEMENTITIOUS SYSTEMS CONTAINING

POZZOLANIC POWDERS
Syed Ali Rizwan1 and Thomas A Bier1
(1) Institute for Ceramics, Glass and Building Materials Technology, Agricolastr. 17, T U
Freiberg, 09599, Germany.

Abstract
This study is an ongoing investigation by the authors on high performance (HP) self
compacting cementitious systems (SCCS) and addresses early volume changes of cementitious
systems using inert and pozzolanic powders. The systems investigated contained lime stone
powder (LSP-relatively inert) and pozzolanic materials like fly-ash (FA), rice-husk ashes
(RHAs both amorphous and crystalline) and as produced powder type silica fume (SF). Two
sand types were used. One had 0-2 mm size fraction (S1) while the other had 80% 0-2 mm and
20% 2-4 mm size fractions (S2). Such systems were generally studied for linear early shrinkage
in two exposure conditions in the laboratory wherein constant temperature and humidity
conditions were maintained.
The results on HP SCMs (self-compacting mortars) indicate that incorporating powdered
superplasticizer (SP) reduced the shrinkage. Covering a formulation also did the same. At higher
water-cement ratios shrinkage got reduced due to dilution effect. Regarding HP SCM systems
using LSP, the early uncovered shrinkage remains almost the same for all the cements used in
both exposure conditions. FA systems showed expansion in covered condition with all cements.
The shrinkage of such systems got reduced when 20% RHA was incorporated into FA. However,
20% addition of RHAP (crystalline) gave a higher expansion in covered conditions with all
cements compared with 100% FA system The effect of sand type demonstrated that coarser sand
S2 showed slightly lesser shrinkage with a higher maximum pore size. The study showed that
suitable ternary binders when used in an appropriate way could reduce early shrinkage of HP
SCCS.
Keywords: High performance. Self-compacting, early shrinkage, secondary raw materials,MIP.
1.

INTRODUCTION
Structural and construction engineers are only interested in the total magnitude of early
shrinkage and certainly not in the contributions of various parallel operating mechanisms
towards the total shrinkage of a cementitious system. This is perhaps the reason why most codes
prescribe the total permissible shrinkage values only. HP SCCS are being increasingly used in

the construction industry. These systems use very high amounts of fillers usually selected from
lime stone powder (LSP), fly-ash (FA), silica fume(SF) and rice-husk ash (RHA) or their
combinations to replace part of the cement and to improve such properties like reduction in water
demand/early shrinkage, high flow, easy placements, high strength and durability. Usually such
systems use low w/c ratio and high flow levels obtained by using superplasticizer (SP).
Volume change of the cementitious systems in early ages has been undertaken by several
investigators using linear or volume measurements with each technique having its own plus and
minus points [1-4] and no standard method for the determination of drying shrinkage
measurement of concrete exists [5]. Moreover no or very little work has been done regarding the
total early shrinkage determination of SCCS especially those containing pozzolanic powders. In
general shrinkage has been attributed to the paste component or to cement content necessitating
the systematic early volume change measurements starting with cement pastes and then moving
on to mortars or concretes. Combination of pozzolanic additions with fly-ash (FA) in concrete
are generally not recommended in Germany although their use in Scandinavian countries has
been successful [6].These aspects were therefore the basis of this investigation. The data on flow,
strength, microstructure, and on the other details of the systems reported herein can be seen
elsewhere [7-9].
2.

EXPERIMENTAL

2.1
Materials
For HP self-compacting paste (SCP) systems, secondary raw materials (SRMs) included SF,
RHA and RHAP. XRD analysis showed that RHA was amorphous (imported from USA) while
RHAP was crystalline (imported from Pakistan). SF was local German as produced powder type.
In paste systems all these pozzolanic powders were 10% of cement mass. Table 1 gives the
properties of powders used. LSP had 92.3% CaCO3 content by mass.
Table 1: Physical and chemical composition of cements and mineral admixtures.

