Aci sp-239-2006

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American Concrete Institute•

Editor: Adooncing concrete knowledge
V. M. MALHOTRA
SP-239 RtDACTEUR SP-239
Copyright American Concrete Institute
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2006
Malhotra
CANMET
Superplasticizers and Other
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Chemical Admixtures
in Concrete
Proceedings
Eighth International Conference
Sorrento, Italy, 2006
V. M. Malhotra
SP-239
<HD American Concrete Institute•

Aduancing concrete knowledfle

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8th CAN MET/ ACI
International Conference on
Superplasticizers and Other
Chemical Admixtures in
Concrete
Editor
V.M. Malhotra
American Concrete Institute®
Advancing concrete knowledge
SP-239
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First printing, October 2006
DISCUSSION of individual papers in this symposium may be submitted in accordance

with g~n~ral requirements of the ACi Publication Policy to ACI headquarters at the
address given below. Closing date for submission of discussion is March 2007. All
discussion approved by the Technical Activities Committee along with closing remarks
by the authors will be published in the July-August 2007 issue of either Act Structural
Journal or ACt Materials Journal depending on the subject emphasis of the individual
paper.
The Institute is not responsible for the statements or opinions expressed in its
publications. Institute publications are not able to, nor intended to, supplant individual
training, responsibility, or judgment of the user, or the supplier, of the information
presented.
The papers in this volume have been reviewed under Institute publication procedures
bv individuals expert in the subject areas of the papers.
Copyright© 2006
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AMERICAN CONCRETE INSTITUTE

P.O. Box 9094
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ISBN: o-87031-216-2

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PREFACE
In May 1978, the Canada Centre for Mineral and Energy Technology
(CANMET), in association with the American Concrete Institute (ACI),
sponsored a 3-day conference in Ottawa, Ontario, Canada on the use of
superplasticizers in concrete. Selected papers from the symposium were
published as ACI SP-62.
In 1981, CANMET, again in association with the American Concrete

Institute, sponsored a second 3-day international conference in Ottawa on
the use of superplasticizers in concrete. The proceedings of the conference
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were published as ACI SP-68.
The purpose of the third international conference in 1989 was to

review the progress made since the meetings in 1978 and 1981, and to bring
together representatives of the chemical admixtures, cement, and concrete
industries to exchange information and to delineate new areas of needed
research. The scope of this conference was expanded to include chemical
admixtures other than superplasticizers. The proceedings of the conference
were published as ACI SP-119.
In October 1994, CANMET, in association with the American

Concrete Institute and several other organizations, sponsored the fourth
conference in Montreal, Quebec, Canada. The objective of this conference
was to bring attention to the new developments in chemical admixtures
since the last conference in 1989. The proceedings of the conference were
published as ACI SP-148.
In October 1997, the Committee forthe Organization ofCANMET/ACI

International Conferences (ACI Council), in association with the American
Concrete Institute and several cement and concrete organizations in Italy,
sponsored the fifth conference in Rome, Italy. This conference was aimed at
transferring technology in the fast-moving field of chemical admixtures. The
proceedings of the conference were published as ACI SP-173.
In October 2000, the Committee for the Organization of CANMETI

ACT International Conferences (ACI Council), in association with several

iii
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organizations in Canada and France, sponsored the sixth conference in Nice,
France. More than 50 papers from more than 20 countries were received and
reviewed by the ACI review panel, and 37 were accepted for publication in
the proceedings of the conference. The proceedings were published as ACI
SP-195.
In October 2003, the Committee for the Organization ofCANMET/

ACI International Conference (ACI Council), in association with several
organizations in Canada and Germany, sponsored the seventh conference
in Berlin, Germany. The conference attracted more than 275 delegates, and
the proceedings of the conference, consisting of 39 papers, were published
as ACI SP-217.
In October 2006, the Committee for the Organization ofCANMET/

ACI International Conference (ACI Council) sponsored the eighth
conference in Sorrento, Italy. More than 60 papers from more than 25
countries were received and peer reviewed by the CANMET/ACI review
panel in Budapest, and 36 were accepted for publication in the proceedings
of the conference. The proceedings were published as ACI SP-239. The
cooperation of the authors in accepting the reviewers' suggestions is greatly
appreciated.
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During the conference, a special dinner was held in honor ofMichele
Valente to recognize his outstanding and sustained contributions in the area
of chemical admixtures, and his continued support of the CANMET/ACI
symposia and conferences.
Thanks are extended to the members of the review panel for

their contributions toward the publication of this volume. The help and
assistance of A. Bilodeau, Chair of the PowerPoint presentations review
panel, is gratefully acknowledged. Thanks are also extended to Pavao
Gupta for coordinating the technical program and for the supervision of
the PowerPoint presentations. The assistance of Gordon Brearley and
Maria Venturino, both of CANMET, and Pierrette Veillette of the Handy
Chemicals Ltd., Candiac, Canada, in the processing of the manuscripts and
other associated duties is acknowledged. Acknowledgement is also made

iv Licensee=UNI OF NEW SOUTH WALES/9996758001
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to Rebecca Hartford and Lindsay Kennedy, both of ACI, for their assistance
in getting the proceedings ready in time for the conference.
The Italian Advisory Committee chaired by Mario Collepardi

deserves special thanks for the outstanding contributions to the success of
this conference.
V.M. Malhotra, P.Eng.

Editor
Chair, Eighth CANMET/ACI International Conference
on Superplasticizers and Other Chemical Admixtures in Concrete
October 2006
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j
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TABLE OF CONTENTS
Preface .................................................................................................................... iii
SP-239-1: Recent Developments in Superplasticizers ............................................... 1

by M. Collepardi and M. Valente
SP-239-2: Use of Chemical Admixtures to Modify the Rheological Behavior of

Cementitious Systems Containing Manufactured Aggregates .................................... 15
by A. Jeknavorian, K. Hazrati, A. Bentur, H. Koyata, D. McGuire, and P. Sandberg
SP-239-3: Development of New Superplasticizer Providing Ultimate Workability .... 31

by D. Hamada, T. Hamai, M. Shimada, M. Shonaka, and H. Takahashi
SP-239-4: Characteristics of Concrete Containing a Shrinkage-Reducing

Superplasticizer for Ultra-High-Strength Concrete ..................................................... 51
by T. Sugamata, T. Kinoshita, M. Yaguchi, and K. Harada
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SP-239-5: Artificial Superplasticized Aggregates for Decorative Applications .......... 67
by G. Ferrari, T. Cerulli, A. Lolli, G. Novella, and R. Pellay
SP-239-6: Behavior of Mortars with Different Dosages of Shrinkage Reducing

Admixtures ............................................................................................................. 77
by A. Bettencourt Ribeiro, A. Carrajola, and A. Gon~alves
SP-239-7: Studying Admixtures with the 5C Rheometer .......................................... 93

by R.J. Flatt and I. Schober
SP-239-8: Properties of New Polysaccharide as a Thickner for Concrete ................ 105

byT.Izumi, 5. Dikty, and H. Yamamuro
SP-239-9: Influence of High Volumes of Ultra-Fine Additions on Self-Compacting

Concrete ................................................................................................................ 117
by R. Cioffi, F. Colangelo, D. Caputo, and B. Liguori
SP-239-10: Novel Slurry Rheology Modifier for Materials of Civil Engineering and
Construction ..........................................................................................................137
by H. Yamamuro, K. Koyanagi, and T. Kojima
SP-239-11: Influence ofThree Types of Superplasticizers on Tricalciumaluminate

Hydration in Presence of Gypsum ........................................................................... 151
by S. Pourchet, C. Comparet, A. Nonat, and P. Maitrasse
SP-239-12: Optimizing Polycaboxylate Polymers .................................................. 169

by I. Schober and R.J. Flatt

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SP-239-13: Effect of High-Range Water-Reducing Admixture Type on Performance
of Self-Consolidating Concrete ...............................................................................185
by K.H. Khayat and S.-D. Hwang
SP-239-14: Intercalation of Polycarboxylate Superplasticizers into C3A Hydrate

Phases ............................................... "···········---·-················································ 201
by J. Plank, Z. Dai, N. Zouaoui, and D. Vlad
SP-239-15: Influence of Sulfates Content in Cement on the Performances of

Superplasticizers ................................................................................................... 215
by R. Magarotto, F. Moratti, and N. Zeminian
SP-239-16: Tailor-Made Superplasticizers for Modern Concrete ............................. 231

by M. Corradi, R. Khurana, and R. Magarotto
SP-239-17: Effectiveness of Commercial Corrosion Inhibitors for Reinforced

Concrete ............................................................................................................... 249
by F. Bolzoni, S. Goidanich, M. Ormellese, M.P. Pedeferri, and A. Lolli
SP-239-18: Cement-Superplasticizers Interaction: The Influence of

Superplasticizers on the Formation of Syngenite ................................................... 269
by H. Kucerova and C. RoSier
SP-239-19: Adsorption of Lignosulphonates on Cement and the Hydration

Products of Cements ................................................................•............................ 285
by B.O. Myrvold
SP-239-20: A New High Performance Drying Shrinkage-Reducing Admixture ........ 297

by M. Masanaga, T. Yamamoto, T. Hirata, and T. Nawa
SP-239-21: An Amphoteric Copolymer as a Concrete Admixture ........................... 309

by K.C. Hsu, J.W. Chen, F.T. Jiang, and D.S. Hwung
SP-239-22: Influence of Surfactant Chemical Admixtures on the Stability and

Pheological Properties of Calcium Carbonate and Cement Pastes ........................... 321
by N. Mikanovic, C. Jolicoeur, and M. Page
SP-239-23: Effect of Organic Admixtures on the Activation Process, Rheological

and Mechanical Properties and Durability of Alkali-Activated Slag Pastes
and Mortars .......................................................................................................... 345
by M. Palacios, F. Puertas, and P.F.G. Banfill
SP-239-24: Interaction between Cements and Superplasticizers .......................... 357

by H. Lombois-Burger, L. Guillot, and C. Haehnel
Copyright American Concrete Institute viii

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SP-239-25: Shrinkage-Free Mortars for Repairing Damaged Concrete Structures ... 375
by S. Collepardi, G. Corazza, G. Fazio, S. Monosi, and R. Troli
SP-239-26: Changes in Cement Paste and Mortar Fluidity after Mixing Induced
by PCP: A Parametric Study ................................................................................... 389
by L. Regnaud, A. Nonat, S. Pourchet, B. Pellerin, P. Maitrasse, J.P. Perez,
and S. Georges
SP-239-27: Rheological Behavior of Fresh Cement Pastes: Interaction between

Superplasticizer and Viscosity-Enhancing Admixture ............................................. 409
by L. D'Aioia Schwartzentruber and]. Cord in
SP-239-28: Effect ofTemperature on Rheological Properties of Superplasticized

Cement Mortars .................................................................................................... 423
by]. Golaszewski
SP-239-29: Hydrophobic Admixtures to Control Corrosion of Galvanized Steel

Reinforcement in Concrete .....................................................................................441
by F. Tittarelli, G. Valenti, and G. Moriconi
SP-239-30: Influence of Cement and Plasticizer Type on the Rheology and

Reactivity of Cementitious Binders ........................................................................ 455
by H. Vikan, H. Justnes, and R. Figi
SP-239-31: Effect of Advanced Hybrid Admixture on High Strength Concrete ......... 471
by K. Saito, M. Kinoshita, K. Okada, and T. Nawa
SP-239-32: Effects of an Inorganic Acid Based Alkali-Free Accelerator on the

Setting and the Compressive Strength Development of a Hydrating Clinker
Containing Different Setting Regulators ................................................................. 487
by C. Maltese, C. Pistolesi, A. Bravo, F. Cella, T. Cerulli, and D. Salvioni
SP-239-33: Effect of Functional Groups on the Performance of Lignosulfonates in

Cement-Water Systems ......................................................................................... 507
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by j. Zhor
SP-239-34: Influence of D-Sorbitol on the Properties of Binders to Immobilize

Acid Nuclear Wastes ............................................................................................. 525
by M. Collepardi, G. Grossi, M. Pellizon Birelli, and G. Ventura
SP-239-35: Effectiveness of Superplasticizers Incorporating Shrinkage-

Reducing Admixture in Recycled-Aggregate Concrete ............................................. 533
by V. Corinaldesi and G. Moriconi

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SP-236-36: Performance of Self-Consolidating Concrete made with Diutan Gum .. 545
by K.H. Khayat, A. Mechaymech, and B. Skaggs
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Copyright American Concrete Institute X

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Recent Developments in
Su perplasticizers
by M. Collepardi and M. Valente
Synopsis: Superplasticizers are considered to be the most important chemical

admixtures in cement mixtures due to their influence on the hardened concrete
properties (related to the water-cement ratio) as well as on those of the concrete in
the fresh state (workability and workabilty loss).
During the last decade a new family of polymers based on polycarboxylate as the
main polymer chain and polyether as side graft chains have been developed. This
new family of products appear to be in general more effective in terms of higher water
reduction, lower slump loss and lower retarding effect at very early ages.
More recently these performances have been enhanced in view of some specific
applications: a) in precast concrete structures, the very early strength (such as at 12-
16 hours) can be increased even in cold climates and in the absence of steam curing;
this effect depends on the number and length of the polyether graft chain which are
responsible for the dispersion effect related to the steric hindrance; b) in ready-mixed
concrete mixtures, the slump maintenance behavior can be designed as a function of
the transport time and placing temperatures, so that fresh superplasticized concrete
mixtures can be transported from the batching plant to the job site without any
slump loss even in summer times; this effect depends on the gradua !liberation of
special molecular groups which are responsible for the adsoption of these polymers
on the surface cement grains; c) a new series of polycarboxylate polymers has been
synthetized in which functional chemical groups, acting as shrinkage-reducing
admixtures, again are gradually liberated by the superplasticizer polymer as a
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function of the pH of the aqueous phase related to the cement hydration.
Keywords: adsorption; polycarboxylate; polyether; shrinkage; slump

loss; steric hindrance; superplasticizer; water-reduction; zeta potential

1
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2 Collepardi and Valente
Mario Collepardi is author or co-author of numerous papers on concrete technology and
cement chemistry. He is also the recipient of several awards for his contributions to the
fundamental knowledge of superplasticizers and their use in concrete.
Michele Valente is President of General Admixtures. He is the Past President of
ATECAP, the Italian Association of Ready-Mixed Concrete and he is the author of many
~~.:i~:nlific papers on concrete technology.
INTRODUCTION
Superplasticizers are unanimously considered to be the most important chemical

admixtures for concrete. This is due to the numerous properties of concrete which can be
improved by using superplasticizers. When superplasticizers are used without any change
in the mixture composition they really act as admixture-enhancing fresh concrete
workability. On the other hand, when they are used at given workability and cement
content, they can act as high-range water reducers and then they can increase both early
and later strength as well as improve durability and water-tightness. These admixtures
can also reduce drying shrinkage and thermal stress of concretes when they are used at
given workability and water-cement ratio (w/c) because of the higher aggregate/cement
ratio ..
Moreover, special high-performance concretes can be manufactured by combining
superplasticizers with mineral additions such as silica fume (high strength concrete), fly
ash (high volume fly ash concrete for mass concrete structures) or granulated ground
blast-furnace slag (chloride-resistant concrete).
DEVELOPMENT OF NEW SUPERPLASTICIZERS
During the last three decades [ 1-2] the main ingredients of the superplasticizers were
synthetic water-soluble polymers such as sulfonated melamine formaldehyde (SMF)
condensate and sulfonated naphthalene formaldehyde (SNF) condensate. These
admixtures are polymers based on a single repeating unit (sulfonated naphthalene or
melamine molecule) which do not allow for much variation of the molecular structure.
Advances in superplasticizers, containing alternative water soluble synthetic products,
have been proposed in the last decade to reduce the slump-loss drawback [3-17]. More
recently, these new superplasticizers - all based on the family of polycarboxylate
polymers (PC) - have been deeply investigated, and numerous papers on these admixtures
have been presented at the CANMET-ACI International Conferences on
"Superplasticizers and Other Chemical Admixtures" [18-24]. Polycarboxylate
superplasticizers are based on two or more structural groups that provide for more
diversity in possible molecular structures with respect to those based on SNF or MSF
[25]: for example, by changing the number of carboxyilic groups per polyether unit, the
adsorption of polymers on the cement surface can be significantly changed; moreover,
the molecular weight of polyether molecule can be adequately adjusted to form polymers
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Superplasticizers and Chemical Admixtures in Concrete 3
with different performance characteristics in terms of reduction in mixing water or
retarding effect on the early cement hydration.
DISPERSION MECHANISMS OF CEMENT AGGLOMERATES
Superplasticizers cause dispersion of particles of coarse agglomerates which

predominate in the cement paste of the concrete [26]. Due to the dispersion effect, there
is a fluidity increase in the cement mixture (Fig.l ). In the past, the dispersion effect was
ascribed only to the development of the same electrostatic (negative) charge on the
cement particles . The electrostatic attractive forces, existing among cement particles and
causing agglomeration, would be neutralized by the adsorption of anionic polymers
negatively charged, such as SNF or SMF, for the presence of S03- groups on the surface
of cement particles. The dispersion of cement particles (Fig.2) would be related with the
electrical repulsion produced by the negatively charged groups (S03 ) on the other side of
the main polymer chain [27).
The electrostatic repulsion of cement particles was determined through zeta potential
measurements. Additional available experimental results did not confirm this mechanism
for the superplasticizing action of the polycarboxylate polymers. These results would
indicate that the dispersion of cement particles, responsible for the fluidity increase
caused by superplasticizer, is not necessarily related to the electrostatic repulsion
associated with zeta potential measurements.
The dispersion mechanism performed by the PC-based superplasticizers (Fig. 3) is
related more to a steric hindrance effect produced by the presence of pendant ethylene
oxide (EO) side graft chains, rather than to the presence of negatively charged anionic groups
(COO) which are responsible for the adsorption of the polymers on the surface of cement
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particles. In other words, the pendant graft chains of the polymer molecules adsorbed on
the surface of cement would hinder by themselves from flocculating into large and
irregular agglomerates of cement particles (Fig. 3).
SLUMP RETENTION
Slump loss appears to be the most serious problem at least for ready mixed concrete
industries. When a concrete mixture must be transported for a long time, particularly in
hot weather, it should keep as far as possible at its initial slump level to avoid the practice
of redosing the concrete with water above and beyond that required in the mixture
proportion. Results of investigations of retempered concrete indicate that many of the
properties of the hardened concrete (strength, durability, abrasion resistance, etc.) are
significantly affected, since retempered concrete does not perform as well as concrete
which has not been retempered [28]. However, slump loss is un-avoidable because ofthe
intrinsic requirement for concrete mixtures which should set and harden in a relatively
short time. Therefore, a right and proper compromise would be a zero-slump-loss
concrete mixture for about 1 hour. By using superplasticizers based on SNF or SMF
polymers it is not easy to achieve this target, because in general slump loss is higher in
superplasticized concrete with respect to the corresponding plain mix at given initial

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slump (Fig. 4). The lower the w/c, the higher is the slump loss for the same initial slump
level. It seems that the lower w/c in superplasticized concrete and the consequent smaller
distance among cement particles (Fig. 5) cause a more significant slump loss when the
same amount of water is lost through evaporation or by reaction with cement during the
transportation time.
Several methods have been adopted tn control thP rate of slump !ass. One rnethcd is
to add the superplasticizer at the point of discharge but there are some practical problems
associated with this approach. For instance, the concrete into the truck-mixer before the
superplasticizer addition would be too stiff when a high-quality concrete, (with low w/c),
should be produced. Moreover, dosing the superplasticizer at the work site is too time
consuming and does not allow an accurate control of the final slump and admixture
dosage.
Other methods to control slump loss include adding a higher than normal dosage of
superplasticizer or using some type of retarding admixture in the formulation. However,
there are some limits in this approach, because sometimes the final effect is to produce
concrete with un-acceptable low early strength or, surprisingly, to aggravate more
seriously slump loss. For instance, slump loss accompanied by a surprisingly quick set
may sometimes occur by using retarders such as sugar, sucrose, com syrup or calcium
lignosulfonate [29]. The cement content, as well as the chemical and mineralogical
composition of cement, play an important role in determining such a singular slump loss
although the detailed mechanism is not clear: it seems that the content of C3A, gypsum
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and alkali, as well as the form of calcium sulfate used as set regulator, can affect the rate
of slump-loss.
Also redosing the superplasticizer at different intervals of time has been suggested
[30] to reduce slump-loss, but this method appears to be not always easy to be adopted in
practice. Moreover, the total dosage of superplasticizer, as well as the relative cost,
cannot be kept under control according to a given plan.
Therefore a superplasticizer is required which by itself is capable to maintain the
slump for a long period of time independently of the temperature or the type and content
of cement. Collepardi et al. [13] studied the effects of a PC-based superplasticizer on the
properties of ready-mixed concrete mixtures. This admixture acts as both an immediate
superplasticizer and a slump loss reducing agent, and appears to be more effective than
that based on SNF. Although the PC-based superplasticizer has been used at a lower
content of active polymer (0.30% versus 0.40%), it was more effective than that based on
SNF for the water reducing capability (w/c = 0.43 versus 0.47) as well as for the
maintainance of the initial slump level (Fig. 6).
Tanaka et al. [17] studied the effect of a CLAP-based superplasticizer (Cross Linked
Acrylic Polymer) on the slump-loss of concrete mixtures. This superplasticizer is a
partially cross-linked copolymer of acrylic acid and polyethylene glycol mono-alkyl ether
(Fig. 7). According to Tanaka and co-workers the cross-linked polymer is hydrolyzed by
the alkaline water phase of the cement paste and then converted into a PC-based polymer
(Fig. 8). The negative carboxylic groups due to the alkaline hydrolysis would be adsorbed
on cement surface of cement particles and then would be responsible for the dispersion of
cement particles and the fluidizing action of the admixture. The low slump-loss effect of
this superplasticizer should be related with increasing number of the protruding side