Oxides

SiO2
Na2O
MgO
Al2O3
K2O
CaO
Fe2O3
SO3
LOI
Particle size,
microns
BET Surface
Area, m2/g
Density ,g/cc

CEM I
42.5R

CEM
II/A-LL
32.5R-

CEM III/B
32.5NNW/HS/NA

LSP
Lafarge

SF

RHA

RHAP

FA

18.92
1.48
1.72
5.09
1.35
63.18
2.27
3.48
2.34
18.91

18.74
1.25
1.38
4.78
1.01
58.97
2.23
3.2
7.09
16.9

31.01
0.86
7.50
8.86
0.70
44.90
0.89
3.76
0.19
11.82

7.07
0.47
1.13
2.53
0.68
48.57
0.88
0.28
38.32
7.176

95
0.10
0.4
0.2
1.2
0.25
0.05
12.2

90.0+
0.14
0.37
<0.01
2.3
0.60
0.32
0.14
4-6
6.8

87.96
0.78
0.90
3.73
1.26
1.49
1.67
0.21
0.28
6.17

51.44
1.23
2.51
26.13
2.63
4.03
5.55
2.71
26.59

0.812

1.353

1.648

4.987

20.5

28.92

2.53

1.65

3.1688

3.1085

2.97

2.748

2.35

2.26

2.45

2.317

The cements used in paste systems were CEM I 42.5R and CEM III/B 32.5 N-NW/HS/NA
from Schwenk Germany. The powder superplasticizer (SP) was Melflux 1641F and 2651 F from
Degussa Germany. For HP SCM systems relatively inert LSP and pozzolanic SRMs like class F
FA conforming to EN 197-1 and ASTM C 618-85 and its 20% mass blends with amorphous and
crystalline RHA and with as produced SF have been used. Mix proportions were 1:1:2 (cement
powder: sand) by mass with w/c=0.40 and w/p=0.2 The cements used in SCMs included CEM I
42.5R, CEM II /A-LL 32.5R and CEM III/B 32.5 N-NW/HS/NA made by Lafarge Germany.
The superplasticizer was Melfux 2500L 30%. Naturally occurring locally available sands of 0-2
mm size (S1, FM=2.8) and 80% 0-2 mm and 20%2-4 mm (S2, FM=3.2) were used in this
powder type HP SCM systems. The target flow level was 31 2 cm.
2.2
Particle shape
It plays a very important role in the response of HP SCP/SCM systems. LSP required the
highest amount of SP to meet target flow and to verify this particle shape through SEM were
obtained and powder porosimetry using MIP was also performed. Fig 1 shows the SEM details
of the powder particles.

Fig 1(a) LSP

Fig 1(b) Fly ash

Fig 1(c) RHA

Fig 1.0 shows SEM pictures of
the powders used. LSP is
irregular and with minute
internal pores while RHA has
visible internal porosity.

Fig 1(d) RHAP

Fig 1(e) SF

The shape of LSP is irregular with rough morphology whereas SF and FA had spherical
particle shapes. RHA (amorphous) had internal porosity while RHAP had little internal porosity
and was crystalline. It is mentioned that irregular particles and those with high internal porosity
require higher SP content for meeting the target flow in SCCS.
2.3 Powder porosimetery
In addition to cement grains, powder particles also adsorb SP and internal pores of bottle neck
type usually result in higher SP demand [10].MIP was done on pure powders to know their pore
porosities. The results are shown in fig 2.

Fig 2(a) Partial MIP diagram of powders.

Fig 2(b) Cumulative MIP diagram of powders.

LSP required highest amount of SP while FA required the lowest amount of SP with all
cements for given flow target as shown in Table 2. The maximum pore sizes of the powders
obtained from fig 2(a) were 54.46, 666, 518, 761 and 1641 nm for SF, RHAP, RHA, LSP and
FA respectively.
Table 2: SP-cement ratio for the three cements with powders for the target flow.
Formulation
C:LSP:S1
C:FA:S1
C:FA+RHA:S1
C:FA+RHAP:S1
C:FA+SF:S1

SP/cement ratio (%) for the target flow with cements

CEM I
CEM II
CEM III
8.27
6.66
7.5
2.90
2.78
2.54
5.43
4.05
4.05
3.02
3.028
2.8
3.68
3.28
3.05

3.0
MIXING
For pastes the dry mixed ingredients were put in mixer bowl containing mixing water. They
were mixed at slow speed (145 rpm) for 30 seconds after which the mixer interior was cleaned. It
was given another 150 seconds high speed mixing (285 rpm). Special mixing technique was
developed for SCMs and consisted of mixing the ingredients dry in 10L Erisch tilted mixer for
30 seconds at slow speed(900 rpm) followed by addition of 80% of mixing water and 30 seconds
slow mixing followed by fast mixing(1800) of one minute. Thereafter mixer interior was cleaned
and remaining 20% mixing water containing liquid type SP was added. The total mixing time
was 5 minutes.
4.0

WATER DEMAND AND SETTING TIMES

Water demands (WD) and setting times were determined as per EN 196-1 December 1994. SF
and RHA had almost similar WD while WD of RHAP was lower than RHA due to lesser surface
area. Addition of 10% crystalline RHAP in cements reduced setting times while amorphous RHA
increased setting times.