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,`,,`---
chains of the acrylic polymer which would prolong the dispersion of hydrated cement
particles through a steric hindrance effect.
Hamada et al. [22] developed a new family of acrylic polymers based on the
following changes with respect to the traditional PC-based superplasticizer:
- a new superplasticizer ,called PE because of the much longer side chains of ethylene
oxide (EO): 130 moles of EO instead of 10-25 moles as in traditional PC-based
superplasticizer (Fig. 9); this change ,combined with a lower number of carboxylic
groups (COO-), produces a lower adsorption speed and reduces the typical retarding
effect related to the early adsorption;
- a modified PE-based superplasticizer where a great number of carboxylic groups are
replaced by a slump-loss controlling agent (SLCA) to achieve a still higher slump
retention with minimal setting retardation: indeed, due to the relatively low number of
carboxylic groups in SLCA (Fig. 10) the initial adsorption and the dispersing effect are
negligible as well as the setting retardation; however, subsequently due to the
hydrolytic effect related with the OH- presence in the aqueous phase of the cement
paste, the number of carboxylic units increases (Fig. 11) and the slump can still
increase by prolonging the mixing time due to the increasing adsorption of the polymer
on the surface of the cement particles.
The behavior of fresh concrete in the presence of PC and SLCA-based
superplasticizers is schematically shown in Fig. 12.
Figure 13 schematically shows the heat of cement hydration and Figure 14 shows the
concrete hardening in the absence and in the presence of PC or PE acrylic
superplasticizers.
Sugiyama et al. [32] synthetized a new series of superplasticizers in which functional
groups called EPBE acting as shrinkage reducing agent (SRA), capable of reducing
surface tension, were attached to the structure of various polycarboxylate polymers (Fig.
15). Figure 16 shows the drying shrinkage behavior of concretes with PC-based
superplasticizer or modified EPBE-PC-based admixture: the drying shrinkage of the latter
is lower than that of the former.
Nakanishi et al. [24] invented another multi-function and multi-purpose admixture
incorporating a shrinkage reducing group (based on diethylene glycol monobutyl ether)
acting as SRA on the PC chain acting as a water reducing agent.
CONCLUSIONS
Superplasticizers are able to enhance the placing characteristics of concrete mixtures

by increasing the workability level at a given w/c. Therefore they allow to make easy
placement of concrete mixtures even with low w/c as required by strength or durability
reasons.
The main drawback of superplasticized concrete mixtures with sulphonated polymer-
based admixtures is the slump-loss. This can reduce the advantage of using these
superplasticizers particularly in hot weather, with long transportation times and reactive
cements.
A new family of superplasticizers based on acrylic polymers is available with
improved placing characteristics: a) flowing concretes can be produced at lower w/c with

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respect to concrete mixtures containing sulphonated superplasticizers; b) the slump-loss
is much more reduced with respect to concrete mixes with sulphonated superplasticizers;
c) multi-purpose superplasticizers with shrinkage reducing properties have been invented
by incorporating special functional groups on the PC chain.
REFERENCES
[1] Ramachandran V.S., Concrete Admixtures Handbook- Properties, Science, and

Technology, Noyes Publication, II Edition.
[2] Rixom R. and Mailvaganam N., Chemical Admixtures for Concrete, E & FN Spon
Publication, Tli Edition.
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[6] Proceedings of Fourth CANMET/ACI International Conference on
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Rome, Italy, 7-10 October, Editor: V.M. Malhotra, (1997).
[8] Proceedings of Sixth CANMET/ACI International Conference on
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Berlin, Germany, 20-24 October, Editor: V.M. Malhotra, (2003).
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Properties of Concrete with a New Superplasticizer. I: Laboratory studies and
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[11) Yamakawa I., Kishtiani K., Fukushi 1., Kuroha K., Slump Control and Properties
of Concrete with a New Superplasticizer. II. High strength in situ concrete work at
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105 (1990).
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[12] Collepardi M., The World of Chemical Admixtures in Concrete, Proceedings of
the Congress "Our World in Concrete and Structures", Singapore, pp 63-72,
Editor: C.T. Tam, (1993).
[13] Collepardi M., Coppola L., Cerulli T., Ferrari G., Pisto1esi C., Zaffaroni P., Quek
F., Zero Slump Loss Superplasticized Concrete, Proceedings of the Congress "Our
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[14] Collepardi M., Advances in Chemical Admixtures for Concrete, Proceedings of the
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Durham, U.S.A., pp. 257-291 (1994).
[15] Collepardi M., Superplasticizers and Air-Entraining Agents: State of the Art and
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399-416 (1994).
[16] Uchikawa H., Hydration of Cement and Structures Formation and Properties oj
Cement Paste in the Presence of Organic Admixtures, Proceedings of the
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3-47 (1995).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
[17] Tanaka M., Matsuo S., Ohta A. and Veda M., A New Admixture for High
Performance Concrete, Proceedings of the "Concrete in The Service of Mankind",
Editors: R.K. Dhir and M.J. McCarthy, pp. 291-300 (1996).
[18] Jeknavorian A.A., Roberts L.R., Jardine L., Koyata H. and Darwin D.C.,
Condensed Polyacrylic Acid-Aminated Polyether Polymers as Superplasticizers
for Concrete, Proceedings of the Fifth International Conference on
"Superplasticizers and Other Chemical Admixtures" Editor V.M. Malhotra, ACI
SP-173, Rome, Italy, pp. 55-82 (1997).
[19] Sakai E. and Daimon M., Dispersion Mechanisms of Alite Stabilized by
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(1997).
[20] Ohta A., Sugiyama T. and Tanaka Y., Fluidizing Mechanism and Application oj
Polycarboxlate-Based Superplasticizers, Proceedings of the Fifth International
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[22] Hamada D., Sato H., Yamamuro H., Izumi T., and Mizunuma T., Development oj
Slump-Loss Controlling Agent with Minimal Setting Retardation, Proceedings of

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Seventh CANMET/ACI International Conference on Superplasticizers and Other
Chemical Admixtures In Concrete, ACI SP-217, Berlin, Germany, 20-24 October,
pp. 127-142, Editor: V.M. Malhotra, (2003).
[23] Compater C., Nonat A., Pourchet S., Mosquet M., and Maitrasse P., The
Molecular Parameters and the Effect of Comb- Type Superplasticizers on Self-
Compacting Concrete: A Comparison of Comb-l'ype Superplasticizer Adsorption
onto a Basic Calcium Carbonate Medium in the Presence of Sodium Sulphate,
Proceedings of Seventh CANMET/ACI International Conference on
Superplasticizers and Other Chemical Admixtures In Concrete, ACI SP-217,
Berlin, Germany, 20-24 October, pp. 195-210, Editor: V.M. Malhotra, (2003).
[24] Nakanishi H., Tamaki S., Yaguchi M., Yamada K., Kinoshita M., Ishimori M.,
and Okazawa S., Performance of a Multifunctional and Multipurpose
Superplasticizer for Concrete, Proceedings of Seventh CANMET/ACI
International Conference on Superplasticizers and Other Chemical Admixtures In
Concrete, ACI SP-217, Berlin, Germany, 20-24 October, pp. 327-342, Editor:
V.M. Malhotra, (2003).
[25] Vickers T. M., Farrington S.A., Bury J.R., Brower L.E., "Influence of dispersant
structure and mixing speed on concrete slump retention", Cern. Concr. Res. 35,
1882-1890,2005.
[26] Collepardi, M.,"Admixtures: Enhancing Concrete Performance", Global
Construction : Ultimate Opportunities; Voi.VII Admixtures-Enhancing Concrete
Perfonnance, Editor: R.K. Dhir, P.C. Hewlett, M.D. Newlands, 217-230, 2005.
[27] Femon V., Vichot A., Le Goanvic N., Colombet P., Corazza F., Costa
U.,"Interaction between portland cement hydrates and polynaphthalene
sulfonates", Proceedings of the Fifth CANMET/ACI International Conference on
Superplasticizers and Other Chemical Admixtures, SP-173, 225-248, Editor: V.M.
Malhotra, (1997).
[28] Anderson F. and Carrasquillo R.L., The Effects of Witholding Mixing Water and
Retempering on Properties of Concrete, Res. Rep. 117 -I, Center for
Transportation Research, The University of Texas at Austin, USA (1988).
[29] Green A., A Setting Problem Involving White Cement and Admixture,
Transportation Research record, N° 564, pp. 21-26 (1976).
[30] Malhotra V.M. and Ramachandran V.S., Superplasticizers, Chapter 7, pp. 410-
506, in "Concrete Admixtures Handbook. Properties, Science and Technology",
Editor: V.S. Ramachandran, 2nd ed., Noyes Publications, Park Ridge, New Jersey,
USA (1995).
[31] Sugiyama T., Ohta A. and Tanaka Y., Shrinkage Reducing Type of Advanced
Superplasticizer, Proceedings of the CANMET/ACI Symposium on "Advances in
Concrete Technology", pp. 189-200, Editor: V.M. Malhotra, (2000).
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Cement grains agglomeration Cement grains dispersion
Superplasticizer
-+
Superplasticlzer
-+
Fig. 1- Relationship between cement grains dispersion and fluidifying
effect on the cement.
SNF
Skle sulphonic group (negatiVely Chai\Jed)
L,
Main potymerchalnrj. . . . . . . . . . . . . .. . .
/
/
Sulphoni<o groupe
responslbt& for Cement grain
actsorptJon
Fig. 2 - Schematic picture of sulfonated polymer (SNF) and its electrostatic repulsion
effect on the dispersion of cement particles.
SIM c•Tbo~yl group lnoo&INety chatgtd)

fhi)OMI~for~n
pol~ll*
0-·"-"''"""'• .....
c;hlln
\
Std• lorJV graft ch..n
l'"'utral)rn.pontlbleiOf'
•tarkhlfl.dr•nc•
Fig. 3- Schematic picture of the polycarboxylate (PC) superplasticizer and its steric
hindrance effect on the dispersion of cement particles.
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300 r--------------,
250
WIC=0.60
E 200 ''
E
'
a:-
:::E
150 '-. '
"'ll
:::i 100 '
WIC=0.45·',..,._~~MIX
0
50 SNFMIX'-.. __
0
- ....
0 30 60 90 120 150
nME,mln
Fig. 4- Slump loss at 20 °( for plain and superplasticized mixes at the same initial
slump. Superplasticizer: 0.4% as dry SNF polymer by weight of cement.
W/C =0.60 WIC " 0.45
MIXING . . . . JUST I
WATER~C?o· .
. U·\:)·. /
. / AFTER......._Q00
?'!3 MIXING ......._ l;)'

G13
ANHYDROUS
CEMENT
Q....
d~~/ 1 HOUR'-.._
AFTER @ .•
~-"·
HYDRATED CEMENT
Fig. 5- Schematic picture of cement paste in a plain (w/ c = o.6o) and

superplasticized concrete (w/c = 0.45).
E 200
E
2~ r-------------~
--------•,--•-~/C=0.43
, _ .
PC (0.30%) - -.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
a: 150
:iii
:J
...I 100
(I)
50
0 30 60 90 120 150
TIME, min
Fig. 6- Slump loss of superplasticized concretes at 20 °( with PC or SNF polymer

based admixtures [13]. Percentages on the curves refer to dry polymer.

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Fig. 7- Chemical Structure of CLAP (cross-linked acrylic polymers). X is the cross

linking group.
IBefore Mixing J
Side long ether Chain
low
[AhrMixlng ~7:;:;:;:;:;:;:;:;~b:::::
Fig. 8- CLAP-based superplasticizer hydrolyzed by the alkaline water of cement
paste: the number of coo-
progressively increases with time and this is responsible
for the low slump loss.
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`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
...,...,..,..._li'CI
-· ...L).
+.-t±(
•
--fc..-~-+f...
•
-4-+
- coo-··· ~··
p•tiD
...,.Looo_...,.AgontCOLCAI
................u,
" • : • • !
+ -4
-~ ___l/... _____1_¥- b-&--1L
~ ~-~~l
... , . i..••.••••••••.••.•
Fig. 9- The chemical structure of polycarboxylate type (PC), polyether type (PE),
and slump-loss-controlling agent superplasticizer (SLCA); q and pare the number of
moles of EO in PC and PE or SLCA polymers [22].
Polycarboxytate based (PC) Poly.- based (PE) Stump Loss Controlling Agent
(SLCA)
::s;iW Jl±J
Fig. 10- The schematic molecular structure of polycarboxylate type (PC), polyether
Carboryl unit
(COO") (COOR)
type (PE) and slump-loss-controlling agent superplasticizer (SLCA)

(adapted from Reference 22).
no adsorpUon innlally adsorption onto cement and

no initial dispersablllty development of dispersability
L;J : :~ I
~~ @)
Fig. 11- The mechanism and the hydrolysis reaction ofSLCA in alkaline condition of
cement paste (adapted from Reference 22).

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300
e
§.
c..
E
:I
Ci5
OL-----------------------------~
0 30 60 90 120
Time (mm)
Fig. 12- Schematic trend in the slump loss behavior with different acrylic
superplasticizers (PC, PE, SLCA, PE+SLCA) in concrete mixtures with CEM II A/L 32.5R
(340 kg/m 3), w/c = 0-45.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~~----------------------~
PE
6
t.-25
1-
~L-----------------------~
0 5 10 15 20 25
Time (hours)
Fig. 13- Heat development in portland cement pastes with PE or PC polymers.
40r---------------------------~
oL---------------------------~
0 12 24
Time (hours)
Fig. 14- Compressive strength development of concrete with PE or PC.

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,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
HiCH.-r-~CH•
r= ~Hs
_'f=O H
.
OM 9 PC
...
"'0)
.,
Si'·z
H CHr¢~n¢~~¢~q H
1 9
(EO)n
H a
OM ?
(EPBE)
b
Fig. 15- Chemical structures of PC and EPBE-PC [32].

EPBE·PC
?;S.3
14
i 5
"' 6
~
g7
8
9 L-------~--------~--------~
0 10 20 30
Age (week)
Fig. 16- Shrinkage of concretes with PC-based superplasticizer or modified PC-based

superplasticizer by EPBE groups [32].

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SP-239-2
Use of Chemical Admixtures to

Modify the Rheological Behavior of
Cementitious Systems Containing
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Manufactured Aggregates
by A. Jeknavorian, K. Hazrati, A. Bentur, H. Koyata,

D. McGuire, and P. Sandberg
Synopsis: Aggregate shape, texture, and grading have been known to have a
significant effect on the rheological performance of fresh concrete. Moreover, while
the optimization of aggregate selection can provide both technical and economical
benefits, the availability of materials and construction operations can often dictate
the use and proportioning of certain aggregate sources, such as manufactured sands,
which can adversely impact the rheology of cementitious mixtures. The use of certain
chemical admixtures has been found to often minimize the need to increase cement
and water contents in orde~ to overcome the loss of workability that can accompany
aggregate sources which feature flat, elongated, angular, and rough particles.
In this study, a wide range of natural and manufactured sands, characterized for
gradation, mineralogy, shape, texture, and cleanliness, are evaluated for their effect
on mortar rheology, with and without a viscosifying-type chemical admixture. While
associations between aggregate characteristics and their impact of mortar rheology
may not be readily evident, the ability of this class of admixture can be shown
to mitigate the rheological effect of certain sands, and in some cases allow for
optimizing the mixture to lower paste contents.
Keywords: aggregates; petrographic analysis of aggregates; rheology;

viscosity-modifying agent; yield stress

15 Licensee=UNI OF NEW SOUTH WALES/9996758001
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16 Jeknavorian et at.
Dr. Ara A. Jeknavorian, Research Fellow, W.R. Grace & Co.- Conn., Cambridge, MA
02140, USA.
Dr. Kati Hazrati, Product Manager, W.R. Grace & Co.- Conn., Cambridge, MA 02140.
Dr. Arnon Bentur, Professor, Technion, Israel Institute of Technology, Department of

Civil and Environmental Engineering, Haifa 32000, Israel
Hideo Koyata, Senior Research Associate, W.R. Grace & Co.- Conn., Cambridge, MA
02140.
Dr. Paul Sandberg, Senior Research Associate, W.R. Grace & Co. -Conn., Cambridge,
MA02140.
Derek McGuire, Technical Specialist, W.R. Grace & Co.- Conn., Cambridge, MA
02140.
INTRODUCTION
Diminishing local availability of naturally occurring sands for use as fine aggregates in
the production of concrete, coupled with regulatory pressures to utilize by-products from
quarry operations, has brought about a growing dependency on manufactured sands [1,2].
Moreover, an economic advantage is often possible when replacing fine aggregates with
manufactured sands. The production of manufactured sands results from by crushing rock
deposits to produce a fine aggregate, which is generally more angular and has a rougher
surface texture than naturally weathered sand particles. Furthermore, rock dust
(microfines), a by-product of the crushing operation consisting of particles less than 75
1-\ID, can amount to as much as 20-30% of the manufactured sand. While some countries
such as India, Spain, and Australia permit from 15-25% microfines in the fine aggregate,
concrete fine aggregate gradation limits such as found in the ASTM C 33 Standard
Specification for Concrete Aggregates [3) permit up to 7% finer than 75 !-LID for some
applications assuming the absence of clay or shale. To comply with various particle
grading standards, the rock dust is removed by washing with water creating a waste
slurry whose accumulation imposes considerable detrimental impact on the aggregate
industry.
When manufactured sands are substituted for naturally sourced fine aggregate, even with
the fine than 75 ~--tm fraction controlled, the workability of concrete mixtures are
generally reduced, and in some cases, the concrete mixture can be more prone to
segregation. Furthermore, the increased friction that results causes higher pumping
pressures, increase the effort associated with concrete placement and finishing operations
[4). These performance attributes associated with manufactured sands result from a
combination of the angular particle shape and rough surface texture [5], both contributing
to increased void space in the aggregate packing. Both factors contribute to increased
surface area, which will require increased water content to maintain consistent
workability.
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To overcome the adverse effects manufactured sands can contribute to concrete mixtures,
one option is to increase the paste volume in the form of either higher cement or cement
along with a supplementary cementitious material (SCM). Chemical admixtures,
especially polycarboxylate-based high range water reducing agents, have been found to
be useful to minimize the need for both increased water and paste contents that could be
required with manufactured sands [6].
This study is concerned with evaluating the interaction of both natural and manufacturing
sands with a bio-polymer type viscosity-modifying agent (VMA), a class of admixture
finding increased use with angular-shaped fine aggregates. From various particle shape
and mineralogical analyses made on sands from five sources, along with yield and
viscosity measurements on mortar mixtures, prepared with and without VMA, predictions
are attempted to associate the key particle attributes responsible for changes in mortar
rheology and the effectiveness of the VMA to maintain mortar workability without
altering mixture components.
TEST PROGRAM
Seven (7) manufactured and eight (8) natural sands, identified in Table I, were tested for
gradation (ASTM C l36 [7]), particle shape and texture (ASTM C 295 petrographic
analysis [8]),% finer than 75 j..lm, and Uncompacted Void Content (ASTM C 1252 [9]).
Mortar mixtures were prepared using the mixture proportions reported in Table l with
each manufactured and natural sand. Yield and viscosity measurements were performed
on the mortar mixtures using a prototype Contec coaxial cylinder rheometer shown in
Figure 1. The outer cylinder rotates at a programmable velocity while the inner cylinder
is stationary and registers the applied torque from the mortar. By assuming the mortar to
flow like a Bingham fluid, the yield value and plastic viscosity are calculated from the
slope (viscosity) and yield value (intercept) in a torque-velocity diagram. In this study,
focus was mainly on the yield value as it has been sown to correlate inversely with slump.
RESULTS
Mortar Rheology
The mortar yield stress results for all the mortar mixtures, prepared at constant w/c and a
constant weight of sand, either from manufactured or natural sources, are reported in
Figure 1. No consistent trend is apparent between the yield stress versus sand type
indicating other factors or combination of factors must be influencing water demand
changes created by the various sand properties. Mortar yield stress results, obtained with
the Contec rheometer, were found to correlate well with mortar flow, and thus help to
validate measurements with the rheometer (Figure 2). Attempts to further characterize
the rheological impact of natural versus manufactured sands by plotting yield stress
versus viscosity as shown in Figure 3 could not discern any specific trends, indicating
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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that certain properties ofthe sands can influence both yield stress and viscosity somewhat
independently.
Petrographic Analysis of Fine Aggregates
All the sand samples were subjected to a petrographic analysis performed according to
ASTM C 295 and C 136 Sieve Analysis. Key parameters noted during the examination
were mineralogy, shape, texture, and cleanliness, and are reported in Figures 4-7 for two
pairs of natural and manufactured sands, which some concrete producers are known to
either blend or use interchangeably. Numerical values, ranging from 1 to 10, were
assigned for shape, texture, and cleanliness, where lower the number implies high quality
and suitability for concrete manufacture. As expected, the manufactured sands designated
with the "HS" code have higher values versus natural sand available from a nearby
location.
Correlation of Sand Properties with Yield Stress
In an attempt to identity the sand properties responsible for effecting the workability of
mortar and concrete mixtures, the yield stress of mortar mixtures prepared with both
natural and manufactured sands were correlated with fineness modulus, percent un-
compacted voids, and a combined factor representing the sum ofthe values assigned for
shape, texture, and cleanliness (Figures 8 -1 0). No clear correlations were readily
evident suggesting that either certain critical sand parameters have yet to be measured, or
that a higher level regression-type analysis is required to uncover more complex
relationships.
Probing Interaction of Sand-type using VMA Modifying Agent and Cement Paste
With the measured sand properties providing limited predictive information concerning
mortar workability, changes in mortar rheology as a function of VMA addition and
increased paste content were next evaluated. Starting with the control mixture described
in Table 2 and prepared with each of the natural and manufactured sands identified in
Table 1, the paste content was increased from 10 to 40% by mass. In addition, the control
mixture with the manufactured sand was dosed with 0.003% VMA actives by weight of
cement(% s/s). Yield stress was measured for the mixtures. A sample plot of the yield
stress as a function of increasing cement paste is shown in Figure 11. Interestingly, the
pair of selected manufactured and natural sands, exhibit a similar drop in yield stress with
increasing paste content. In the case of the VMA -treated mortar containing the
manufactured Mari-HS sand, a 75 Pa drop in yield stress was observed. Extrapolating the
lower yield stress to the yield stress-cement paste plot, the VMA appears to have the
potential of lowering the paste content by about 12% without altering the yield stress.
In Figure 12, the reduction in paste content observed with the addition of 0.003% s/s
VMA to II mortar mixtures prepared with the various manufactured sands. Interestingly,
the sands appear to have quite a diverse response to the VMA additive, exhibiting a six
(6)-fold change in yield stress.
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Increasing the paste content of the control mortar mixture had a similar effect on yield
stress compared to the VMA (Figure 13). Once again, the mortar mixtures prepared with
the various manufactured sands exhibit a different response to added paste content
expressed as percent reduction in yield stress normalized for percent cement paste added.
To understand if the yield stress reductions observed by both the addition ofVMA and
increased paste content have a similar mechanism in reducing the increased frictional
particle-to-particle forces associated with manufactured sands, the change in yield stress
produced by the VMA was correlated to the ratio of percent change in yield stress to
percent added paste (Figure 15). A somewhat unexpected qualitative trend suggests that
sands with a low to moderate yield stress response to the VMA have a high response to
increasing cement paste. This could possibly be explained by the proposed mechanisms
illustrated in Figure 16, where the increased paste content enables more significant
particle-to-particle separation under various degrees of shear, whereas the effect ofVMA
on yield stress is probably more shear history dependent.
CONCLUSIONS
Rheology measurements with a rheometer has been found to be a useful method to

differentiate the effect that different natural and manufactured sands can have on the
workability of mortar mixtures. Despite significant characterization of the various sands,
no simple correlation has been identified to associate sand properties with effect on yield
stress. A multiple regression analysis might possibly provide a predictive relationship
between some set of physical parameters associated with manufactured sands and mortar
and concrete workability. Moreover, changes in yield stress of a control mortar mixture
hatched candidate sands, and subsequently modified either by the addition of a VMA or
increased paste content, could have some potential use for concrete producers as a means
of predicting the need for a change in mixture proportions to assure adequate placing and
pumping operations.
Acknowledgement
The authors wish to thank Derek Brown, senior petrographer at the Grace Research
Laboratories, for the characterization of the sand samples.
References
1. McCaig, M., Aggregates Manager, September 2002.
2. Hunt, J. "Manufactured Sand Industry Overview and Trends," Extractive Industry

Association, Manufactured Sand Seminar, December 2000.
3. ASTM Manual 04.02, p 10,2005.
4. Hudson, B., "Manufactured Sand- How it Effects Concrete," Quarry 4 (5), 30-39, 1996.
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20 Jeknavorian et al.
5. Aggregates for Concrete, ACI Education Bulletin No. El-99, 1999.
6. Krinkle, M.J. "Effect of Admixtures in Concrete Containing Manufactured Sand,"

Dissertation, University of Southern Queensland, ENG4111/2 Research Project, 2004.
7. ASTM Manual 04.02, p. 88,2005.
8. ASTM Manual 04.02, p. 193, 2005.
9. ASTM Manual 04.02, p. 677,2005.
Table 1. Location and Type of Sands
Manufactured Sands (liS) Natural Sand (NS) Location

EN Standard Sand- Europe
GC-HS HC-NS Central California
HSLO-HS HSLO-NS Central California
MARl-HS NS Arizona
CP-HS CP-NS Arizona
BARGE-HS HV-NS Southern California
S·HS DUR-HS Southern California
D-HS -· Illinois
FL-HS FL-NS Florida
Table. 2 Mortar compositions with increased paste contents
Control Control Control+ Control+ Control+ Control+

w/VMA 10% Paste 20% Paste 30%Paste 40%paste
Cement 400 400 440 480 520 560
Sand 800 800 800 800 &00 800
Water 188 188 207 225 244 263
VMA, 0.0035 - . . -
%sis
Table 3. Cbemical Composition of Cement

#170
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
ASTMC 150 T-I

Si02 21.11
Al203 4.59
Fe,03 3.30
CaO 64.39
MgO 2.86
so, 2.32
Total Alkali as Na20 0.45
LOI 0.83
Bogue Compounds
c,s 57
c2s 17
C,A 7
C.,AF 10
C,AJSO, 3.0
Fineness, Blaine m2/g 368

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T
450 ~~~~~~~~--------------------------------~
400
350 +--------------------------------------
300 +---~------------------------~~~
250 +-~---------------------~-~----.-
200 +---.~
150
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100
50 -t-BI~III::--M-.--111111---f' !---li':J------~1'..ll--r.A-'I~.t---vl--1"...r-tlll-iB:-,..,.h
Q ~~~~~--~~~~~~~~~U4~~~~
R ~ ~ ~ 0 ~ W • ~ ~ ~ ~ G • ~ ~ ~
~ ~ ~ ~ ~ H ~ w oo ~ ~ d c ~ w n ~
~ $ M ~ ~ ~ ~ ~ ~ ~ ~
HS
Figure 1. Yield measurement of mortar mixtures prepared with natural and

manufactured sands as well as blends of both sands.
WithoutVMA
+MNS
rn MGCRB
HM
~;CGC
&. FL
oO
130
E 120
E
l 110
~100
~
90
90
70
100 ..
, 200 200
Yield Stress, PA
300 350 •oo
Figure 2. Correlation of mortar flow with yield stress.

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EN
!IIIMarii'IS
450 aMariHS
X H M HS {Barge)
<>Ge CHS
FIHS
400 D-HS
... HVNS
aHCNS
y 350 FINS
IIIIHSlOHS
I A.HSlONS
E 300 IIIICPHS
L .t.CPNS
D OCP2575
ACP4060
250 )f(CP6040
•CP8020
•NS
10 20 30 40 50 60 70 80
Figure 3. Mortar rheology as a function of yield stress versus viscosity.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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HSSLO HS
100
.
= 8070
90
I. 60
1E
50
40
30
""
.... 20
10
11200 #100 #SO #30 #16 #8 #4

Selve Sizo
Mineralogy: Medium fine sand composed of crushed crystalline rock

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
quartz dominant with feldspar and a moderate amount of mica flakes.
Shape: 4 Predominantly more elongated particles

Texture: 3 Sub angular to sub rounded
Cleantiness: 2 Clean with dusty mica plates
STC Factor: 9
Figure 4. Petrographic analysis of harsh sand HSLO.
100
90
."'
.5
60
..
!l
~
6()
50
l 40
E"30
..."
u
20
10
#200 #100 #SO #30 #16

Seive Size
Mineralogy: River gravel sand containing rock fragments, (sandstone)

no micas obvious
Shape: l Equant
Texture: 4 Sub angular
Cleanligess: I Clean
STC Factor: 6
Figures. Petrographic analysis of natural sand HSLO.

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24 jeknavorian et al.
Central Phoenix HS
100
90
{ 80
70
:. 60
~ 50
"'
.!!
~ 40
E 30
,.
~
(,)
20
10
#200 #100 #50 #30 #16 #8 #4

Selve Size
Mineralogy: : Medium to tine well graded sand of mixed lithology

with little to no micas.
Shape: 3 Elongated and Equant

~ 3 Sub Angular to sub rounded
Cleanliness: 4 Dirty
STC Factor: 10
Figure 6. Petrographic and sieve analysis of harsh sand CP.
Central Phoenix NS
100·~---~
90~:
so FM: 2.93
10 %Passing #100: 1.8
eo %UCV: 43.7
50 G'; 312.5 Pa
40 W:52.5J>a
30
20
10
#200 #100 #50 #30 #16
Mineralogy: : Medium to fine river gravel I sand of mixed lithology

with some micas
Sbape: 3 Elongated and Equant

Texture: 4 Sub Angular
Cleanliness: I Clean
STC Factor: 8
Figure 7· Petrographic and sieve analysis of natural sand CP.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Ill EN
450 llil Florida Limestone HS
DolomiteHS
• Granite Canada HS
0 Maricopa River Bottom HS
400 e Hanson Mexican HS (Barge)
1> Maricopa NS
A Hanson Vulcan NS
•
<> Hanson Califomia NS
<> Florida Umestone NS
350 Central Phoenix HS
0 Central Phoenix NS
OCP2575
y 300
0 QCP4060
t>CP6040
I A+ <>CP8020
0 Hanson Durbin NS
E Hanson SLO HS
250 0 Hanson SLO NS
L ([]
•<>o.
d
G' 200
(Pa)
150
100
<>
• 0
50
2 2.5 3 3.5 4 4.5
FM
Figure 8. Correlation of yield stress versus fineness modulus (FM).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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26 Jeknavorian et al.
450 a EN
.,.,_,...
a Florida Urrestona HS
400.
• Granite Canada~
• Mtricapa River Bottom HS
• Hanson M:Jxican HS (Barge)
6. Mlricopa HS
•
A Hanson Vulcan NS
350
• Henson Califom8 NS
o Florida Unestone N5
CentraiftloenixHS
o Cerrtral Ftloenix NS
D CF'2515
•
0 Cf'ro60
h 0'0040
0
••
300 oCI'8020
o Hanson OJrbin NS
Hanson SLO HS
e HansonSlONS
(, 250
:!!
0 0
.!!!
>-
200- • 4,
150
••
<>
100- •
50
35 37 39 41 43
% Uncompacted Voids
Figure 9· Correlation of yield stress versus% uncompacted voids.
450
400
DolomiteHS
350
o Grarille Canada HS
300 • Maricopa River Bottom HS
• Hanson M!xlcan HS (Barge)
'i' tJ. M3ricopa NS
e.,. 250
... Hanson SLO HS
b
:!! 200 0 Hanson SLO NS
~ • Hanson Dur!Jin NS
-' Central Phoenix HS
150
.t. Central Phoenix NS
100
50
0
3 4 5 6 7 6 9 10 11 12 13
STC Factor (Shape+Texture+Cieanliness)
Figure 10. Correlation of yield stress with combined aggregate properties of shape,
texture, and cleanliness.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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450.------------------------------.
400
~ 350
~
Ill
300
e 25o
Ill
Ui 200
't:l
1150
>-
100
50 1 - - - - - - - - - - , - . - - - - - - - - - - - ' - - - l
0 20 40
%Additional Cement
Figure 11. Change in mortar yield as a function ofVMA and cement paste
addition for mortar mixtures prepared with natural and manufactured sands.
18
c 16
0
=~ 14
!.$ 12
10
Ill
..
Ctl
CL
c
Cll
8
6
4
E
Cll
0 2
.~ 0
~
:;; 0 0
.. ~
:q" 1l
(.)
&~
8_ E
~
0
0
0:
0
1£ ~ 0 il
::; ~.!!
Milder Harsh _ _ _ _ _ _ ____. More

HarshDifficult
Sand
Sand
Figure 12. Reduction in cement paste content with 0.003% VMA s/s at
constant yield stress.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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`,,`,`,,`---
Figure 13. Reduction in yield stress as a function of added cement paste.
20
~16-
18 •
Stress 14
• •
w/\IMA
12
••
10
8 •
6 ••
4
2
•
o-
0 2 4 6 8
Change in Yield Stress(% added paste
Figure 14. Correlation ofVMA and cement paste additions on yield stress of mortar
with various harsh sands. Sands with low response to VMA appear to respond well to
added cement paste.

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V-MAR3 lubricates Not enough energy for Polymer alignment
....
grain surface polymer alignment creates sliding surface
•
Addition of -~'1
-..m
MortarmlX / .•
~'4f
Under low energy Under high energy
(Gravity, finishing) (Pumping, Vibration,
'" ~- '* ....

lab Rheology)
Cement paste ~
Paste volume Grain separation allows Enough separation
separates grains adequate flow creates sliding surface
Figure 15. Mechanism of yield stress reduction as a function ofVMA and

cement paste additions.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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`,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Development of New Superplasticizer
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Providing Ultimate Workability
by D. Hamada, T. Hamai, M. Shimada, M. Shonaka,

and H. Takahashi
Synopsis: Recently, the concrete workability has become regarded as much more
important due to large demands for high durable concrete with low water content
and unstable quality of concrete ingredients. The new superplasticizer was found to
provide better workability controlling the rheological properties of the fresh concrete
than the previous polycarboxylate type superplasticizers regardless of the quality
of concrete ingredients. The framework structure of the new superplasticizer was a
hyper-branched polymer in which specific function monomers were co-polymerized.
The new polymer of the hyper-branched structure was more condensed than that of
polycarboxylate type polymers and was highly adsorptive to cement particles, which
made a higher density of the polymer adsorption onto cement surfaces possible.
This dense and strong adsorption of the superplasticizer polymer molecules provided
the unique rheological properties of the concrete or the mortar such as the lower
viscosity of the concrete giving much easier handling. This new superplasticizer also
provided the robustness against varieties of the concrete ingredients qualities. This
superplasticizer for new generations has already been made practicable successfully
for several constructions, and this technology will bring various possibilities and
merits in concrete construction fields such as shortening the construction period
thanks to better workability.
Keywords: adsorption; cement; EO chain; hyper-branched polymer;

plastic viscosity; rheology; superplasticizer; yield value; workability
Copyright American Concrete Institute 31

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32 Hamada et al.
Daisuke Hamada is Research Chemist of Petfonnance Chemicals Research Laboratories, Kao
Corporation, Japan. M. Eng.
Toshimasa Hamai is Research Chemist of Petfonnance Chemicals Research Laboratories, Kao

Corporation, Japan.
Masaaki Shimoda is Research Chemist of Perfonnance Chemicals Research Laboratories, Kao

Corporation, Japan.
Masafumi Shonaka is Group Leader of Perfonnance Chemicals Research Laboratories, Kao

Corporation, Japan. M. Eng.
Hiromichi Takahashi is Section Manager of Perfonnance Chemicals Research Laboratories of

Kao Corporation, Japan. M. Eng.
INTRODUCTION
The rheological property of fresh concrete or mortar is one of the most important
parameters to detennine the workability in pumping, placing, and filling in a concrete framework.
The fresh concrete has been generally treated as a Bingham fluid [I] according to the following
equation (1) and Fig.l
r = (r - ry) I ?Jpi (1)
where r is the shear rates ofthe Bingham fluid; r is the shear stress; rv is the yield value;
is the plastic viscosity.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
7J p1
The shear rate r which is detennined by the plastic viscosity 7J pi and the yield value
r y represents the mobility of the fluid when the shear stress r is imparted. Therefore, r can
be considered as the representative of a fresh concrete workability. r 1 and 7J p1 can be
controlled by the mixture proportions of the concrete and the superplasticizer, while r depends on
the working condition at the construction site. Thus, the dispersion state of the cement particles by
the superplasticizer in the concrete would affect on the meological parameter r1 and 7J pi •
The dispersion state is controlled by the adsorptive states that are determined by the chemical
features of the superplasticizers.
In recent years, there is an increasing trend toward higher durability of concrete and, for

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example, concrete is endowed with high strength by reduction of the amount of water used therein,
and this trend is estimated to increase in the future as well. The reduction of the amount of water
is effected mainly by using a polycarboxylate-based superplasticizer excellent in water-reducing
properties and fluidity-retaining properties [2, 3, 4, 5, 6, 7]. As the amount of water is reduced,
however, the plastic viscosity 77 p1 and the yield value r Y of the fresh concrete is increased, and
thus there is a problem of reduction in workability. This problem of an increase in the plastic
viscosity 77 pi and the yield value r y is not completely solved even by the polycarboxylate-based
superplasticizer and there is a need for a new superplasticizer having a higher effect of reducing the
plastic viscosity 77 pi and the yield value rY of concrete for the better workability.
Furthermore, various kinds of cements have tended to be used worldwide for ecological
considerations in these days. Hence, the superplasticizers have been also required to meet the
cement compatibilities. The adsorptive properties of polycarboxylate-based superplasticizers were
reported to be effected by the concentration of SO/ ions that was known as the representative
affection by the cement variations on the dispersability [8]. Therefore a more robust, new
superplasticizer, that is not affected by the sol ions concentration and the cement variations, is
desired to be developed in these days.
In this study, a new polymer was developed as a new superplasticizer to provide the
ultimate workability with the lower plastic viscosity TJ pi and the lower yield value r y. and also
provide stable performance independently of cement variations.
MATERIALS AND EXPERIMENTAL METHODS
Molecular and Chemical Structure ofSupemlasticizers
The chemical structure and the molecular structure of the new superplasticizer polymer
(NHBP) are shown in Fig. 2 and Fig. 3 in comparison with the conventional polycarboxylate based
superplasticizer (PC). Polycarboxylate-based superplasticizers (PC) or polyether-based
superplasticizers (PE) have carboxyl units and EO polymer units as the side chains, which are
believed to impart electrostatic repulsion and steric repulsion, respectively [2, 3, 4, 5, 6, 7].
In the new superplasticizer molecule, the carboxyl units are chemically modified by the
hydrophilic anionic groups (Z) to create a stronger adsorptive function. Moreover, the
difunctional monomers are introduced in the structure, so that the molecular structure of the new
superplasticizer is a hyper-branched polymer not like a linear polymer of a polycarboxylate based
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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34 Hamada et al.
superplasticizer shown in Fig. 3.
Figure 4 shows the relationship between the molecular weight and the intrinsic
viscosity of the superplasticizer polymers with the side chain of EO 9 moles, measured by Tri-SEC
RALLS System (Viscotek Model IDA 300 ) which was the integrative analysis system for the gel
permeation chromatography (GPC) with a light-scattering detector, a differential pressure
viscometer and a RI detector. The configuration of the polymer can be estimated by the
coefficient a of Mark-Houwink-Sakurada's viscosity formula (2), the intrinsic viscosity
dependence on the molecular weight.
[77 J = KM" (2)
where T) is the intrinsic viscosity; M is the molecular weight; K, a are Maik-Houwink
coefficients. The index a of PC ( a rc) and NHBP ( a l\'HllP) could be calculated by the
approxlination curve of Fig. 4 as follows.
aPC=0.58 aNJffip=0.22
The smaller a value of the new polymer (a NJ-IBP) indicated more condensed
structure of higher segment density. Generally, a becomes 0.5 ~ 1.0 for a linear polymer and
a becomes- 0.5 for a hyper-branched polymer [9]. This result suggested that the new polymer
structure is a hyper-branched one.
Cement Adsorption Test
Cement and water mixed with 3000 ppm of the superplasticizer were placed in a
cylindrical vessel at W/C = 1.0. Mixing was carried out for 30 seconds. The supernatant liquid
was sep<mtted centrifugally at 3000 rpm from the paste. The total organic carbon content of this
liquid was then measured using Shimadzu TOC-5050A, and the concentration of the
superplasticizer remaining in the supernatant liquid was obtained from a calibration curve prepared
in advance. This yielded the amount of the superplasticizer adsorbed into the cement as the
difference between the amount of superplasticizer added and that remaining in the liquid.
In an other set of tests, 2000 mol/L of Na2S04 wa~ added together with the
superplasticizer solution. The adsorption amount of the superplasticizer with Na2S04 was also
measured to evaluate the effect of SOl ions, on the adsorption amount of the superplasticizers.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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~ortarPTeparatlon
Cement and sand and water mixed with the superplasticizer were placed in the stainless
vessel of a capacity of 1000 ml (and of0 120 mm inside diameter). The mixture proportions and
the ingredients of the mortar are listed in Table 1. Mixing was carried out for 3 minutes at the
rotational speed of 200 rpm by the stirrer Z-2310 (of 0 110 mm with six choppers of 30 mm
height) manufactured by EYELA, measuring the electrical torque that corresponded to the mortar
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
viscosity. The mortar preparation apparatus is shown in Fig. 5. The mortar fluidity was
evaluated by the spread measured when a truncated cone (of 0 I00 mm and 0 70 mm diameters,
and 60 mm height) filled with the mortar was pulled away vertically.
Rheological Properties
The :rheological properties of the mortar samples as referred to the above were
measured by KMS Ball measuring system (where the ball diameter was 12 mm; the arm radius
was 37 mm; the thickness of mortar sample was 50 mm; the vessel diameter was 0 115 mm; the
ball center position was 18 mm higher from the bottom) of MCR500 manufactured by Paar
Physica (Fig. 6). The shear stress dependence of the shear rate was measured (from I0 Pa to 130
Pa for 40 seconds).
Cement Compatibility Test
Cement and sand and water mixed with the superplasticizer were placed in a mortar
mixer at W/C = 0.5. Four kinds of European cements were used for the evaluations. The
mixture proportions and the used ingredients of the mortar are listed in Table 2. Mixing was
carried out for 2 minutes at the low rotational speed of 62 rpm. The mortar fluidity was evaluated
by the spread measured when a truncated cone (of 0 100 mm and 0 70 mm diameters, and 60 mm
height) filled with the mortar was pulled away vertically.
Concrete ~nufacturing
A biaxial-forced mixer with a capacity of 50 liters was used to mix 30 liters of concrete.
The cement and both sand and gravel were placed in the mixer and mixed for 10 seconds, then