5.0

APPARATUS FOR THE LINEAR SHRINKAGE MEASUREMENT

A modified version of German classical Schwindrinne meaning shrinkage channel

apparatus measuring 4x 6x 25 cm interfaced with computer was used at 201C and RH of
315% with specimens in uncovered and then in fully covered conditions obtained by using
plastic sheet and adhesive tape.The duration of measurement time was initial 24 hours
6.0
EFFECT OF PLASTICIZER AND COVER ON THE EARLY SHRINKAGE
MEASUREMENTS OF PASTES
The effect of plasticizer addition and of covering, the neat cement pastes, on the shrinkage
response is shown in figs 3 and 4. For these pastes, powder type PCE SP by Deggusa Germany
was used. to obtain the target flow of 200 %( 30 cm spread as measured on Haggermanns minislump cone). The cement content for HP SCP systems at 20 and 40% water content was 1484
and 1070 Kg/m3 respectively for CEM I while for RHA and SF pastes at these water contents it
was 1366,1009, 1372 and 1011 Kg/m3 respectively. In uncovered conditions plastic and drying
shrinkage mechanisms seem to be operative while in covered conditions plastic and chemical
shrinkage seem to be operative If mixing water is less than the water demand of the cementitious
system, self-desiccation can be expected [11] in pastes with powders and 20% mixing water.

Fig. 3. Effect of plasticizer and plastic cover

Fig. 4. Effect of plasticizer and plastic cover.

In fig 3 shrinkage response of CEM I paste containing 40% water w.r.t cement mass is shown.
The following aspects can be noted by comparing the relevant curves.
1.
Effect of plasticizer on uncovered sample shrinkage.
2.
Effect of plasticizer on covered sample shrinkage.
3.
Effect of cover on unplasticized paste shrinkage.
4.
Effect of cover on plasticized paste shrinkage.
It can be seen that addition of plasticizer to unplasticized paste reduces early shrinkage in
uncovered condition possibly due to decrease in surface tension by SP which allows easy escape
of 1-3% of entrapped air [12] and in covered condition HP SCP system without SP shows greater
expansion than that with SP Covering the plasticized paste produces a slight expansion at the end
of 24 hours measurement. A little shrinkage recovery is clearly seen in all curves after bout 8
hours possibly due to three parallel operating mechanisms consisting of 100% relative humidity
[13], decreased rate of heat escape and to creation of expansive species especially large Ca(OH)2

crystals. The reduction in shrinkage due to SP has also been pointed out by other researchers
[13].Reduced surface tension due to SP seems to reduce the shrinkage and increase the
expansion in uncovered and covered conditions respectively. Same comments are offered for
CEM III formulations shown in fig. 4 with the difference that it shows more shrinkage in
uncovered condition and more expansion in covered conditions possibly due to its finer particle
size[14].Literature suggests surface area of cement[15], total alkalis, C3A and SO3 contents of
cement as major sources of shrinkage[5].
7.0

HP SELF-COMPACTING PASTES (SCP) WITH POZZOLANIC POWDERS

Firstly HP SCP systems with pozzolanic admixtures were investigated for early linear
shrinkage and their responses are shown in figs 5 and 6. At 20% mixing water and to get 30 cm
spread, high SP contents were needed especially for SF and RHA systems.

Fig. 5 Effect of powder type and cover

Fig. 6 Effect of powder type and cover

Figs 5 and 6 show the response of similar HP SCP systems at 20% and 40% (w.r.t cement
mass) mixing water contents. At 20 % mixing water content (fig.5), SF and especially RHA
systems show a rather delayed setting in uncovered conditions due to very high SP content,
availability of insufficient water which had been continuously lost due to evaporation and
consumption during hydration. In covered condition they show a comparatively faster setting
with obviously lesser shrinkage. Crystalline RHAP seems to be better than amorphous RHA, in
terms of giving lesser shrinkage despite faster setting. At 40% mixing water (fig. 6), the trends
were almost similar except that the shrinkage values were reduced because of the lesser cement
and SP contents with rather earlier setting due lower SP content and adequate water availability
even in uncovered condition. RHA systems show delayed setting possibly due to high unburnt
carbon content. It is estimated that eliminating the evaporation reduces shrinkage by about 100%
and even more. at 20% and 40% mixing water (w.r.t cement mass) respectively.
8.0