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36 Hamada et al.
water containing the superplasticizer was added and the mixing continued for further 90 seconds.
The mixture proportions and the ingredients of the concrete are listed in Table 3. The temperature
of the concrete during mixing, and also the laboratory ambient ternpemture, were held at 20 ±
0.5 oc.
Flowing speed test (Workability)
The concrete flowing speed that was the characteristic index of the workability was
measured when the concrete ran down the tilting lane (23oC) by Tilting Flow Tester manufactured
by Newtech shown in Fig. 7.
RESULTS & DISCUSSION
Adsomtive properties
Figure 8 shows the adsorption amount of the superplasticizers (PC, NHBP) at W/C
= 1.0 with or without Na2S04• The polymer samples for the evaluation were selected to fix the
length ofEO chains (pin Fig.2, p = 9, 23 moles) and 1he molar mtios of the EO chain units (min
Fig.2) in their polymer structures. The new hyper-bmnched polymer (NHBP) showed much
larger adsorption ammmt and was less influenced by sot ions than the polycarboxylate-based
polymer (PC).
The higher adsorption amount ofNHBP could be explained by the compactly arranged
adsorption of the condensed hyper-branched structure on the cement particle surfaces.
The adsorptive force of PC was weaker than SOl ions so that the adsorption of PC
was inhibited by sot ions, as previously reported [8]. On 1he other hand, the adsorptive force of
NHBP was thought to be so strong that the adsorption was not inhibited by SOl ions.
Mortar viscosity
Figure 9 shows the relationship between the mortar fluidity and the viscosity that was
converted from the electrical torque during the mixing. NHBP showed much lower viscosity than
PC at the same mortar fluidity. The lower viscosity meant that the amount of the committed water
by the gathering cement particles was smaller, which suggested that NHBP dispersed the cement
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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particles more finely than PC.
Rheological properties of mortar
To investigate the difference of the rheological properties ofPC and NHBP in details,
their dynamic rheological properties were studied. Figure I0 shows the shear stress dependences
of the shear rate of PC and NHBP at the same mortar fluidity of200 mm. Both PC and NHBP
exlubited the rheological behavior like Bingham fluids. Table 4 shows the plastic viscosity and
the yield value for each mortar sample. As the paste volume in the mortar mixture for PC type
was increased while W/C ratio was constant, both of the plastic viscosity and the yield value were
decreased dramatically, which could be supported by the excess paste theory [I 0].
As can be seen from the figure, NHBP showed much lower plastic viscosity and lower
yield value than PC though the mixture proportions and the mortar fluidity of them were same.
The lower plastic viscosity ofNHBP than that of PC could be explained by the higher
adsorption amount of the superplasticizer molecules, that lead to the denser adsorption state of EO
chains on cement surfaces [11].
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The lower yield value ofNHBP might also be explained by the denser adsorption state
of EO chains on cement surfaces. A yield value of a slurry is supposed to be reflected in the
coagulation state of the particles. The dense adsorption state of EO chain on cement surfaces (m
I) was considered to enhance the repulsive force (Pp) according to the following formula (3)
[12, 13], so that the dispersion state at the dynamic condition became stable and the coagulation state
at the static condition became soft:
PR(h)==kT7ramF [(D0 !hf3 + 1] (3)
where a is the particle radius (m); h is the distance between particles (m); D 0 is the thickness of
adsorbed layer (m); K is Boltzmann constant; Tis the absolute temperature (K); m is the number of
EO chains in one molecule; r is the number of adsorbed molecule per unit area.
The lower plastic viscosity and the lower yield value ofNHBP based superplasticizer
would conduce to better workability in the concrete than PC based one. Furthermore, as can be
seen in Table 4, the required cement paste volume in a concrete mixture design might be able to be
reduced to get the predefined workability for NHBP compared to PC.

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38 Hamada et at.
Cement compatibilities
Figure II shows the compatibility test results ofNHBP compared with the commercial
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
PC based superpiasticizers, PC-EI and PC-E2. The dosage of the each superplasticizer was
determined to get the fluidity of 2I 0 ~ 220 nun when testing CEM I . Although the significant
differences of the mortar fluidity were obseiVed between the cements for the PC based
superplasticizers, NHBP based superplasticizer showed stable mortar fluidity independent of
cement varieties. The robustness against cement varieties of NHBP might be explained by the
stronger adsorptive force.
Concrete tests
Table 5 shows the flowing time, the slump retention and the hardening properties of the
concrete with NHBP based superplasticizers, (NHBP-1, NHBP-2, NHBP-3), the EO chain length
and molar ratio of the components of which were varied each other, and with the commercial PC
based superplasticizer (PC-A). The concrete were manufactured according to the mixture
proportions (WIC ~ 0.35, 0.55) shown in Table 3.
The excellent workability of NHBP based superplasticizers was observed in the
concrete tests. The flowing speed of NHBP-A was much faster than that of PC-A, so that the
better workability ofNHBP was confirmed also through the concrete tests. Figure 12 shows the
comparison of the fresh concrete prepared with NHBP-A and PC-A just after the initial slump test
The fresh concrete prepared with NHBP looked much softer and much more workable as the
gravels in the concrete were homogeneously covered by the mortar layer.
The slump retention and the required dosage ofNHBP-A were similar to those of PC-A,
and NHBP-B and NHBP-C showed better slump retention with higher dosage than PC-A The
setting time ofNHBP-A was almost same as that of PC-A, and the setting time ofNHBP-B and C
were a bit longer than that ofPC-A. Therefore, the slump retention and the setting time ofNHBP
could be controlled freely by adjusting the polymer structure.
The strength developments ofNHBP were slightly better than that of PC. The finer
dispersion state by NHBP based superplasticizer that would lead to the improvement effect of the
cement hydration might explain the superiority in the compressive strength by NHBP.
NHBP based superplasticizers have already been used in many applications both for
ready-mixed concrete and precast concrete, and are currently being used on a daily basis. The

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ultimate w01kability ofNHBP has come to recognition in the rruuket
CONCLUSIONS
I) The hyper-branched polymer with the hydrophilic anionic group was developed as the new
superplasticizer (NHBP).
2) NHBP based polymer showed much higher adsorption amount and stronger adsorptive
force to cement particles than the conventional polycarboxylate type polymer (PC).
3) The plastic viscosity and the yield value of the mortar prepared with NHBP were much
lower than those with PC, which could be explained by the denser adsorption state of EO
chains on cement surfuces.
4) NHBP based superplasticizer appears to be much more robust in terms of stable
performance of the initial fluidity against the cement variations.
5) The better workability induced by NHBP based superplasticizer was confirmed through the
concrete tests.
6) The basic performances ofNHBP based polymer required as a superplasticizer such as the
fluidity retention and the strength development were confirmed through the concrete tests
including the job-site evaluations.
REFERENCES
[I] Tanigawa, Y., "The Fluid Properties ofFresh Concrete", Cement Journal, 2004.
[2] Shonaka, M., Kitagawa, K., Satoh, H., Izumi, T. and Miztmurna, T., "Chemical Structure
and Performance of New High-Range Water-Reducing and Air-entraining Agents",
Superplasticizers and Other Chemical Admixtures in Concrete, Proceedings; Ed. Malhotra,
V., M., 5th CANMET/ACI International Conference, Rome, Italy, 1997, pp.599-614.
[3] Hamada, D., Sato, T., Yamato, F., and Mizunuma, T., "Development of New
Superplasticizer and Its Application to Self-Compacting Concrete", Superplasticizers and
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Other Chemical Admixtures in Concrete, Proceedings; Ed. Malhotra, V., M., 6th
CANMET/ACI International Conference, Nice, France, 2000, pp.269-290.
[4] Izumi, T., Satoh H., Yamamuro, H., Hamada, D. and Mizunurna, T., "A New Hybrid Type
Superplasticizer", 7th CANMET/ACI International Conference, Berlin, Germany, 2003,
Supplementary Papers, pp.67-81, available from CANMET, Canada

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40 Hamada et al.
[5] Ohta, A, Sugiyama, T., and Tanaka, Y, "Fluidizing Mechanism and Application of
Polycarboxylate-Based Supe~plasticizer", Superplasticiz.ers and Other Chemical
Admixtures in Concrete, Proceedings; Ed. Malhotra, V, M., 5th CANMET/ACI
International Conference, Rome, Italy 1997, pp.359-378.
[6] Kinoshita, M., Suzuki, T., Soeda, K. and Nawa, T., "Properties ofMethaciylic Water-soluble
Polymer as a Supe~plasticizer for Ultra High-strength Concrete", Supe~plasticizers and
Other Chemical Admixtures in Concrete, Proceedings; Ed. Malhotra, V, M., 5th
CANMET/ACI International Conference, Rome, Italy, 1997, pp.143-162.
[7] Sakai, E. and Daimon, M., "Dispersion Mechanism of Alite Stabilized by Superplasticizer
Containing Polyethylene Oxide Graft Chains", Supe~plasticiz.ers and Other Chemical
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Admixtures in Concrete, Proceedings; Ed. Malhotra, V, M., 5th CANMET/ACI
International Conference, Rome, Italy, 1997, pp.187-202.
[8] Yamada, K., Ogawa, S. and Hanahara, S., "Working Mechanism of Poly-Beta-Naphthalene
Sulfonate and Polycarboxylate Supe~plasticizer Types from Point of Cement Paste
Characteristics", Superplasticiz.ers and Other Chemical Admixtures in Concrete,
Proceedings; Ed. Malhotra, V, M., 6th CANMET/ACI International Conference, Nice,
France, 2000, pp.367-382.
[9] Aoi, K., Kakimoto, M., "Dendritic Polymer'', N.T.N., 2005.
[10] Kennedy, C. T., "The Design of Concrete Mixtures", Proc. ACI, 28, 1932, pp.419448.
[11] Shirota, K., et al., "Effects of Structures of Polycarboxylate Dispersants on Viscosity in
Concentrated Slurries", J. Am. Ceram. Soc., to be published.
[12] de Gennes, P. G, "Polymers at an Interface; A Simplified View" Review Article, Advances
in Colloid& Interface Science, 27, 1987, pp.189-209.
[13] de Gennes, P. G, "Scaling Concepts in Polymer Physics", 1979.

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Table 1- Themixtureproportionsofthemortarat W/()=(1.40.
Unit content (kWm)
Mix W/C :yip
Water Cement Sand
1 0.40 0.93 289 724 1266
2 0.40 0.86 300 749 1218
3 0.40 0.80 311 777 1166
MaterWI
Cement Nonnal portland cement -Japanese standard type (s.g.: 3.16)
Sand Pit sand (s.g. : 2.63, F.M :234 ;size0-5mm)
Superplasticizer Polycarboxylate polymer (PC EO =9 mol)

New hyper-branched polymer (NHBPEO =9 mol)
sip : volume ratio ofsand to paste s.g. : specific gravity F.M : fineness I1lOdulu<!
* The mixingvolumeofthemortarwas 553 ml/bat.
Table 2- The mixture proportions ofthe mortar at W/C=Q.SO tbrthe cementoompallbility.
Unit content (g)
W/C
Water I Cement I Sand
0.50 225 I 450 I 1350
MaterWI
Cement CEM I 42.SR(Gennany)
CEMIIAM42.5N (AllS1ria)
CEMIIIA32.5 (Italy)
CEMNA42.5R (Italy)
Sand CENs1andardsand DINEN196-1
Supetplastici= Polycarboxylate polymer

(European connnercial products; PC-El, PC-E2)
New hyper-brancbed polymer(NHBP)
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42 Hamada et at.
Table 3- The mixtureJl!UIXXIions ofthe concrete.
S/a Unit content (lqifm3)
Mix W/C
(%) Water Cement Sand Gravel Air
1 0.55 49.7 170 309 895 933 4.5
2 035 48.1 175 500 803 894 4.5
Matniah
Cement Normal portland cement -Japanese standard type (s.g.: 3.16)
Sand Mixture ofpit sand, cnWled sand and mountain sand (40:25:35)
(s.g. : ;2.62 F.M. :2.71 ; size0-5mm)
Gravel Crushed limestone (s.g.: 2.72, F.M. :7.03 ; size 5-20 mm)
Superplasticizer Polycarboxylate type superp~cizer

(Japanese commercial product; PC-A)
New hyper-bnmched polymer (NHBP-A, NHBP-B, NHBP.q
s.g. : specific gravity FM.: fineness modulus
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 4- The meological oonstant ofthe mortar at W/c---0.40.

sip
Mortar Yield value Plastic viscosi1y
sand/paste Superp~cizer
mixture ~y (Pa) 1lp (Pa·s)
vohune ratio
I 0.93 130 13.5
PC
2 0.86 88 12.3
(E09mol)
3 0.80 56 9.1
NHBP
1 0.93 88 7.6
(E09mol)
sip : volume ratio of sand to paste Mortar flow 200 mm

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SP W/C
0.55 0366 165" 6;35 8;50 31.8 41.8
J'C.A
0.35 0.293 <yf3 4;40 6:35 57.4 71.0
0.55 0325 364., 6:40 9:05 33.4 44.5
NHBP
-A
0.35 0275 149" 4:45 6:50 62.8 74.7
0.55 9:40 33.0 44.6

NHBP
-B
035 0313 7:35 62.5 742
0.55 0.450 10:50 32.8 44.5

NHBP
-C
30min
035 0,400 60min 8:25 61.5 74.8
90min
I The dosage was determined to get lhe initial slump of200 mm.)
0~2 The pictures ofthefresh con.cn:te shown in Fig.l2.)
(*3 The flowing speed was measured just after the initial slump test.)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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44 Hamada et al.
·>-
-en
CD
I!!
....
ro
I
I
CD
:J::.
(/)
l:'y
.
Shear stress -r
Fig. 1 -- The rheological behavior of Bingham model. The shear stress dependence of
the shear rates. (-r v : yield value, 11 pt : plastic viscosity)
PC type
NHBP type -fcH,- c

CH,
I
j~ CH~f"'""""""~~:-+.1·;·"""""")
I
cH,-c
'
cH,-c
I
i!
l m I n: I I:
COO(EO)pCH, cooZ j coc: !
: X :
·""'""'";,;""''"~. . . / f,--r )
difunctional monomer cH,
1!
!:...................................!
:
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 2-- The chemical structures of the polycarboxylate polymer-based

superplasticizer (PC) and the new hyper-branched polymer-based

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PC type NHBPtype
EO chain
1111111111111~ ~\............,........,..
Main chain
Fig. 3 -- The molecular structures of the polycarboxylate polymer-based

superplasticizer (PC) and the new hyper-branched polymer-based
0 r-----------------------------~
-0.2
-0.4
~
8 -0.6
Ul
5 -0.8
()
·u;
:S -1
c:
;; -1.2
.3
-1.4 ----~- NHBP ___ _
(E0=9mol)
-1.6
a=0.22
-1.8 L.-______.________...._______...._______.
3.5 4 4.5 5 5.5

Log [Molecular Weight]
Fig. 4-- The relationship between the molecular weight [M] and the intrinsic viscosity
[TJ] oft he superplasticizer polymer with the side chains of EO 9mols.
(Tri-SEC RALLS System)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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46 Hamada et at
1000ml
stainless
vessel
110mm
Fig. 5 -- The complete projection of the mortar preparation.
Fig. 6-- The measuring instrument of the rheological properties, MCRsoo

manufactured by Paar Physica.
Fig. 7 -- The tilting flow tester manufactured by Newtech.
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,```,-`-`,,`,,`,`,,`---
2~00
c
Q)
E
Q) 2000
tf
-
en
en 1500
:!.
c 1000
"E
0
"'c::
0 500
e.
0
"'
"0 0
"' PC-1 PC-2 NHBP-1 NHBP-2
(E0=9) (E0=23) (E0=9) (E0=23)
Fig. 8 -· The adsorption amount of the superplasticizer at W/C = 1.0 with or without
Na 2 50 • (3000 ppm of superplasticizer, 2ooo mol/L of Na2 50)
4
Q)
:::>
~ 3200
Q)
:5 3000
E
,g "'2aoo
al ~
"Iii ~2600
>~
c:
8 2400
~
§ 2200 i-- -------:---
·:;; 2000 ...__ _....__ ___._ ___..._ ____.__ ___.
125 150 175 200 225 250

mortar flow (mm)
Fig. 9 -- The relationship between the mortar fluidity (flow) and the viscosity
converted from the electrical torque when mixing.

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,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
48 Hamada et al.
30.0
''
mortarflO..V :
25.0 --2oomm: -----------:-----------
'i 20.0
!11 . - -
~ l:l.U
----------~---------
- - - - - - - - - - t - - - - - - - - - - _;_
: I •
•
-~~~1!1-~l_ ~----------
m ' '
iii 10.0 ----------~-----------~-----------L----------
:pc
5.0
0.0
0 50 100 150 200
Shear stress E'aJ
Fig. 10 -- The shear stress dependence of the shear rates of the mortar prepared with
PC and NHBP (at W/C = 0-40 and the mortar flow of 200 mm).
280 r:::====~-------,
260 I!ICEM I 42.5R
ClCEMllAM42.5N
240 EICEMmA32.5
~ 220 Ji---=-:=:.:.:..:..:c:.:.::=-:___.J_
-; 200
0
': 180
~
~ 160
140
120
100
PC-E1 PC-E2 NHBP
Fig. 11-- The test results of the cement compatibility in the mortar
(W /C = o.so, PC-E1, PC-E2; European commercial products)

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 12 -- The comparison of the fresh concrete prepared with PC-A and NHBP-A after
the slump test. (W/C = o.ss)

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so Hamada et al.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-23_9_=4
Characteristics of Concrete Containing

a Shrinkage-Reducing Superplasticizer
for Ultra-High-Strength Concrete
by T. Sugamata, T. Kinoshita, M. Yaguchi, and K. Harada
Synopsis: In Japan, the applications of ultra-high-strength concrete having a design

strength of 100 MPa are increasing. Such high-strength concrete offers a number of
advantages: reduced column cross section for greater useable floor area; broader
elasticity range for suppression of earthquake-induced cracking; and longer service
life to meet recent demand in Japan. The potential for the use of this class of concrete
will increase in Japan. However, ultra-high-strength concrete of this strength range
suffers from critical autogeneous shrinkage strain due to its low water-binder ratio
(Silica fume is normally used in such the strength range in Japan). The authors
developed a shrinkage-reducing superplasticizer by mixing a glycol-based shrinkage
reducing component with a superplasticizer for ultra-high-strength concrete
developed by the authors, and studied the properties of concrete containing this new
shrinkage-reducing SPin this strength range.
Compared with plain concrete (without shrinkage reducing component), the
shrinkage-reducing SP reduced the autogeneous shrinkage strain by 15 to 30%,
and drying shrinkage strain by 3 to 25%. The rate of reduction increased as the
W/C decreased and the amount of shrinkage component increased. The authors
determined that the new shrinkage-reducing SP is effective in reducing the
autogeneous shrinkage strain in ultra-high-strength concrete.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Keywords: autogeneous shrinkage strain; compressive strength;

setting time; shrinkage reducing; superplasticizer; ultra-high-strength
concrete

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52 Sugamata et al.
T. Sugamata, Dr. Eng., Research Supervisor of R&D, NMB Co., Ltd. Central
Research Labs.
T. Kinoshita, Researcher of R&D, NMB Co., Ltd. Central Research Labs.
M. Yaguchi, Research Supervisor of R&D, NMB Co., Ltd. Central Research

Labs.
K Harada, Manager of R&D, NMB Co., Ltd. Central Research Labs.
INTRODUCTION
In Japan, the applications of ultra-high-strength concrete having a design strength of

100 MPa are increasing [1]. As of October 2005, the application of concrete having a
strength as high as 130 N/mm 2 was reported [2]. The authors have already reported the
development of a polycarboxylate-based superplasticizer (SP) that imparts high
deformability and reduces viscosity during the period from mixing to final placement of
the concrete in this strength range [3]. Such high-strength concrete offers a number of
advantages: reduced column cross section for greater useable floor area; broader
elasticity range for suppression of earthquake-induced cracking; and longer service life
to meet recent demand in Japan. The potential for the use of this class of concrete will
increase in Japan. However, ultra-high-strength concrete of this strength range suffers
from critical autogeneous shrinkage strain due to its low water-binder ratio (W/B) [4].
To reduce this shortcoming is an important challenge.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
In this study, the authors have developed a new shrinkage-reducing SP by mixing a
shrinkage-reducing component into a SP for ultra-high-strength concrete, and have
studied the effects of this new admixture on both shrinkage reduction and strength
development of concrete. In particular, the effect on strength development was studied
under conditions at high temperature history and of standard curing.
STUDIES ON THE AUTOGENEOUS SHRINKAGE STRAIN OF ULTRA-HIGH-

STRENGTH CONCRETE
Figure 1 shows the results of studies by Kojima et a! concerning the autogeneous

shrinkage strain of ultra-high-strength concrete [4]. The explanatory note in the figure
represents the W/B. The latter indicates the replacement ratio of silica fume. For
example, 20-7.5 represents concrete having a W/B of 0.2 and replacement ratio with
silica fume of 7.5%. The autogeneous shrinkage strain (20-7 .5) of the concrete with a
W/B=20% (7.5% of the ordinary portland cement was replaced with silica fume) reached
600j.Jm at the age of 28 days, and 800J.Jm up to the age of 1 year. As seen in Fig. 2, the
authors used low-heat portland cement with 10% replacement with silica fume as the
binding material, and determined the autogeneous shrinkage strains (up to the age of 1
year) of concretes having low W/B ratios in the range of 0.12 to 0.22. The lower the
W/B, the higher the autogeneous shrinkage strain. The autogeneous shrinkage strain in
concrete with a W/B = 0.12 reached 900J.Jm at the age of I year. On the other hand, the

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drying shrinkage strain, as seen in Fig. 3 [5], decreased as the W/B decreased. That at the
age of 1 year was 400 to 500J..Lm. In other words, in contrast to ordinary-strength
concrete, it is more important to reduce autogeneous shrinkage strain than to reduce
drying shrinkage strain.
So-called lower-alcohol-based and glycol-based shrinkage reducing admixtures have
been used to reduce drying shrinkage [6], and it has been reported that they are effective
in the reduction of autogeneous shrinkage strain [7] in the same manner. In this study, the
authors selected a glycol-based shrinkage-reducing component that had a chemical
structure exhibiting low air entrainment in concrete. This was mixed into the SP for ultra-
high-strength concrete to develop a SP enabling high dispersibility and high reduction in
shrinkage. A study of the physical properties of the concrete containing this new
shrinkage-reducing SP was conducted.
SUMMARY OF TESTING
The authors created three types of newly developed SP (SPSR(l) to SPSR(3))

containing varying amounts of the shrinkage-reducing component. SPSR(3) contained the
greatest dosage of shrinkage-reducing component, followed by SPSR(I) and SPSR(2) in
that order. SPSR( I) contained the standard dosage.
Table 1 shows the test level. The authors used concrete having three levels of water-
cement ratios (hereafter W/C) of0.22, 0.18 and 0.15, and used shrinkage reducing types
SPSR(l) to (3) compared with an superplasticizer (SPH) for ultra-high-strength concrete.
Table 2 shows the mix proportions of concretes. The mix proportion is specified for
the constant water content and constant volume of coarse aggregate per unit volume of
concrete.
Table 3 shows the physical characteristics of the material used. The authors used a
premixed cement containing ordinary portland cement, blast furnace slag, and silica fume
at the ratio of 7 : 2 : 1, that is used for ultra-high-strength concrete in Japan. Andesite-
based crushed sand and stone were used as the fine and coarse aggregates, respectively.
To mix the concrete, the authors used a forced biaxial mixer with a capacity of 100
liters. Mixing was carried out in the following order: I) fine aggregate and cement (for 10
sec.), 2) water and SP (concrete with W/C = 0.22: mixed for 120 sec, 0.18: for 150 sec,
and 0.15: for 360 sec), and 3) addition of coarse aggregate (mixed for 90 sec). Per I
batch, 75 liters concrete was mixed. Immediately after mixing, the authors conducted
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
various measurements and prepared specimens to test the hardened properties. The test
temperature was set at 20°C.
The measured properties of fresh were slump flow, time taken for the flow to reach
the 50-cm point, air content and setting time. The hardened properties were compressive
strength up to the age of 91 days (by standard curing and simple adiabatic curing), and
autogeneous and drying shrinkage strains. The method of measurement for each item is
shown in Table 4.
For simple adiabatic curing, the authors prepared 10 cylindrical specimens (diameter
of 10 em x 20 em in height) sealed-cured and placed in an insulated box (outer
dimensions of 80 x 80 x 80 em, inner dimensions of 40 x 40 x 40 em) as shown in
Figure 4. The internal temperature of one specimen was measured. After sealed curing in

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54 Sugamata et at.
the insulated box for 7 days, the specimens were sealed and cured at 20 degree centigrade
until each age of measurement.
The autogeneous shrinkage strain was measured as follows [8]: An electric strain
transducer with a thermoelectric couple was installed in the center of the mould with
inside dimensions of 1Ox 1Ox40cm as seen in Figure 5. Immediately after placing concrete
into the mould, the whole mould was wrapped with film and placed in a plastic sheet to
be sealed. The start time of the measurement of the autogeneous shrinkage strain was
corresponded with the initial setting time of concrete. The concrete was demolded at the
age of l day after hardening, and the specimen was wrapped again with film and placed
in a plastic sheet to continue to be measured.
Properties of fresh concrete
Table 5 shows the results of the tests of fresh properties. The dosage of SP required
to obtain a slump flow of 70 em increased as the amount of shrinkage reducing
component increased. It increased by 0 to 15% compared with SPH. The dosage of
SPSR(l) containing the standard amount of shrinkage-reducing component increased by
approximately 8%.
The setting time was delayed as the dosage of shrinkage reducing agent increased.
The setting time of SPSR(l) containing the standard dosage of shrinkage-reducing
component was retarded by 15 minutes in concrete with a W/C = 0.22, 20 minutes in
W/C = 0.18 concrete, and 1 hour in W/C = 0.15 concrete compared with SPH.
Properties of hardened concrete
Compressive strength
In general, when concrete with a specified strength of 80 MPa or less is placed into a
concrete column having a relatively large sectional area, it is subjected to high
temperature history at an early age due to a build-up in internal temperature. It is well
known that the compressive strength at the age of 7 days of concrete in an actual structure
is higher than that of concrete cured by the standard method. On the other hand, after the
age of 28 days, the compressive strength of the actual structure is lower than that of the
standard-cured concrete, as seen in Figure 6. However, in Japan, there are some examples
(including the authors' results) of concrete having the specified strength range of 100
MPa or more and exposed in high temperature history at early age, exhibiting a much
higher strength development than that of standard-cured concrete even at the age of 91
days [9,10], as seen in Figure 7. The reason of this is because the W/B ratio is extremely
small in this strength range. As a result, hydration cannot proceed easily under standard
curing conditions, and even by the age of 91 days it is still less than the hydration level of
concrete that has been subjected to a high temperature history at an early age. In other
words, if concrete in an actual structure is subjected to a higher temperature history,
strength development up to the age of 91 days will increase. Therefore, if a shrinkage
reducing admixture that retards setting time of concrete is used in ultra-high-strength
concrete, the retardation will affect the internal temperature history. Therefore, one has to
be aware of the decrease in both the maximum temperature and accumulated temperature.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Figure 8 shows the temperature history during simple adiabatic curing. The effect of
the shrinkage reducing component on the setting varies with the W/C; the times of SPSR
to reach the peaks in the concretes with W/C = 0.22 and 0.18 were almost the same as
that of concretes containing SPH; however, the maximum temperature was somewhat
lower. On the other hand, in concrete with a W/C = 0.15, the time taken to reach the peak
temperature was somewhat retarded compared with SPH, but the maximum temperature
was almost equal.
Table 6 shows the results of the tests of hardened properties. The compressive
strengths up to the age of 91 days by standard and simple adiabatic curing were equal to
or slightly lower than that of SPH, and there was a difference of 5 MPa at the maximum.
However, the strength as a percentage of that of SPH was 97% in the minimum case,
which is a small difference. Strength slightly decreased as the amount of shrinkage
reducing component decreased.
Autogeneous shrinkage
Figure 9 shows the autogeneous shrinkage up to the age of 91 days. The autogeneous
shrinkage of ultra-high-strength concrete containing SPSR decreased by 15 to 30%
compared with that of SPH concrete. The reduction in autogeneous shrinkage increased
as the dosage of the shrinkage-reducing component increased. The absolute value of
reduction increased as the W/C ratio decreased. The autogeneous shrinkage strains of
concrete with W/C = 0.22, 0.18 and 0.15, containing SPSR(l) at the age of 91 days
decreased by lOOJ..Lm, 150J..Lm, and 220J..Lm, respectively, compared with SPH concrete.
The autogencous shrinkage strain of W/C=0.15 concrete containing SPSR( 1) can be
reduced to a level equivalent to that ofW/C=0.22 plain concrete (without the shrinkage-
reducing component).
Drying shrinkage strain (length change)
Figure 10 shows the drying shrinkage strain up to the age of 91 days. The drying
shrinkage of ultra-high-strength SPSR concrete decreased by 3% to 25%, compared with
SPH concrete. In the same manner as the autogeneous shrinkage strain, the shrinkage
reduction increased as W/C decreased. However, there was a difference in the reduction
rate between drying shrinkage strain and autogeneous shrinkage strain in terms of the mix
proportion or amount of shrinkage-reducing component. In W/C = 0.22 concrete,
SPSR(l) at the standard dosage lowered drying shrinkage strain by 15% or so, almost
equal to the 17% achieved by SPSR(3); however, SPSR(2) containing less component
lowered the drying shrinkage strain by as much as 5% or so. In addition, SPSR(l) at the
standard dosage decreased the drying shrinkage strain by l 5% and SPSR(2) containing
less component decreased it by approximately 8% in W /C = 0.18 concrete.
CONCLUSIONS
To reduce the autogeneous shrinkage of ultra-high-strength concrete having the

specified strength of 100 MPa, the authors developed a shrinkage-reducing SP by mixing
a glycol-based shrinkage reducing component with an SP for ultra-high-strength concrete
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
56 Sugamata et at.
developed by the authors, and studied the properties of concrete containing this new
shrinkage-reducing SP in this strength range.
Compared with plain concrete (without shrinkage reducing component), the
shrinkage-reducing SP reduced the autogeneous shrinkage strain by 15 to 30%, and
drying shrinkage strain by 3 to 25%. The rate of reduction increased as the W/C
decreased and the amount of shrinkage component increased. The authors determined
that the new shrinkage-reducing SP is effective in reducing the autogeneous shrinkage
strain in ultra-high-strength concrete. On the other hand, the following negative factors
were also determined: 1) the dosage required to obtain the prescribed slump flow
increased by 5 to 10%, 2) setting time was retarded by 30 minutes to 1 hour, and 3) the
compressive strength decreased by 1 to 5 MPa compared with plain concrete having a
compressive strength of 150 to 170 MPa. We will make efforts to improve these negative
factors.
REFERENCES
1. Yoshimasa Kodama, "Survey on the Actual Placement of High-performance

Concrete," Monthly Ready Mixed Concrete, Vol. 19, No. 4, pp. 59-64, 4, 1999. (in
Japanese)
2. Syusuke Kuroiwa et a!., "Placement of Ultra-High-Strength Concrete with a Specified
Strength of 130 N/mm2 ," Concrete Techno, Vol.23, No.6, pp.9-13, 2004.1. (in
Japanese)
3. Takumi Sugamata et al., "The Effects of a new High-Range Water-Reducing Agent on
the Improvement of Rheological Properties," 2003 Seventh CANMET/ACI
Superplasticizers and Other Chemical Admixture in Concrete, Editor V. M. Malhotra,
SP173-10, 2003, pp. 187-201.
4. Takayuki Kojima et a!., "Study on Shrinkage Characteristics of High-Strength Silica
Fume Concrete," Seventh CANMET/ACI International Conference on Fly Ash, Slag
and Natural Pozzolans in Concrete, Editor V. M. Malhotra, SP199-41, 2001, pp. 719-
735.
5. Akira Ogawa eta!., "Crack Control of reinforced Concrete Structures," Concrete 2000,
Economic and Durable Construction Through excellence, 1993, pp.433-446.
6. Eiichi Tazawa et a!., "Autogeneous Shrinkage Caused by Self Desiccation in
Cementitious Material," 9'h International Congress on the Chemistry of Cement,
Vol.4, 1992 pp.7l2-718.
7. Takumi Sugamata et a!., "Study on the Fresh and Hardened Properties of Concrete
Containing Superplasticizers for Ultra High-Strength Concrete," The First fib
Congress 2002, Session9, pp.87-96.
8. The Japan Concrete Institute, "Method for the Autogeneous Shrinkage test of High-
Plowable Concrete", The Report of Committee on Super-Flowable Concrete (2),
1994, pp.209-210.
9. Hiroshi Jinnai et a!., "Development and Construction Record on High Strength
Concrete with the Compressive Strength Exceeding 150MPa, 7th International
Symposium on the Utilization of High-Strength/High-Performance Concrete, ACI
SP228-65, 2005, pp.1 045-1062.

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`,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
10. Takumi Sugamata et al., "Effect of Silica Fume on the Strength Development of
Concrete Having a Water-Binder Ratio of 18% or Below," ConMat'OS Third
International Conference on Construction Materials performance Innovations and
Structural Implications, 2005.
Table 1 Test level
W/C Kind ofSP

SPH
SPSR(1)
0.22
SPSR(2)
SPSR(3)
SPH
0.18 SPSR(1)
SPSR(2)
SPH
0.15
SPSR(1)
Table 2 Mixture proportions of concrete
3
s/a Unit content (l<g/m )
W/C SP
Water Cement Sand Gravel
(%) Kind Dosflge
SPH Cx1.3%
SPSR(1) Cx1.4%
0.22 48.1 150 682 768 828
SPSR(2) Cx1.35%
SPSR(3) Cx1.5%
SPH Cx1.55%
0.18 43.4 150 833 634 828 SPSR(1) Cx1.65%
SPSR(2) Cx1.55%
SPH Cx1.7%
0.15 37.1 150 1000 489 828
SPSR(1) Cx1.85%
Table 3 Physical characteristics of material
70% ordinary Portland cement

20% blast-furnace slag gypsum
Binder
10% silica fume
3
(Density 2.99g/cm )
Fine Andesite-based crushed sand
3
aggregate (Density 2.63g/cm , Percentage of absorption 2.3%, Fineness modulus 2.812_
Andesite-based crushed stone
Coarse 3
(Density 2.63g/cm , Percentage. of absorption 2.1%, Solid content 60.0%,
aggregate
Maximum size 20mm)

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58 Sugamata et al.
Table 4 Method of measurement
Slump flow JIS A 1150:2001

Time of50cm "Method of test for slump flow of concrete"
JIS A 1128:1999
Air content
"Method of test for air content of fresh concrete by pressure method"
JIS A 1147:2001
Setting time "Test method for time of setting of concrete mixtures by penetration
resistance"
Compressive JIS A 1108:1999
strength "Method of test for compressive strength of test specimens"
Autogeneous Japan Concrete Institute
shrinkage strain "Method for the autogeneous shrinkage test of High-Fiowable Concrete"
JIS A 1129-3:2001
Length change "Method of test for length change of mortar and concrete, Part3: Method
with dial gauge"
Table 5 Properties of fresh concrete

Superplasticizer Slump Air Setting time
W/8 Dosage flow content (hour-min.)
kind
(Cx io)
0
(em) (%) Initial FinishinQ
SPH 1.3 72.5 1.7 5-00 7-00
SPSR(2 1.35 74 1.6 5-10 7-10
0.22
SPSR(1 1.4 75 1.7 5-20 7-15
SPSR{3 1.5 74.5 1.5 5-35 7-25
SPH 1.55 75.5 1.5 5-30 7-00
0.18 SPSR(2 1.55 76.5 1.4 5-50 7-20
SPSR{1 1.65 77 1.3 6-00 7-30
SPH 1.7 70 1.7 4-55 6-45
0.15
SPSRI1 1.85 73.5 1.9 5-50 7-45
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 6 Properties of hardened concrete

Superplasticizer Compressive strength (MPa) Aumgeneous shrnkage Dry ng shrnkege
W/B Dosage Standard Sinpe ad abate Shrinkage test
kind 28day 56day 91day ?day 28day 56day 91day
(Cx%) ?day_ 28dav 56dav 91day ?day 28day 91day
SPH 1.3 112 134 144 150 141 144 147 Strain (•10"") -501 -522 -538 -180 -290 -340 -380
Strain (•1o"") -432 448 -459 -180 -280 -320 -360
SPSR(2) 1.35 111 134 144 146 141 143 144
Reduction{%) 13.8 14.2 14.7 - 3.4 5.9 5.3
0.22 Strain (•10"") 406 -417 -424 -170 -250 -290 -320
SPSR(1) 1.4 108 131 142 148 139 141 144
Reduction (%) 19.0 20.1 21.2 - 13.8 14.7 15.8
Strain (•10-") -359 -364 -366 -160 -240 -280 -305
SPSR(3) 1.5 106 132 139 145 137 139 142
Reduction(%) 28.3 30.3 32.0 - 17.2 17.6 19.7
SPH 1.55 120 140 152 156 158 158 164 Strain ( •1 O-") -614 -638 -651 -150 -240 -290 -330
Strain (•10"") -526 -540 -546 -140 ·220 ·270 -300
SPSR(2) 1.55 123 141 154 155 154 154 160
0.18 Reduction{%) 14.3 15.4 16.1 - 8.3 6.9 9.1
Strain (•10"") -478 -485 -488 -130 -200 -250 -270
SPSR(1) 1.65 119 135 154 153 153 153 159
Reduction (%) 22.1 24.0 25.0 - 16.7 13.8 18.2
Not for Resale, 08/10/2015 01:25:47 MDT
Licensee=UNI OF NEW SOUTH WALES/9996758001
SPH 1.7 123 150 - 158 156 162 170 Strain (•10"") -770 -790 -802 -110 -210 -250 -290
0.15 Strain ( •1 O"") -552 -560 -569 -90 -160 -190 -225
SPSR(1) 1.85 122 152 - 165 158 169 169
Reduction (%) 28.3 29.1 29.1 - 23.8 24.0 22.4
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6o Sugamata et al.
1200
e Metllod 111iag· tlae -bedded
-=tooo
..&
.)II.
1: 800
electric strain pu• traaadacer
•t:
.l!
Ill
Ill 600
~
0
Cl>
1:
Cl>
400
1 200
~
0
1200
-¢-50-0 -Q-50-7.5 -l:r-5&-15 *-30..0
! Cl>
1000 +3o-7.s -o-3o-ts +2o-7.s
"'
~ 800
-e
.c
Ill
Ill 600
=
2
1:
Ill
400
Cl
.s 200
.¥
0
t to 100 1000
Time (Ages)
Explanatory note represents:
The former: Water-binder ratio

The latter: Replacement of silica fume
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
e.g.)
20-7.5: Water-binder ratio 0.2
Replacement of silica fume 7.5%
50-15: Water-binder ratio 0.5

Replacement of silica fume 15%
Figure 1 Result of autogeneous shrinkage strain by Kojima [4]

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`,,,,```,-`-`,,`,,`,`,,`---
200~----------------------------------~
0 --~~ ~---~----·----~---------~---··----~---···---:----·-····:·---------:-···
. ' . ' . . '
c:
:g
Ill
-200 ____ .. J.;~--~--~.-~..J.;.-:-:..~..-:-:--~__j_~~..~---:-:..-:..-:7..:.-:-:..:-:-:..:-:-:..:-:-:..;..:.:-;:,..:-:-..,.,........~.:L:Pc~o·~~----
: : LPC+SF 0.18 : :
G)
til
I o
'I .:
0
~ -400 -- ..... - .' .... -.....' -.... -........