HP SCM SYSTEMS WITH POZZOLANIC POWDERS

Thereafter HP SCM systems were studied. The flow level was maintained at 31 2 cm The
formulations with LSP, FA, and its 20% by mass blends with RHA, RHAP and SF with CEM I
and sand S1 had cement content of 541, 522,521,523 and 522 kg/m3 respectively.Incorporating
FA in cementitious systems delays setting times due to higher carbon content [16] and it acts like

a calcium sink and removes the calcium ions from pore solution. This depresses calcium ions
concentration during the first hours and delays the CH and CSH nucleation and the
crystallization causing retardation in hydration [17]. In general SP requirements for SCM
formulations decreased from CEM I to CEM III as their clinker content, particle size and
densities also decreased in this order. The shrinkage response of mentioned powders with three
cements in HP SCM systems is shown in figs 7-10. In fig 7 LSP in HP SCM systems shows
highest and almost similar shrinkage with all cements in two evaporation conditions.

Fig 7: Early shrinkage response of LSP with

three cements and two exposures

Fig 8: Early shrinkage response of FA with

three cements and two exposures

Fig 9: Response of FA+RHA with three

cements and two exposures.

Fig 10: Response of FA+RHAP with three

cements and two exposures.

The higher shrinkage is attributed to the faster setting, high SP contents entrapping and
releasing more air during self-compaction process and higher pore sizes. Fig 8 shows that FA
powder in SCM system gave the lowest shrinkage with all cements in uncovered conditions
possibly due to delayed setting resulting from high unburnt carbon content.In covered conditions
all gave expansion due to.higher effective water content in the presence of FA encouraging the
creation of expansive species including calcium hydroxide. In fig 9, the addition of 20% RHA in
FA increases the shrinkage in uncovered conditions (compared with FA system) while the
expansion in covered condition is reduced. This may be due to reduction in CH crystal content
and their size as the SiO2 in RHA reacts with it.Water entrapment in RHA particles can also be a
reason. Fig 10 is another interesting response having 20% RHAP in FA. This system gave almost
similar shrinkage and expansions in covered and uncovered conditions respectively with all
cements. Crystalline RHAP further increases the effective water (due to its relatively lower WD

and lower pozzolanic activity) and hence seemed to favor the growth of hydration products more
than other powders in covered conditions. In fig 11 the response. of 20% SF blend of FA in HP
SCM system. is shown This combination gave total shrinkage more than FA+RHA combination
with the latter appearing to be the most efficient powder combination .CEM I and CEM II gave
almost identical shrinkages in covered condition while CEM III with FA+SF registered almost
nil shrinkage/expansion in the covered condition possibly due to lower clinker content.

Fig 11: Early shrinkage response of FA+SF

with three cements and two exposures
9.0

Fig. 12 Effect of sand type on age-pore

size relation.

MIP STUDIES

MIP was done with the help of Autoscan 33 Porosimeter. The contact angle was taken as 140.
Specimens were oven dried at 110C for 24 hours. Fig 12 shows MIP results of HP SCM
systems.A side investigation showed that with coarser sand S2 the trends of shrinkage/expansion
response were the same as those with sand S1 except that shrinkage was slightly reduced in
uncovered condition and expansion, was slightly increased. in covered condition The strength
was also slightly increased.Higher pore sizes with S2 resulted possibly due to higher effective
water content. At the age of 3 and 7 days, SF and RHA brought almost similar microstructural
improvements. A slight reduction in shrinkage values with S2 could be due to higher strength
and hence higher modulus of the resulting system.
10.0

CONCLUSIONS

Based on this study the following conclusions can be drawn.

1.
Addition of certain types of third generation PCE based SP reduces the shrinkage of
cement paste systems and delays the setting times.
2.
Covering unplasticized HP SCP reduces more shrinkage than covering a plasticized one
and sometimes a small expansion is registered during early 24 hours linear measurement.
3.
Crystalline RHAP in the paste systems seems to be more effective than amorphous RHA
for shrinkage reduction in uncovered condition.
4.
If evaporation after placement could be prevented, FA+RHA in 80:20 ratio seems to be
useful combination.
5.
In HP SCM systems, crystalline RHAP as a partial FA substitution results in expansion in
covered condition.

6.
Despite massive literature reported use in self-compacting systems, LSP gives the
maximum early linear shrinkage, the lowest strength and the highest maximum pore size in
comparison to other powders used in both the exposure conditions.
7.
In general early linear shrinkage response trends of SF and RHA in HP SCP/SCM
systems are comparable.
8.
Increasing the coarse particles fraction in sand results in slight reduction of the shrinkage
of HP SCM systems.
ACKNOWLEDGEMENTS
The authors are thankful to Mr. Karl Kiser, Plant Manager, Agrilectric International
Technologies, Lake Charles, LA USA for providing the amorphous RHA used in this
investigation. Thanks are due to Dr. Muhammad Sharif Nizami, Ceramics and Glass division,
PCSIR laboratories Lahore, Pakistan for providing crystalline RHA used. We are grateful to Mr.
Javed Bashir Malik, Associate/Structural group leader, Carter &Burgess, Houston Texas, USA
for bearing the expenses of the ash transportation.
REFERENCES
[1].