-~.-
.' -.---- ......
. --.".- .... ---
c:
·;:
. ; ; LPC+SF 0.22
~ -600
Ill
:I
2c: -800 . ..
__ .,__________ ... _________ .__________ .____ _LPC+SF .. ----,-
0.15
' '
& . . .
.9 -1000 ········· --------+--------~---------:----------:-- LPC+SF 0.12:----
:::1 ' • ' ' '
<( : : : : :
-1200 +---r---r·--"T·---r·--"T·-------.·___,
4 12 20 28 36 44 52
Age(weeks)
Figure 2 Result of autogeneous shrinkage strain by the authors
0.02 ~----------------f.~::0::jLUPiCC~+:SS~F00~.1iil2
~LPC+SF 0.15
0.00 +--ill-
""-------------1~LPC+SF 0.18
~ ~LPC+SF 0.22
+-.....,,'LT:l.....~:::::-::---)..-----__,
.!o
;
j
~
c -0.04
Ill
'fi
-0.02
t--~,~~~L~~~~~~~~~~~~~~~~~~
~
+----"'·"'-..---------------1
....... OPC 0.55
~ ~ -~
~
g' -0.08 +-----------=~~-
-0.06
-.----... . . . .-.===~----~
....•
-0.10 + - - - - - - - - - - - - - - - - - - - - t
-0.12 +---""'T"--r-.------..........,--..,-._-r....,~,....-.4
4 12 20 28 36 44 52
Age(weeks)
Figure 3 Drying shrinkage strain by the authors [5]

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62 Sugamata et at
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
80cm
Figure 4 Diagram of simple adiabatic curing method
Electric strain transducer with

a thermoelectric couple
r l :.~ ; 'l}om
L.ll<ll~:~~~-:_-:_-_-_-_-_-_-_-40-c_m__-_-_-_-:_-_-_-:~'~'..,~-.J"'~cm
Figure 5 Specimen of autogeneous shrinkage
1 28 58 91
Age(days)
v' Standard cumd specimen /s used to control the strength of

structural concNte up to 91 days
v' it is specified W/B to satisfy the requlmment by pre-adding
the amount of decrease in the strength of structures
Figure 6 Image of strength development around 6o or Bo MPa

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7 28 56 91
Age (days)
" Conventional control method of strength development may not be applied
- Applying another quality control method

by using other special cured specimen
Figure 7 Image of strength development of more than 100 MPa

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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64 Sugamata et al.
80
lw/c=0.221 --SPH
0 70
--SPSR(1)
I!!
3 60 • ·- ·SPSR(2)
!:! - - SPSR3)
a. 50
Ill
E
.! 4!!
i1.)
c
0
t)
30
20
10
80
0
t lw/C=0.1al
2 3
?::l
4 5
--SPH
6 7
0 70
--SPSR(1)
I!! 60
~Ill
· ·- ·SPSR 2)
a. 50
E
s 40
sI!!
1.)
30
c
0 20
t)
10
0 2 3 4 5 fl 7
80
,...
0 70
e
a!:! 60
a. 50
ID
E
.s 40
.se 30
1.)
1:
0 20
t)
10
0 2 3 4 5 6 7
Age Oays)
Figure 8 Temperature history of simple adiabatic curing method
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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0 ~---------------------------,
~
.... lwJc=a.221
~
Gl
J -200 + - - - - - - - - - - - - - - - - - 1
.f
.c
Ill / SPSR(3) SPSR(1)
Ill
::I
------------~-------
1-400
Cl
r~~::::~=========~ SPSR(2)
s::I
4( -600 +---"T"""---r----~---r-----r SPH
0 20 40 60 80 100
Age(Days)
0
{;"
.... lw/C=a.1sl
~
&-200
~
c
·;: SPSR(1)
~ -400
Ill
~ /
·....-r- SPSR(2)
:I
g
5i -600
Cl
"::::
s:I '-._SPH
4( -800
0 20 40 60 80 100
AQe(Davs)
0
.... IW/C=0.151
~ -200
Gl
Cll
·e.c~ -4oo / SPSR(1)

Ill '---
gj -600
2c
& -800
s:I
........_SPH
4( -1000 .-
0 20 40 60 80 100
Age(Days)
Figure 9 Autogeneous shrinkage strain
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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66 Sugamata et al.
0~------------~====~
i; -<r-SPH
E. -100 ~r------------i ~SPSR(1)
-~ -a - SPSR(2)
l
'lii -200 --<>-SPSR(3)
41
i ~00
-~ 4oo ro;===~---------~--J
i!' I W/C=0.221
0
~oo+---,----r---r--~--~
0 20 40 60 80 100
AAe(Days)
0~------------~====~
i; -<r-SPH
:'E.-100 +-'lr-----------l~SPSR(1)
.5 -o - SPSR 2)
i~oof-~~~~~~---~::::::::~
Cll
:f
~~00+--------~~--~~~~-4
"C
~
"'a40oro===~-----------i
~ IW/C=0.18I
c ~0 +----.-----.------.-----.----1
0 20 40 60 80 100
AaeiDavsl
i;
E. -100 1-"H"-....::----------j
c ~~~~"
~ -200 +------==:::::.;:~=====:::il-..__=--,------l
41
"'
~-300+-------------~~~
"C
~
"'
~4oor.;===~----------~
·~ lwtc=o.1sl
0
~00+---,------r--~---,--~
0 20 40 60
Age(Days)
80 100
Figure 10 Drying shrinkage strain
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,``````,,,,```,-`-`,,`,,`,`,,`---
Artificial Superplasticized Aggregates

for Decorative Applications
by G. Ferrari, T. Cerulli, A. Lolli, G. Novella, and R. Pellay
Synopsis: Natural stones have always represented major aesthetic factors in building
construction. One ofthe more ancient and important applications, is the production
of decorative floorings. The most famous example in the flooring field is the "Terrazzo
alla Veneziana". ln recent years, the extensive exploiting of quarries and consequent
environmental problems have reduced the availability of good low cost quality stone.
In the present work, artificial superplasticized aggregates have been produced and
used as decorative elements in this new "Terrazzo" flooring. The substitution of
natural stones with these artificial materials is a first application of new practice.
These aggregates are produced by combining inorganic binders, finely divided
carbonaceous and/or siliceous minerals, superplasticizers and water. The use of
nanostructural polycarboxylate superplasticizers allows to obtain very low water to
cement ratios and, consequently, the final products are characterised by physical
and mechanical properties, similar to those of natural stones. Additional ingredients,
such as pigments and other materials have been added in order to obtain artificial
aggregates with the desired properties and outstanding aesthetic characteristics.
Keywords: artificial aggregates; artificial "Terrazzo" flooring;

superplasticizers

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68 Ferrari et al.
Giorgio Ferrari is research consultant ofMapei, Milan, Italy for new concrete admixtures
and cement additives and is author of several papers and patents on concrete technology
and cement chemistry. He is also expert in environmental sciences and is Government
Delegate for the water pollution control in Venice, Italy and is author of several papers in
this field.
Tiziano Cerulli graduated in organic chemistry at the State University of Milan, Italy.
Since 1989 he has been working as chief in charge of the analytic department of Mapei
Research Laboratory in Milan. He is author of several papers and patents, most of them
in the cement field.
Alberto Lolli graduated in civil engineering at the State University of Milan. He is

presently co-operating with Mapei as expert of applicative tests at the concrete
department of Mapei Research Laboratory in Milan. He is author of several papers on
concrete technology and cement chemistry.
Giovanna Novella graduated in architecture at the State University of Milan. She is

presently co-operating with Mapei in the technical assistance service of the Building
Products Department of Mapei in Milan.
Roberto Pellay is managing director of IN. T.EC., Venice, Italy, a company specialised in
the research and application of new technologies in the environmental field. He is author
of several patents in this field.
INTRODUCTION
Natural stones have always represented an important factor in construction and

architectural design. Since the Hellenistic age, river stones were bound with lime and
clay to create decorative floorings. In the Roman age small stones of different colours
and shapes were incorporated in a mixture of lime and "pozzolana" to cast mosaic floors
(opus tassellatum). It is during the Venetian Republic, that the use of coloured flooring
stones, achieved the highest aesthetic development and the "Terrazzo alla Veneziana"
became famous all over the world (1). Considerable amount of selected stones are used
all over the world, for the aforementioned applications. The desired size of stones is
obtained by crushing blocks of marble, of selected colour and quality. The resulting
ground material can be sieved to obtain fragments characterised, by average dimensions,
in the range 4 to 40 mm. The increasing demand of valuable marbles, has given
significant boost to the decorative applications. However, uncontrolled quarry
exploitation has created, in many cases, environmental problems such as the deforestation
of large areas, with the consequent landscape defacement and the increase of
hydrogeological risks. Furthermore, the storm water washout of the quarries can dissolve
trace metals from the rocks (Pb, Cd, Hg, Ni, Cu, Zn). These trace metals then can be
dispersed in the surrounding areas, increasing the pollution of surface waters and
groundwater. Another environmental aspect is related to the marble block crushing
process, for the small fragment production used in the decorative applications. In fact, a
considerable amount of the blocks pulverised during the crushing process, cannot be
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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conveniently used. The resulting marble powder is a waste material and must be disposed
in controlled sites, with increased costs and further environmental problems. Due to the
aforementioned problems, there are increasing limitations in the availability of stones,
characterised by the desired quality. This is a disadvantage for both the mechanical and
the aesthetic characteristics of the final work.
This paper describes the production and the characteristics of artificial cement
aggregates and their application for the production of artificial stone ("Terrazzo")
floorings. This technique, produces artificial stones of selected colour and size, which are
incorporated in a fresh binder matrix, according to predetermined mixture proportions.
After the hardening of the binder, the subsequent smoothing and polishing operations
emphasize the design and the colour stone effect. The traditional and most ancient
technique, for the casting of the "Terrazzo", employs calcium hydroxide as binder but,
more recently, portland cement and epoxy resins have also been used. In other
applications, selected coloured stones can be combined with different types of binders,
based on both cement and organic resins, in precast elements of various shapes. These
precast elements are used for the creation of decorative objects, such as linings, tiles,
shelves and bases for furniture. Furthermore, natural stones, without a binder, can be used
as important elements in interior and exterior decorative gardens and flower-beds.
PRODUCTION OF ARTIFICIAL AGGREGATES
Process of production
Artificial aggregates are produced by mixing an inorganic filler, such as finely

divided calcium carbonate, with cement, water, pigments, superplasticizers and other
additives. The inorganic filler may consist of other fine inorganic inert materials, such as
silica sand, however the powder material coming from the marble crushing is a suitable
raw material for the production of these aggregates. The production process is normally
conducted by mixing all the ingredients until the mass, which appears like a wet soil,
begins to agglomerate in small grains, having dimensions in some millimeters. In the
second step, these "grain seeds" are transferred in a rotating plate, where the growth of --`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
the grains and the production of a roundish granular material, with the desired size, is
accomplished. The curing of the fresh grains may be conducted in bulk, at ambient
temperature or by thermal treatment. The artificial aggregates, obtained by the
aforementioned process and used for the "Terrazzo" flooring, are shown in Fig. l.
Materials
Six different types of artificial aggregates were produced by mtxmg the

ingredients, in the proportions indicated in Table 1. White type III portland cement,
according to ASTM C-150 with low iron content (Fe20 3 content of0.16 %), was used to
heighten the pigment colour in the final aggregates. The composition and the main
properties of the cement used are reported in Table 2. Ground calcium carbonate with
average fineness of 325 J.lm, was used as filler. Pigments based on metal oxides and
organic dyes powder form, were used to impart the desired colours to the aggregates.

Daneshlink.com
70 Ferrari et at.
Nanostructural superplasticizer (2) (Dynamon SP3 in powder form by Mapei) was used
to reduce the mixing water and to correspondingly improve the physical and mechanical
characteristics of the aggregates. These superplasticizers, because of their particular
chemical structure characterised by polyoxyethylene side chains of very high molecular
weight (Fig. 2, from Ref. 1), modify the morphology and the stability of the early cement
hvdration oroducts. This characteristic is responsible for the favourable induction oeriod
of the ce~ent hydration. The reduction ~f the induction period produced by the
nanostructural superplasticizers, is compared to conventional polycarboxylate
superplasticizers (Fig. 3, from Ref. I). This acceleration of the setting and the hardening
of cement paste, is essential to prevent the deformation and the coalescence of the grains
of artificial aggregates in the fresh state. Calcium stearate, in powder form, was used as
hydrophobic agent to reduce the water absorption of the hardened aggregates. Each
aggregate batch was cured in separate vessels, at 23° C and 95% R.H.
CHARACTERISTICS OF ARTIFICIAL AGGREGATES
Physical and Mechanical Characteristics
The typical artificial aggregate particle size distribution is shown in Fig. 4. It is

important to observe, that the most abundant fraction size (4 - 12 mm) is the most
preferred for decorative applications. In addition, the fractions passing the 2 mm mesh
sieve and retained on the 12 mm mesh sieve arc very low. This indicates that the process
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
produces artificial aggregates of suitable gradation and excellent yield. These aspects, in
conjunction with the strict control of colour by the dosage of the selected pigment or
mixtures of pigments, make these artificial aggregates much more uniform, in term of
aesthetic characteristics, as compared to natural stone. Table 3 shows the physical and
mechanical characteristics of the different artificial aggregates. These results confirm the
combined effect of the reduction of W /C and the addition of calcium stearate in reducing
water absorption of the aggregates. Particularly, the addition of calcium stearate is
necessary to reduce water absorption below 4 per cent. Furthermore, the addition of
calcium stearate does not produce any adverse effect on the resistance to abrasion and
wear, which resulted comparable to those of natural stones (3).
Water to cement ratio- The mixing mass, during the production process appears
quite different from that of conventional cement mixtures. Although the concept of
flowability cannot be applied in this case, the results confirmed a surprising and
remarkable effect of the superplasticizer on the amount of the water necessary to form the
artificial aggregates. As already pointed out by other authors (4), the addition of the
superplasticizer to a cement mixture results in the liberation of the water that normally is
entrapped inside cement particle agglomerates. In this case, the higher amount of
available water makes the mixture more wet and increases the plasticity and the
stickiness of the "grain seeds". The rotating plate generates larger agglomerate growth to
the final aggregate size. The test results of Table 3 confirmed that the reduction of the
mixing water greatly improves all the physical and mechanical characteristics of the final
product.

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Density -- The density of all artificial aggregate samples were measured
according to EN 1097-6 method. The results indicated that only the aggregates with the
lowest water to cement ratio (sample 4, 5 and 6) met the quality standards ofUNI 8520-2
norm (MY> 2300 kg/m 3). Superplasticizer is an essential ingredient for the production of
aggregates meeting the requirements of this aggregate standard for concrete.
Water absomtion - Water absorption was measured according EN 1097-6

method for all the samples. In this case, only aggregate sample 6, which showed a water
absorption lower than 1 per cent, met the requirements for structural concrete in the most
severe applications (reinforced concrete exposed to freezing and towing cycles and
deicing salts, class XF according to norm 206-1 ), while aggregate samples 4 and 5, which
showed water absorption of 4.5 and 2 per cent, respectively, met the requirements for
concrete not exposed to corrosion risk (classes XO and XCI, according to norm EN 206-
1). These results indicate that calcium stearate, thanks to its hydrophobic effect, is
essential, in combination with the superplasticizer, to reduce the water absorption of the
artificial aggregates and to meet the acceptance requirements ofUNI 8520-2 norm (water
absorption s I %).
Colour stability - The pigments used for the production of artificial aggregates
are based on metal oxides or organic compounds stable to the light and in the alkaline
environment of cement mixtures and no change in the colour of the aggregates was
observed with ageing. Furthermore, the addition of calcium stearate can effectively
prevent the efflorescences from calcium hydroxide produced by cement hydration, when
the aggregates are used for outdoor applications.
Resistance to abrasion and wear -- Abrasion and wear tests were conducted only
on samples from 4 to 6 according to methods EN 1097-2 and 1097-1, respectively. In all
the cases, the results indicated that the aggregates showed an excellent resistance both to
abrasion and wear, comparable to or higher than the natural aggregates. In fact, as
reported by other authors, typical values of the Los Angeles abrasion test for basalt,
limestone, quartz and granite are 14, 26,28 and 38, respectively (5).
TERRAZZO FLOORING PRODUCTION PROCESS
A mixture of different colours of artificial aggregates (red, yellow and brown)

produced in accordance with the proportions of Sample 6 were used to cast a "Terrazzo"
flooring of an apartment in Venice (Italy). A fast setting and early high strength
superplasticized levelling mortar was used as a binder for the aggregates (Ultratop by
Mapei). This premix mortar is based on a combination of quick-drying and quick-setting
binders, silica sand, synthetic resins and superplasticizers. The mixture hardened very
quickly, so that after few hours the flooring could be walked on. After two days, the floor
could be subjected to the smoothing and polishing operations.
Preparation and Casting of the Mixture - Artificial aggregates, water and mortar were
added to the cement mixer in the following proportions.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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72 Ferrari et al.
Artificial aggregates Binder (Ultratop) Water
25 kg 25 kg 5 kg
The cement mixtures were poured and levelled over a concrete screed,
previously treated with a synthetic primer, at a thickness of about 20 mm by means of a
levelling bar. The paving was air cured for two days, before starting smoothing and
polishing operations.
Smoothing and Polishing the Hardened Mixture - The hardened raw surface was
worked with a dry-smoothing machine to remove the first 5 mm of the surface, which
exposes the aggregate colour and shape. A phase of the smoothing process in shown in
Fig. 5. By changing the fineness of the abrasive heads, the same machine has been used
for polishing operations, giving a final surface with large colour attraction (Fig. 6). In Fig
7, the appearance of the final beautiful "Terrazzo" flooring is shown. Finally, the floor
was treated with a synthetic sealant and waxed.
CONCLUSIONS
The results of this work describes a new application of superplasticizers, for the
production of artificial aggregates, which can be used for decorative applications with
excellent aesthetic characteristics. The function of the superplasticizer is to disperse
cement particles, and release the water entrapped by the cement and the filler
agglomerates. The superplasticizer also makes "grain seeds" previously formed and
favours their agglomeration in a rotating plate. The use of nanostructural superplasticizer
combined with hydrophobic agents, such as calcium stearate, allows high yield
production of artificial aggregates, with physical and mechanical characteristics, suited to
be used as concrete aggregates. On of the most fascinating applications of the artificial
aggregates is the production of"Terrazzo" flooring.
REFERENCES
1. Crovato, A., "Pavimenti Veneziani", L'Altra Riva, 1989 (in italian)

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
2. Clemente, P., Dal Negro, E., Ferrari, G., Gamba, M., Surico, F., "Nanostructural
Superplasticizers for In-Lining Concrete in Underground Projects", in
Applications of Nanotechnology in Concrete Design, Editors R.K. Dhir, M.D.
Newlands, L.J. Csetenyj, Thomas Telford Pub!, 2005, 97-104
3. Orchard, D.F., "Concrete Technology", Vol. Ill, Properties and Testing oj

Aggregates, Applied Science Publisher, London, 1976
4. Dodson, V., "Concrete Admixtures", Van Nostrand Reinhold, New York, 1990,
pp. 39-40
5. Collepardi, M., "Scienza e Tecnologia del Calcestruzzo", Hoepli, 1987, p. 263

(in italian)

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Table 1. Composition of the different artificial aggregates
Sample Calcium
Cement Water CaC03 Pigment Superplasticizer
Stearate W/C
N. (%) (%) (%) (%) (%)
(%)
I 24.9 12.5 61.2 1.8 0.0 0.0 0.50
2 25.9 8.7 63.4 1.9 0.1 0.0 0.34
3 26.3 7.3 64.3 1.9 0.2 0.0 0.28
4 26.4 6.9 64.4 1.9 0.4 0.0 0.26
5 26.3 6.9 64.3 1.9 0.4 0.2 0.26
6 26.2 6.9 64.1 1.9 0.4 0.5 0.26
Table 2. Composition and characteristics of the cement used
Cement brand Composition/Characteristic

ASTMType III
Si02 % 26.22
AI,Ol % 3.62
Fe,03 % 0.16
CaO % 64.79
MgO % 0.92
K 20 % 0.14
Na20 % 0.74
sol % 3.24
Ti02 % 0.05
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
CrzOJ % O.o7
Mn02 % 0.05
c,s % 39.9
c,s % 45.1
C 3A % 9.3
C.AF % 0.5
Mean particle size J.liD 29.70
Volume of particles below 40 ~m % 80.2

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74 Ferrari et at.
Table 3. Physical and mechanical characteristics ofthe different artificial
aggregates
Resistance to Resistance to
Sample Density Water Absorption
Abrasion Wear
N. (kglm3) (%)
(LA units) (MnE units)
I 1990 10.0 - -
2 2060 6.9 - -
3 2290 5.5 -
4 2350 4.5 22 13
5 2340 2.0 21 13
6 2340 1.0 22 14
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 1- The artificial aggregates used for the "Terrazzo" flooring.
High Mw PEO I
I (4,000-6,500) ~
E
c
....
lowMwPEO
(750-1,500) ...
0
4.5 nm *l!!ll!ll!l!!!!l!l!l!!ll!l!lll!
29.5 nm 19.3 nm
Conventional PC Nanostructural PC
Superplastlclzar Superplasticizar
MW50.000 MW61.000
Fig. 2- Schematic and simplified representation of the molecular structures and

dimensions of conventional (left) and nanostructural (right) superplasticizers
(from Ref. 2).

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30
NANOSTRUCTURALPC CONVENTIONAL PC
28
.u
""
1-
26
24
22
20
0 5 10 15 20 25
TIME (HOURS)
Fig. 3- Thermal development curves of cement mixture containing conventional and

nanostructural PC superplasticizers cured at 20°( (from Ref. 2).
50
Q40
w
;!;
~30
w
a:
Z20
s~ 10
11.
12 8 passing 1
SIEVE MESH (mm}
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 4 ·Typical particle size distribution of artificial aggregates.
Fig. 5- Detail ofthe dry-smoothing process of the "Terrazzo" flooring.

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76 Ferrari et al.
Fig. 6- Particular of the "Terrazzo" after dry-polishing and finishing.

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 7- The final "Terrazzo" flooring with the artificial aggregates.

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SP-239-6
Behavior of Mortars with

Different Dosages of Shrinkage
Reducing Admixtures
by A. Bettencourt Ribeiro, A. Carrajola, and A. Gon~alves
Synopsis: To analyze the performance of two shrinkage reducing admixtures (SRA),

tests have been performed, in order to evaluate the influence of increasing dosages
of the admixtures. Shrinkage, compressive strength and weight loss have been
measured. The efficiency of the admixtures in controlling autogenous and drying
shrinkage was evaluated using sealed and unsealed specimens. As the accepted
mechanism of action of these products is the reduction on surface tension of the
capillary liquid of concrete, surface tension of water solutions was also determined
to compare the shrinkage reduction with the decrease of surface tension. Mixtures
with four different dosages of each SRA were prepared. The results indicate that
shrinkage reduction is not proportional to the decrease of surface tension. Secondary
effects such as changes in the evaporation rate and in the compressive strength
of specimens have to be considered. Results of sealed specimens are not fully
consistent with the accepted main mechanism of action of these products.
Keywords: shrinkage; shrinkage reducing admixtures; surface tension

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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78 Bettencourt Ribeiro et al.
A. Bettencourt Ribeiro is PhD researcher, concrete division of materials department,
Portuguese National Laboratory of Civil Engineering.
Ana Carrajola is civil engineer, Master of Science
Arlindo Gon~alves is Principal research officer, chief of concrete division of materials

department, Portuguese National Laboratory of Civil Engineering
INTRODUCTION
The control of shrinkage is needed when external or internal restraint induces stresses
higher than the tensile strength of concrete. The reduction of shrinkage may also be
necessary in long bridge structures due to an increase of second order effects. In order to
decrease shrinkage deformation of concrete, a simple solution is the use of shrinkage
reducing admixtures (SRA) 1-6 . The accepted mechanism of action of these non-expansive
products is surface tension reduction of capillary pore solution 1•6 . Knowing that the
surface tension of a solution of water and SRA is proportional to the content of SRA, and
considering surface tension decrease the only effect of these admixtures on concrete, we
can expect proportionality between shrinkage reduction and admixture dosage, assuming
valid the liquid depression given by Young-Laplace equation (1/:
2cr
p -p 1 =-case (I)
g r
where Pg is the gas pressure, PI the liquid pressure, cr de surface tension of liquid, e the
contact angle and r the capillary radius. In fact, this is not the case and the use of a SRA
leads to changes on concrete other than surface tension reduction of pore liquid8- 11 •
Shrinkage mechanism, at constant temperature, may be divided in two parts: autogenous

shrinkage, which includes chemical shrinkage and self-desiccation shrinkage; and drying
shrinkage which is due to water evaporation. Self-desiccation and drying shrinkage leads
to decrease of relative humidity (RH) in the pore structure. The RH decrease promotes
depression on the capillary water, changes in disjoining pressure and increase of surface
free energy 12- 17 • With a SRA, the presence of molecules of the chemical admixture in the
interstitial pore liquid may also change the rate of evaporation and, consequently, the RH
profile, and possibly affect the surface energy of the solid, assuming that the adsorbed
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
liquid contains SRA molecules. The change in surface tension not only has a direct effect
of decreasing the liquid depression, but also indirectly changes the mobility of the
adsorbed water in the pore structure 18 •
This study does not investigate the existence of these different mechanisms in mortars
with SRAs, but rather evaluates the overall influence of increasing dosages of two
different SRAs on total (unsealed specimens) and autogenous shrinkage, flexural and
compressive strength, and mass loss of mortar specimens. The results help to identify
changes in these properties that can be used to better understand secondary effects when
using this kind of products.

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MATERIALS
Nine mortar mixtures were prepared using portland cement, CEM I 42.5 R, (Table l ), in
accordance with EN 197-1; siliceous sand, in accordance with CEN standard sand
described in EN 196-1, two liquid SRAs, SRA-0 (high molecular weight polyglycol) and
SRA-K (alkyl-ether), Table 2, and distilled water. The mixing of mortars was performed
following EN 196-1. The dosages of each batch are presented in Table 3. The SRAs were
diluted in distilled water.
TEST METHODS
The following tests were performed on the nine mixtures: flexural strength, compressive
strength, weight loss, total shrinkage and autogenous shrinkage. The compressive
strength was measured according EN 196-l standard. Mass loss and shrinkage were
measured on 40 mm x 40 mm x 160 mm prisms, prepared according to EN 196-1. The
prisms were removed from the moulds at 18 hours. The prisms for autogenous shrinkage
measurements were then sealed with several plastic sheets and placed in a closed plastic
box, to avoid water drying, in a laboratory room at 20±2 °C. The prisms for mass loss and
total shrinkage measurements were put in a laboratory room at 20±2 oc and 65±5 % RH.
In addition to tests on mortars, surface tension measurements were performed in solutions
of distilled water and SRA. The measurements were made with a Kl2-Tensiometer, from
KROSS GmbH, using the plate method, at 20 oc.
Shrinkage deformations of each specimen were measured using a length comparator,

sensitivity of 1 J.lm, and gage studs on the end sections of the mortar prisms. Stability of
the length comparator was checked by a reference invar bar. The mass loss was measured
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
on the prisms for shrinkage tests. Each result presented is the average value of three
measurements.
RESULTS AND DISCUSSION
Influence of SRA on strength
Tables 4 and 5 present flexural and compressive strength results, respectively. The
strength decrease, in percentage, with the SRA dosage is presented in Figs. 1-2. Fig. 1
shows a significant decrease of the flexural strength with increasing SRA dosage at 18
hours. However, at later ages the difference between reference and SRA mixtures is
reduced, being very small at 90 days. Fig 2 shows a similar trend on compressive
strength, but the difference remains clear at later ages, being about 20 % at 90 days with
the highest dosage of SRA. The different behavior on flexural and compressive strength
al later ages may be related with the conservation of the specimens. The prisms for these
two tests were kept under water, as specified in EN 196-1. The flexural strength mainly
depends on the tension resistance of surface layers of the specimens. For long periods of
contact between mortar and water, the leaching of interstitial pore liquid on the surface
leads to a similar superficial pore structure of the prisms with or without SRA. This
phenomena has minimal influence on compressive strength which mainly depends on

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So Bettencourt Ribeiro et al.
mass behavior. The two SRAs, 0 and K, show a tendency to decrease the strength, but
the influence of the dosage of SRA does not show similar trends at all ages. The
reduction of initial hydration rate by the two SRAs is evident by the analysis of the
results at 18 hours. However, at early ages the mortars with lower dosages of polyglycol-
based SRA (0) show a tendency to exhibit lower strength reduction. On the contrary, at
later ages and for higher dosages of SRA, the results show an opposite behavior. It means
that the two SRAs have different influences on hydration rate and hydration extent.
Influence of SRA on surface tension
Fig. 3 shows surface tension of solutions made with distilled water and the SRAs. The
graphic on the right, Fig. 3b, is an enlargement to show better surface tension changes for
usual contents on interstitial pore structure. The SRA 0 is shown to be more efficient in
reducing surface tension. The product alone, 100 % SRA, has a surface tension of about
30 mN/m, at 20 °C.
Influence of SRA on mass loss
Fig. 4 shows the mass loss ofthe specimens used for total shrinkage measurements. Mass
loss of the specimens used for autogenous shrinkage was also measured, and the higher
result obtained was 0.18% at 181 days (an evaporation rate lower than 0,001 %/day),
which was considered low enough to despite the mass exchange.
In general, the mass loss of non-sealed specimens of SRA mortars was higher than the
mass loss of reference specimens. The evaporation increased for higher SRA dosages.
The performance of the two SRAs tested was similar for low dosages, but diverge for
high dosages. Particularly, the mixture with 3% of polyglycol-based SRA 0 evidenced a
high initial drying rate. The main difference between the mortars 04 and K3 was detected
at two days. This worse behavior of04 can be attributed to the low surface tension of the
interstitial pore liquid and to the low initial rate of hydration (see also strength increase
between 18 hours and 2 days, Figs. 1-2 and Table 4-5). The results show that the mass
loss does not depend only on the surface tension, but also on the pore structure. Figs. 3-4
show that the surface tension variation of the pore liquid between 03 and 04 is small, but
the increase of mass loss is very high. Changes in pore structure, which leads to different
mass losses, may modify not only RH profiles but also hydration conditions of surface
and inner parts of the specimens. These phenomena may have major effects on total
shrinkage results.
When extrapolating these results for concrete specimens it is necessary to account for
different surface/volume changes. As reported by others4•6•8•9 •10, the mass loss of SRA and
reference mixtures is not much different. In fact, with the exception of mixture 04, which
had a significant increase of water evaporation in the first days, despite the high value of
surface/volume of the specimens and the short period of cure, the difference between
reference and SRA mortars is less than 1%. For concrete specimens with much lower
surface/volume values and longer periods of cure, the negative effect of the possible
increase of water evaporation rate due to SRA is not expected to be significant in
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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increasing shrinkage. However, the change of mobility characteristics of the pore fluid,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
due to changes in surface tension 18 , and possible curing effect promoted by increase of
SRA concentration at the surface9 , is expected to have beneficial effects on reducing
shrinkage.
Influence of SRA on autogenous shrinkage
Fig. 5 shows autogenous shrinkage of the nine mortar mixtures (contraction represented
by positive values). The results indicate that the two products perform differently but
both are effective in reducing autogenous shrinkage. The differences between SRA 0
and SRA K mortars are not only on the amplitude of shrinkage reduction, but also on the
relative behavior, which depends on SRA content and age. At later ages SRA 0 seems to
decrease continuously the autogenous shrinkage with the dosage, which is not the case
with SRA K, which shows approximately the same shrinkage at 181 days for all dosages
of SRA. At early ages, and for 2-4 % of admixture, the results indicate a higher potential
of the alkyl-ether SRA (K) to decrease autogenous shrinkage.
The influence of SRA on autogenous shrinkage may be due to: changes in chemical
shrinkage rate, modification of the solid part of the pore structure due to differences in
hydration rate, changes in internal pore filling and mobility of the pore liquid due to
surface tension reduction; modification of surface free energy and disjoining pressure due
to the presence of SRA molecules in the pore structure. The different chemical nature of
the SRA products, polyglycol (0) and alkyl-ether (K), may have influence on all these
mechanisms. The chemical structure of SRA molecules was not provided by the
manufacturers. However, if the SRA molecules are adsorbed on the C-S-H particles, a
high molecular weight of the polyglycol SRA may increase the gap between two
neighboring C-S-H surfaces, which increases the drying shrinkage 15 , but not the chemical
shrinkage. On the contrary, the hydration delaying effect of SRA should decrease the
chemical shrinkage. Analyzing Figure 2, it is clear a higher influence of SRA on
compressive strength at early ages. Comparing this indirect measure of the hydration
level with the autogenous shrinkage shown in Figure 5, which shows a higher effect of
the SRA at later ages, it is suggested that the effect of SRA on the hydration reactions is
not the dominant mechanism of shrinkage reducing provided by SRA. The autogenous
shrinkage depends on the hydration level as well as the viscoelastic behavior of the
mortars. Using the compressive strength as an indicator of elastic modulus and relaxation
capacity, mortars with higher content of SRA are expected to exhibit, for the same
chemical shrinkage, higher autogenous shrinkage at early ages and lower autogenous
shrinkage at later ages. The higher shrinkage at early age is due to the decrease of elastic
modulus. At later ages, the presumed higher relaxation capacity of the mortars with more
SRA (in fact, it is well known the deep increase of creep coefficients when the structures
are in charge at early ages 19) is responsible for lower autogenous shrinkage values. To
better understand the early age results of autogenous shrinkage it should be taken into
account that shrinkage deformations were measured only after 18 hours. Beginning the
measurements at this time, part of the deformations due to chemical shrinkage was not
recorded. Considering the chemical shrinkage between 18 hours and 2 days as charge on
the specimens skeleton, due to the internal restrained decrease of volume, and using the

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
compressive strength of the specimens as a measure of the hydration during this period, it
can be concluded that all the specimens have approximately the same charge (increase of
about I 0-13 MPa on compressive strength). This is not absolutely correct, once a
difference of 3 MPa may be relevant, but this simplification can be useful for the
analysis. Considering equal chemical shrinkage, higher deformation on the specimens
with more SRA may be expected, due to their lower strength. However, from the
autogenous shrinkage results, the increase of SRA seems to counteract this tendency. At
later ages, the effect of SRA on strength decrease is less pronounced, and the prevalent
phenomenon is the beneficial effect of the SRA on internal forces causing shrinkage.
Influence of SRA on total shrinkage
Fig. 6 shows total shrinkage. Total shrinkage may be considered as a sum of autogenous
and drying shrinkage. However, when measuring autogenous and total shrinkage in
different specimens, drying shrinkage is not the difference between total and autogenous
shrinkage, since the hydration conditions are not the same in free and sealed specimens.
In spite of this, the autogenous part of total shrinkage in unsealed specimens and the
autogenous shrinkage of sealed specimens should exhibit similar tendencies of variation
with increased SRA dosages.
As observed for the sealed specimens, the influence of the SRAs on total shrinkage is
higher at later ages, but with different effects. Additional dosages of SRA 0 seem to be
effective only until about 1.5 %. Comparing with Fig. 5 after 28 days, it can be observed
that for dosages greater than 1.5 % there is an inverse tendency of autogenous shrinkage
in relation to total shrinkage. This indicates a significant increase in drying shrinkage
with higher dosages of SRA 0, the polyglycol product. Fig. 4 indicates only a small
increase of mass loss after 28 days, but in Fig. 6 a significant increase of total shrinkage
is observed, which suggests a worse behavior in drying shrinkage of mortars with high
content of high molecular weight polyglycol (SRA 0), which is consistent with the
hypothesis of an increased gap between C-S-H surfaces.
The increase of the dosage of alkyl-ether product (SRA K) was efficient until 3 %. A
slight increase of the total shrinkage was observed between 3 % and 4 % of this SRA, at
all ages. Fig. 4 indicates a continuous increase of water loss with increasing dosage of
SRA. The autogenous shrinkage of SRA K mortars indicates no systematic variations
with increase of SRA dosage, showing similar values at 181 days. At this age, the
different behavior on total shrinkage can be attributed to drying shrinkage. The
simultaneous effect of decreasing the surface tension and increasing the rate of
evaporation may have opposite global effects on drying shrinkage. Between 1% and 3 %
the first effect seems to be dominant, assuming capillary pressure the mechanism of
shrinkage reducing, while, for higher dosages the increase of the water evaporated
becomes as relevant as the additional decrease of surface tension. However, this simple
analysis does not take into account other physical phenomena that may occur in the pore
structure due to changes in solid and liquid phases. In fact, surface free energy and
disjoining pressure depend on surface area of hydration products, al well as, the
dimension of the pores, and they are not only dependent of surface tension or rate of

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evaporation. The nature and the amount of the molecules present in interstitial solution
interfere in the solid pore structure formed during hydration and on the relation between
amplitude of deformations due to chemical or drying shrinkage.
Additionally, it is important to note that extrapolation of results on small mortar

specimens for large specimens of concrete should be made with care. The influence of
changes on humidity gradient, due to SRA, depends on the porosity of the concrete and
on the environmental conditions. Furthermore, in this study the specimens were subjected
to a very short period of cure, 18 hours. Despite differences in specimen size and period
of cure, the results obtained in this study and in other work performed in concrete
mixtures 6, provide comparable values of total shrinkage reduction.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
CONCLUSIONS
Based on the results obtained, with two commercial SRAs, the following conclusions
may be drawn:
• SRA tends to delay hydration reactions and decrease the long term strength;
• SRA is efficient in reducing both autogenous and total shrinkage;
• shrinkage reduction is not proportional to decrease of surface tension;
• an optimum dosage of SRA to decrease total shrinkage that depends on the type of
SRA exists;
• shrinkage reduction seems to depend not only on surface tension reduction but also on
changes of disjoining pressure and surface free energy;
• early and long-term shrinkage reduction due to the use of SRAs seems to depend on
changes of viscoelastic properties at early ages and on molecular weight ofSRA.
REFERENCES
1. Shah, S.P.; Karaguler, M.E.; and Sarigaphuti, M., 1992, "Effects of Shrinkage-
Reducing Admixtures on Restrained Shrinkage Cracking of Concrete", ACJ
Materials Journal, V.89, N° 3, May-June 1992, pp. 289-295.
2. Berke, N.S.; Dallaire, M.P.; Hicks, M.C.; and Kerkar, A., 1997, "New
developments in Shrinkage-Reducing Admixtures"; Superplasticizers and Other
Chemical Admixtures in Concrete: Proceedings of the Fifih International
Conference CANMETIACJ, Rome, Italy, 1997 (SP-173), ed. V.M. Malhotra,
American Concrete Institute, pp 971-978.
3. Folliard, K.J. and Berke, N.S., 1997, "Properties Of High-Performance Concrete

Containing Shrinkage-Reducing Admixture", Cement and Concrete Research,
Vol.27, No.9, September, pp. 1357-1364.
4. Ribeiro, A.B.; Goncalves, A.; and Carrajola, A., 2002, "Shrinkage Reducing by
Chemical Admixtures", Structural Concrete 2002: National Meeting, Lisbon,
November 27-29, ed. Grupo Portugues de Betao Estrutural (Portuguese National

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Laboratory of Civil Engineering, LNEC) pp 87-96 (only available in
Portuguese).
5. Gettu, R.; Roncero, J.; Martin, M.; and Agull6, A., 2002 "Experimental Study of
Concretes Incorporating Shrinkage Reducing Admixtures", Report C-409811,
Universitat Politecnica de Catalunya, Barcelona, Spain, March, 15 pp.
6. Ribeiro A.B.; Carrajola. A.; and Gonvalves, A., 2003, "Effectiveness of

shrinkage reduction admixtures on different concrete mixtures",
Superplasticizers and Other Chemical Admixtures in Concrete Proceedings oj
the Seventh CANMETIACJ International Conference, Berlin, Germany, October
2003 (SP-217), ed. V.M. Malhotra, American Concrete Institute, pp 299-310.
7. Adamson, A.W., Gast, A.P., 1997, Physical Chemistry of Surfaces, 6th Edition,
Wiley-Interscience, John Wiley & Sons, Inc., New York, pp 784.
8. Roncero, J., Gettu, R. and Martin M., 2003, "Evaluation of the influence of a
shrinkage reducing admixture on the microstructure and long-term behavior of
concrete", Superplasticizers and Other Chemical Admixtures in Concrete
Supplementary papers of the Seventh CANMETIACI International Conference,
Berlin, Germany, October 2003, pp 207-226.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
9. Bentz, D.; Geiker, M.; and Hansen, K., 2001, 'Shrinkage-reducing admixtures
and early age desiccation in cement pastes and mortars", Cement and Concrete
Research, V. 31, N° 7, July, pp 1075-1085.
10. A. B. Ribeiro, A. Gonvalves, A. Carrajola, 2006, "Effect of Shrinkage

Reduction Admixtures on the Pore Structure Properties of Mortars", Materials
and Structures, V. 39, May, RILEM Publications.
11. Weiss, J. and Berke, N., 2003, "Admixtures for reduction of shrinkage and
cracking", RILEM Report 25: Early Age Cracking in Cementitious Systems,
RILEM Publications, pp 323-335.
12. Powers, T.C., 1965, "Mechanism of shrinkage and reversible creep of hardened
cement paste", The Structure of Concrete and Its Behaviour Under Load:
Proceedings of an International Symposium, London, Septemberi965, Cement
and Concrete Association, pp. 319-344.
13. Baroghei-Bouny, V. and Godin, J., 2000, "Experimental study on drying

shrinkage of ordinary and high-performance cementitious materials", Shrinkage
of Concrete - Shrinkage 2000: Proceedings of an International RILEM
Workshop (PRO 17), Paris, October, RILEM Publications, pp. 215-232.
14. Hansen, W., 1987, "Drying shrinkage mechanisms in portland cement paste",
Journal ofthe American Ceramic Society, V. 70, N° 5, pp. 323-328

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15. Beltzung F. and Wittmann, F.H., 2005, "Role of disjoining pressure in cement
based materials", Cement and Concrete Research, V.35, N° 12, December, pp.
2364-2370
16. Baroghel-Bouny, V., 2003, "Hydration and moisture distribution", RJLEM

Report 25, Early Age Cracking in Cementitious Systems, RILEM Publications,
pp. 39-45.
17. Bisschop, J., 2003, "Drying shrinkage cracking at early ages", RJLEM Report
25: Early Age Cracking in Cementitious Systems, RILEM Publications, pp. 47-
55
18. Srinath, M., 2002, Wetting on flexible substrates: formulation, PhD thesis,
Drexel University, Philadelphia, 318 pp.
19. Lange, D.A. and Altoubat, S.A., 2003, "Early Creep," RJLEM Report 25: Early
Age Cracking in Cementitious Systems, RILEM Publications, pp. 57-62.
Tabl e I -- Prroperttes o f cement CEMI425

Physical Chemical
Compressive strength - 2 days (MPa) 27,3 Chlorides (%) 002
Compressive strength • 28 days (MPa) 50 3 Sulphates (%) 3,0
Soundness (mml I Insoluble residuel%) 0,8
Initial setting time (min.) 148 Loss on ignition (%) 3,4
Fineness (Blaine) m 2/kg 401
Density 3,12
Table 2 -- Chemical admixtures•

Admixture Main component Recommended dosage
high molecular weight 3
SRA-0 7.5 L/m
polyglycol
SRA-K alkyl-ether 0.5-2% of weight of cement
*Information provtded by the manufacturer
Table3- M'JXture roporttons

SRA
Cement Sand Water %of
Mortar K 0
(g) (g) (mL) cement
(mL) (mL)
weil[ht
REF. . . 0
01 - 3.4 0.8
02 - 6.7 1.5
03 - 10.1 2.2
04 450 1350 225 - 13.4 3.0
Kl 4.5 - 1.0
K2 9.0 - 2.0
K3 13.5 . 3.0
K4 18.0 - 4.0
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Table 4 --Flexural strength (MPa
REF. Ol 02 03 04 Kl K2 K3 K4
18h. 3.87 3.31 3.40 2.72 3.09 2.97 2.42 2.59 2.16
2d. 5.33 4.84 4.92 4.47 4.68 4.50 4.27 4.53 4.19
7d. 7.06 6.95 6.23 6.40 6.30 6.25 6.00 6.02 6.01
28d. 8.11 7.85 7.82 7.73 7.42 7.31 7.46 7.61 7.37
60d. 8.56 8.44 8.07 7.81 7.47 7.97 7.93 7.88 8.28
90d. 8.16 8.13 8.09 7.72 7.67 7.57 8.14 7.86 7.98
Table 5 --Compressive strength (MPa)

REF. Ol 02 03 04 Kl K2 K3 K4
ISh. 15.6 15.3 13.8 9.9 9.2 11.8 9.5 9.8 7.7
2d. 27.3 27.2 24.7 21.8 19.6 24.6 21.4 22.2 20.7
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
7d. 41.1 41.2 36.4 36.0 30.6 36.8 33.0 34.9 32.2
28d. 50.3 49.0 49.6 46.8 39.5 47.6 47.7 45.1 42.5
60 d. 56.6 56.0 50.3 46.8 44.1 51.2 51.9 48.4 45.7
90d. 58.4 56.8 51.8 51.0 47.4 51.5 53.8 49.6 47.2

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---·~--------====---.
18 hours I•K •ol 100 -----'-'--'"--------,

I• K •ol
i'Ett:s§i2
50 .
0.0% 1.0% 2.0%
.
3.0%
.
4.0%
~
i
90
80
gc 70
11
t=-";~~~:::::::t:=-----1
-t-------~~~
60-t------------~
ro+---,----.--.--~
0.0% 1.0% 2.0% 3.0% 4.0%

SRAdosage SRAdosage
7days 28days ~
e- 1oo ·~--.::::=~----------, e _1oo
;: ~ 90 r==_-;;:.~.~~~=i il ~ 90
.....= 8070 -+-------·~-==""='--j
~ ~ i 80 +---- ----1
~
~!
c t------------j
60 - t - - - - - - - - - - - - j
ti..
~
70
60+----
~ ro+------,--------l ro+---.---.--.---~
0.0% 2.0% 4.0% O.OOA. 1.0% 2.0% 3.0% 4.0%

SRAdosage SRA dosage
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
60 days I• K • o I 90days ~
_1oo l='=1t::!S~:::;~~~
e~~90 e _1oo
~ il:;. 90
:. =
> c
eo +---------------_,
"' 70 +----------------1
~ ~ 80 - ------·-
i! 60
~
---------
50 +--.,----.,----.-----1
>i :~ -----·--
0.0% 1.0% 2.0% 3.0% 4.0% 0.0% 1.0% 2.0% 3.0% 4.0%
SRAdosage _ _ _ _ _SRA dosag_e_ _ _
Figure 1 -- Relative flexural strength between reference and SRA mortars.