[2].
[3].
[4].

[5].
[6].

[7].

[8].

[9].

[10].

Jensen, O. M; and Hansen, P. F., Influence of temperature on autogenous deformation and

relative humidity change in hardening cement paste, Cement and Concrete Research 29
(1999) 567-575.
Jensen, O. M; and Hansen, P.F. Autogenous deformation and RH-change in perspective,
Cement and Concrete Research 31 (2001) 1859-1865.
Geiker, M; and Knudsen, T., Chemical shrinkage of Portland cement pastes. Cement and
Concrete Research 12 (1982) 603-610.
Neubauer, C. M; Bergstorm, T. B; Sujata, K; XI, Y; Garboczi, E. J :and Jennings, H. M., Drying
shrinkage of cement paste as Measured in an environmental scanning electron microscope and
comparison with microstructural models, Journal of Material Science, 32 (1997) 6415-6427.
Lawrence, C. D. Physico-chemical and mechanical properties of Portland cement in Chemistry
of Cements and Concrete by Lea., 4th Ed. (Editor: P. C. Hewlett), pp 390,391.
Wiens, U., Briet, W and Schiessl, P., Influence of high silica fume and high fly ash contents on
alkalinity of pore solution and protection of steel against corrosion, Proceedings of . Fifth
international conference on Fly ash, Silica fume, Slag and natural pozzolans in concrete, ACI SP
153-39 Vol. 2(Ed. V. M. Malhotra) Milwaukee, Wisconsin, USA 1995. pp 741-761.
Rizwan, S. A and Bier, T.A., Inclusion of mineral admixtures in cement pastes for high
performance concrete, 2nd International Conference on 'Concrete and Development', CD 7-004,
April 30-May 2, 2005, Tehran, pp 1-12
Rizwan, S. A and Bier, T. A., Role of mineral admixtures in high performance cementitious
systems , International Conference on Concrete and Reinforced Concrete, 2nd All Russian
International Conference on Concrete and Reinforced Concrete-Development Trends, Vol.
3,Concrete Technology, 5-9 September 2005, Mosco, Russia. pp 727-732.
Rizwan, S. A: and Bier, T.A., High performance self-compacting Mortars containing pozzolanic
powders, Paper accepted for BMC-8, The Eighth International Symposium on Brittle Matrix
Composites, 23-25 October 2006, Warsa, Poland,.
Magarotto,R., Moratti,F.,and Zeminian,N.,Characterisation of limestone and fly ash for a
rational use in concrete, Proceedings of international conference,Dundee,Scotland,UK , 5-7 July
2005, Ed(R.K.Dhir, T.A.Harrison and M.D.Newlands), cement combinations for durable
concrete, pp71-80.

[11].
[12].
[13].
[14].
[15].

[16].
[17].

Jiang, Z; Sun, Z: and Wang, P., Autogenous relative humidity change and autogenous shrinkage
of high performance cement paste, Cement and Concrete Research 35 (2005) 1539-1545.
Ramachandran, V S: and Malhotra, V. M., Superplasticizers, in Concrete Admixtures
Handbook, (ED. V. S. Ramachandran), Noyes Publications, 1984, pp 233.
Brandt, A.M., Cement Based composites, Materials, Mechanical Properties and Performance,
E& FN Spon publishers, 1995, pp 302.
Tazawa, E; and Miyazawa, S., Influence of cement and admixture on autogenous shrinkage of
cement paste, Cement and Concrete Research 25 (1995) 281-287.
Cohen, M. D: Olek, J: and Dolch, W. L., Mechnaism of Plastic Shrinkage Cracking in Portland
cement and Portland cement-silica fume Mortar, Cement and Concrete Research 20 (1990) 103119.
Massazza, F., Pozzolana and pozzolanic cements in Chemistry of cements and concrete by
Lea., 4th Ed. (Editor: P. C. Hewlett), pp 553.
Baert, G. Buysse, R. and Belie, N.De., Influence of large volumes of fly ash on the hydration of
cement pastes International Conference on Concrete and Reinforced Concrete, 2nd All Russian
International Conference on Concrete and reinforced Concrete-Development trends, Vol. 3,
Concrete Technology, 5-9 September 2005, Mosco, Russia. pp 469-476.