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18hours ~ 2 days I•K •ol
~
. 1001 ··--.s·
~~90
!tE =s:
.---~ 60
.
JJ'Ej~s%q
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
& 40+---~---.---.--~
0,0% 1,0% 2,0"/b 3,0%
SRAdosage
4,0%
(."' "' '·"" '·"' '·"" '·"' SRAdosage
7 days 28 days c;K..-o]

. 100.-~-------------. . 100--~--~------------,
h· 90 +-'-".c.::-:-:-::,.,~
. .,....=-:--.----c::---\ I :;- 90 ~-----~-=--=·s·.::::'~:::•=-·-...-.~--1
ti ~g t====-=--=--=-~-=-~~·,_·...;·_·;.;.~~·o=·
-~;;.;;· ""1.,..
[ c BO -l---------.;::.:_:--'ii·=·-·.-J
~ i 70 +-----------------1
..
~Esc+---------------~ =: j BO +-------------------1
.; .. 50 +---------------~ i .. 50 +---------------1
a: 40 +---~---.---.--~ a: ~+----~---.--~------1
0,0% 1,0% 2,0% 3,0% 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
SRAdosage SRAdosage
60days ~ 90 days I• K • o I
,; 100 .. ,...__ . • .; 100 .,_,.._=,..,..._~----.---------,
~""""'.,._,~~------j
.. - 90 +------II eieo+---~---~~~~=-----1
~ ~ BO +-------~--~ ..,·_··..,•.--·_::_··:._,·~-.,.. "-- BO +----·--___-.:..:...:..:_·~·,--,;.:!l~·c.:;.·-~·="·•._.
~,70+------------------~~ Ei 70 +---------------.;---1
..8 !c so +-------------------1
i~so++==============j
&"'50
40+---~---.---.---4
Jl! .. 50 +-----------------~
~ 40+--~--~--.--~
0,0% 1,0% 2,0% 3,0% 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
SRAdosage SRAdosage
Figure 2 -- Relative compressive strength between reference and SRA mortars.
80 -,-------------------, so~--------------·
~70 fro
sao r:;:Kl S.so 1-iH<l
~
c
~
~~
140 t-- --- --------
------------------ !so -
Jl 40
La
"
Ul
~~
0
3
-----------------
" 20+-~--.--~--.-~
~+--~--~-----.--~
0% 20% 40% 80% 80% 100% 0% 2% 4% 6% 8% 10%
SRA content ('lQ SRA content('IQ
(a) (b)
Figure 3-- Surface tension of solutions with distilled water and SRAs.

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Superplasticizers and Chemical Admixtures in Concrete
~0 2 days 7 days 1--K -+-ol

7,0 ~-----------,
6,0 - 6,0
~5,0 ~
., 5,0
~4,0 J 4,0 ---------------------

i3,0
i 2,0 .....=~ .... ~'=-::-::-:":c-::-::-:-:1 I ::~ ~- --------~ ~ ~ ~ ~ ~ ~ ~
1~ ---------------------
1,0 ------------------- I
0,0 +---~----,--~-....,
0,0
0,0% 1,0% 2,0% 3,0% 4,0%
0,0% 1,0% 2,0% 3,0% 4,0%1
SRA dosage(%) SRA dosage(%)
7,0
6,0
li=.
5,0
4,0
3,0
:;; 2,0
1,0
0,0 0,0 -1---~--~-~--J
0,0% 1,0% 2,0% 3,00,(, 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
SRA dosage (%) SRA dosage(%)
90 days --- K -+- o

7,0
~0 ---------- -- 6,0 - - - -- - - - - - - - - - - -- - - - --
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~ 5,0 ~ 5,0 -- --- ------ --- --
i 4'0 L:.::;::~:;_::....,..~.:ot'-'=-=-1 k=:~~=-,A.----:--:-:_--,

ift 4,0
j~::;
3,0
o.o
0,0% 1,0% 2,0%
·'
3,0% 4,0%
I
II! 2,0
1,0
- - - -- - - - - - - -- - - - - - - - -
---------------------
0,0 -+--~---.--~--1
0,0% 1,0% 2,0% 3,0% 4,0%
SRA dosage (%) SRA dosage(%)
Figure 4 --Mass loss of the prisms used for total shrinkage measurements.

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90 Bettencourt Ribeiro et at.
2 days 1.-K -+-O 7 days
~ ::: ~ - - - - - - - - - - - - - - - - - - -I o,5o 1 j
!
~ i :·::s-~~~~~~~~~~~~~~~~~~
ji" E. o,2o
0" 030+ ---------------
1i 0:201~~~~--------------- '
----- -----------
~~ 0,10t::=s?:::----t ~~ 0,10t---~
0,00 0,00
0,0% 1,0% 2,0% 3,0% 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
SRA dosage (%) SRA dosage (%)
28 days 1---K -+-01 60 days

0,50 ~----------.
0,50 , - - - - - - - - - - - - ,
.;-0,40 -------------------- .;- 0,40--------------------
.0
1 i0,30 ~--------=-=._---- --- g 0,30T
~
j .li! 0,20 - - - - - - - -~..,_,,_;:,...,_~,_., t E o20 - - - - -_--.~""-=---------..1
" c
oO('C ~ ·E ' I
~0,10 -------------------- ~ 0,10 ~-------------------
0,00 -1-----~--~-___j 0,00 +1 --~--.--~-___j

0,0% 1,0% 2,0% 3,0'A. 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
SRA dosage(%) SRA dosage (%)
....._K...,._O
181 days
0,50 , - - - - - - - - - - - - - - - - ,
.;- 0,40
!~
g .e 0,30
j} 0,20
~.e
i 0,10
0,00 .J-----~--~--- 0,00 +----~---.------,----1
0,0% 1,0% 2,0% 3,0% 4,0% 0,0% 1,0% 2,0% 3,0% 4,0%
SRA dosage (%) SRA doaage (%)
Figure 5 --Autogenous shrinkage.

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7 days
... 0.80 . . . - - - - - - - - - - - . . ,
.E 0.60 '~
! 0.60 --------------------
t
·E .ro.4o ~ ~ 0.40 --- -
!ii 0.20 --------------~----j ~• ~ rl-:~~,_,-~~~~,.;::;::-~--.1

0.20 + ,..
0.00
.......... :::-;:__ I 0.00 +-----~-----1
0.0% 1.0% 2.0% 3.0% 4.0% 0.0% 1.0% 2.0% 3.0% 4.0%
SRA dosage ('IQ , SRA dosage(%)
28days GO days
0.80...-------------,
! 0.60 & 0.60 ~ --- -- ....-- --------

i.r -..:::::: ...___
~'b f ;! 0.40 ------~ ------------
~ .... 0.40
~.!!.
·~
~ 0.20 ~ 0.20
0.00 -l--~--~--...----1 0.00 +--------,...--~

0.0% 1.0% 2.0% 3.0% 0.0% 1.0% 2.0% 3.0% 4.0%
4.0% I
SRA dosage (0~
SRA dosage (%)
~------------------------~
-a-K-+-0 181 days ---K-+-0

90 days
080 ,,- - - - - - - - - - - - , 0.80 . , - - - - - - - - - - - - - ,
& 0.60 --- j 0.60

i- '
~ ~ 0.40 - - - - -- - - - - -- - --- - --- ~ 'f 0.<40
!·~
0.20 - - - -- - - - - - - - - - - - - - -- J-" ~
0.20
0.00 -l--~---,----.----i
0.00 +--~--~--...----1
0.0% 1.0% 2.0% 3.0% 4.0% 0.0% 1.0% 2.0% 3.0% 4.0
SRA doaaga (%) SRA dosage (%)
Figure 6 --Total shrinkage.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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92 Bettencourt Ribeiro et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-7
Studying Admixtures with the

sC Rheometer
by R.J. Flatt and I. Schober
Synopsis: Testing of admixtures performance is done routinely in industrial

laboratories with spread tests in which a cylindrical mould is filled with cement paste
and then lifted. The sample spreads and the measured diameter is used to infer the
efficiency of the admixture. Recent results link this measurement quantitatively to
yield stress. On the other hand, expressions for the dependence of yield stress on
interparticle forces and volume fraction of cement have been proposed. In this paper,
it is shown that the combination of both approaches brings new insights into the
mechanisms by which admixtures modify the rheology of cementitious materials.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Keywords: admixtures; adsorption; rheology; superplasticizers

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,,,,```,-`-`,,`,,`,`,,`---
94 Flatt and Schober
Robert J. Flatt is head of inorganic chemistry in Corporate Research at Sika Technology
(ZUrich, Switzerland). He has a PhD (1999) in materials science and a chemical
engineering diploma from the Swiss Federal Institute of Technology in Lausanne (EPFL).
In 2003, he was awarded the RILEM Robert L'Hermite Medal in recognition of his
contributions to the understanding of admixture behavior in cement and concrete.
Irene Schober received her Ph.D. in Chemistry from the Technical University of Vienna.
She is head of the Polymer Synthesis Department of Corporate Research at Sika
Technology AG in Zi.irich, Switzerland.
INTRODUCTION
The rheology of cementious materials is profoundly affected by dispersants as in
any agglomerating system. In the case of cementitious, materials, one must worry not
only about interparticle forces but also about the impact that dispersants have on cement
hydration, which may not only affect the strength development but also rheological
properties in the fresh state.
In cementitious materials, dispersants are referred to as superplasticizers. The
latest type of these are comb-type copolymers with an poly-carboxylic backbone and side
chains of polyalkylene oxide. The ionic groups on the polymer backbone allow the
polymer to adsorb on the surface of fine particles that include cement, fly-ash, filler and
silica fume (if enough positive ions can assist the adsorption), while the polyethylene
oxide side chains induce steric repulsion that causes dispersion of these particles.
This type of polymer offers the possibility to perform a wide range of changes in
the molecular structure of the polymer. Also, producers of admixtures for cementitious
materials seek to understand the impact of varying molecular structure on the rheology of
cementitious materials. In doing so, they are confronted to systems in which not only the
degree of dispersion but also hydration can impact a given macroscopic property.
While trying to master these effects, industrial researchers largely opt for simple
and quick tests that offer an indication of the flow properties of the materials. In the case
of admixtures, a mini slump test consisting of a cylindrical mold of 50mm in diameter
and 50mm in height can be used to assess flow (see for example Kinshita et al2000). The
mold is filled with the suspension and then lifted, and the diameter of the spread sample
is measured. Surprising relations are reported in a separate paper (Schober and Flatt
2006) showing a linear relation between this diameter and polymer adsorption (Figure 2).
In this paper the possible origin of this unexpected result is examined in the perspective
of mechanistic characterization of the performance of superplasticizers.

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BACKGROUND
Yield stress and spread

In recent papers, Roussel and coworkers was established that, at low spreads, the
diameter of the spread is related to yield stress by (Roussel and Coussot 2005 and
Roussel et al2005):
T =4 pVg (1)
0 .J3 nD2
where pis the density of the sample, Vis its volume, g is the gravity constant and Dis the
spread diameter.
The result in the above equation differs only slightly from what was initially
proposed by Murata (1984), but Pashias and coauthors probably came up with the most
eloquent description of this test "the 5c rheometer"(Pashias et al. 1996).
At large spreads, the same authors indicate that the link between spread diameter
and yield stress is given by:
2
(2)
T
0
= 55.904pV 2 D- 5 - AD
4V
where Jc is a constant linked to the liquid vapor interfacial energy and the wetting angle
on the plate.
The value of A. is fitted to the model and is given by Roussel et a! (2005) to be

0.005. This factor becomes important at spreads larger than 230 mm for the case of
samples from a cylinder 50mm diameter and 50mm high, which is examined here.
Furthermore, for that mould geometry, Flatt et al. (2005) proposed to use an
exponential function to interpolate between both functions. The graphics reported in
support of this are given in Figure Ia, where the predictions of equations (I) and (2) are
shown. Figure I b gives the proposed interpolation.
Thus, the spread diameter can be related to the yield stress with an exponential
function:
T0 = a£exp(-bD) (3)
Po
where a and b are fitting parameters given in Figure I b and which depend neither on the
polymer nature nor on the volume fraction of the suspension. It must be emphasized that
those coefficients are for a cylinder of 50mm diameter and 50mm high. The reference
density Po is 2.25 g/cm3 for the value of a given in the Figure 1.
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Correlation between spread and adsorption
In another paper submitted to this conference, the spread results obtained with
different polymers, all dosed at 3 mg/g with respect to cement mass are reported and
show a linear relation with the adsorbed amount of polymer (Schober and Flatt 2006).
Details on the experimental protocol which involved determining adsorption by solution
depieiion are given in the same paper. These resuits concern a given "famiii; ot
polacrylate type polymers and therefore cannot be extended to any other type of polymer
without precaution. Nevertheless, within the given type of polymer studied, a rather wide
variety of chemical structures was investigated.
DISCUSSION
The relationships presented between yield stress and spread are rather
unexpected and are now examined in further detail. It should be emphasized that the
dominant effect of superplasticizers on fluidity of cementitious systems is attributed to
changes of interparticle forces (Yoshika et al. 1997, Lewis et al. 2000, Flatt 2001, Flatt et
al 2004). Thus the existing knowledge about yield stress from other suspensions than
cement can be used.
An important reference in this respect is found in a review of work of Boger's
group (Zhou et al. 2001 ). Indeed, their results show that yield stress can be written as a
product between interparticle force and a function of the volume fraction of solids <j>. This
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
function can be written to account for the number of interparticle contacts as well as a
divergence as maximum packing is approached (Flatt and Bowen 2005):
(4)
where Fmax denotes the maximum attractive force among particles, a is a numerical
constant and./(¢) is a function that accounts for the volume fraction dependence of yield
stress.
Such expressions were developed for homogeneous systems. However, in the
case of cement suspensions, not only are the particles composed of various phases, but in
most cases of practical interest, their surfaces are not fully covered by the added
dispersant. Nevertheless, it is assumed that equation (4) remains valid provided an
adequate average force is used.
Combining Eqs. (3) and (4), the spread diameter can be written as:
(5)
which, for a given volume fraction, can be written in a more convenient way by
introducing a constant, {J, that only depends on the volume fraction of solids <j>:
1 (6)
D = P--Ln(F
b max
)

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This approach has shown good results for flocculated alumina suspensions (Flatt
and Bowen 2005) and MgO suspensions with various superplasticizers adsorbed to full
surface coverage (Kjelsen et a!. 2005). However, limitations appeared in that case when
incomplete surface coverage occurred. A solution was proposed to evaluate the average
interparticle forces, by determining an average force based on the weighted contributions
of forces among two surfaces both without polymer, both with polymer or one with and
the other without polymer:
Fmax ~ ((1- ey Fmax,B-8 + 28(1- B)Fmax,B-P + e2 Fmax,P-P) (7)
where {}is the fraction of the total surface covered by the polymer indices, B and P refer
respectively to portions of the surface that are either bear or contain adsorbed polymer
(ex: Fmax,B-B is the maximum attractive force among two particle that are in contact with
protions of their surfaces that do not contain adsorbed polymer).
If the dispersant is powerful enough to cancel attractive forces between any two
surfaces of which at least one is covered with the said polymer, then:
~ (1- e)
2
Fmax FmaxB-B (8)
The authors emphasize that the surface coverage should be expressed in terms of
the saturation plateau of an adsorption isotherm, but with respect to real complete
coverage. Assuming that under the later condition all these polymers would occupy the
same surface area per unit mass of polymer, then Bcould be expressed as:
(9)
Equations (6), (8) and (9) lead to:
2 {10)
D = {3 2 - y;Ln(moo- m)
An alternative approach is to assume that the average force between the surface
is estimated from a separation distance, 8, that is assumed to be proportional to surface
coverage. In this case Fmax can be expressed as (Flatt and Bowen 2005):
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
F
max
::::::5-2 :::::: g-2 (11)
which leads to:
2 (12)
D= /33 +-Ln(m)
b
The above equation does not require any assumption with respect to the value of
the saturation dosage. It turns out that a logarithmic fit to the data gives a fit which is just
as good as the linear relation previously proposed, as indicated in Figure 3.

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Despite the fact that the nature of the dependence between yield stress and
admixture adsorption can be correctly captured, its magnitude is not correct. Indeed, the
prefactor of the logarithmic fit is 186, while as the value expected from Eq. (12) would be
60 (the value of b is 0.035 mm' 1). If it is assumed that the saturation level is between 2
and 3 mg/g, which is consistent with the adsorption plateau of the most strongly
adsorbing polymer, then the fit would be similarly insufficient with Eq. (10).
There are a number of possible explanations for these discrepancies. One reason
might be that part of the polymer is lost to hydration reactions. Indeed, Flatt and Houst
(200 I) argued that this can happen with hydrating aluminate phases, probably leading to
the formation of some amorphous phase that does not contribute to dispersion (Flatt and
Houst 200 I). The difficulty resides in providing a reliable estimate of this amount of
adsorbed polymer.
Alternatively, adsorption isotherms are considered. When plotted as adsorbed
amount versus polymer that is remaining in solution, all polymers seem to show an initial
vertical rise (Figure 4). This can be associated to an irreversible adsorption. Furthermore,
as indicated in Figure 4, all polymers can be fitted assuming the same initial irreversible
adsorption, m0 , and the same saturation plateau, moo, using a modified Langmuir isotherm
of the type:
(13)
where msoi is the amount of polymer in solution.

The irreversible adsorption step can probably be associated with higher
interaction energies, which is not easily handled by Eq. (7). A solution to this problem is
to use a corrected surface coverage excluding this irreversibly adsorbed portion such as
shown in Figure 4 and which would lead to:
2 (14)
D= /] 3 + -Ln(m- m 0 )
b
when the value ofm 0 is set to 0.84 which is estimated from the fitted curves in Figure 4, a
much better correlation could be found as indicated in Figure 5.
In this case, the agreement is much better between the experimental data and the
predicted behavior. However, the assumption of excluding the irreversibly adsorbed
amount as well as its estimation would need further validation. A number of alternative
solutions could also be considered to account for the same initial discrepancy between the
measured and predicted values. This is, however, beyond the scope, of this paper, but will
be reported elsewhere at a later date. Thus, at this stage this result should only be taken as
an indication that the general approach to analyzing simple flow experiments in terms of
interparticle forces may provide much more insightful information than expected up to
now.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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CONCLUSIONS
In this paper, yield stress measurements were interpreted using the 5c rheometer.
In this test, the spread radius of a cement paste initially placed in a cylindrical mold can
be linked to yield stress. On the other hand, it is assumed that the dependence of yield
stress on interparticle forces and volume fraction of solids are separable. Both
assumptions lead to a logarithmic dependence between spread and adsorption that is
observed experimentally. However, the magnitude of this dependence was not captured
quantitatively. There is a possibility that reversible and irreversible adsorption must be
considered separately. Assuming the initial irreversible adsorption step as well as the
same saturation plateau for all polymers, a much better quantitative relation between
experiment and theory can be found. Although this result remains preliminary, it strongly
suggests that simple spread experiments may provide much deeper information than they
have been assumed to do so far. This is good news for industrial laboratories that use
these tests daily because of their extreme simplicity.
REFERENCES
Flatt R.J., 2001, "Dispersants in concrete", Chapter 9 in Polymers in Particulate Systems:
Properties and Applications, Ed. Hackley V.A., Somasundran P. and Lewis J.A.,
Surfactant Science Series. Marcel Dekker Inc., pp. 247-294.
Flattt R.J. and Houst Y.F., 2001, "A simplified view on chemical effects perturbing the
action ofsuperplasticizers", Cern. Caner. Res., V. 31, pp. 1169-1176.
Flatt R.J., Martys M. and Bergstrom L. , 2004, "The rheology of cementitous materials",
Mat Res Bull. V. 29, No.5, pp. 314-318.
Flatt R.J., Larosa D. and Roussel N., 2006, "Linking yield stress measurements: spread
test versus Viskomat", Cern Caner Res, V. 36, pp. 99-109.
Flatt R.J. and Bowen P., 2006, "YODEL: a Yield Stress Model for Suspension", J. Am.
Ceram. Soc, V. 89, No.4, pp. 1244--1256.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Kinoshita M., Nawa T., Iida M. and Ichiboji H., "Effect of Chemical Structure on
Fluidizing Mechanism of Concrete Superplasticizer Containing Polyethylene Oxide Graft
Chains", 6th CANMET/ACI International Conference on Superplasticizers and Other
Chemical Admixtures in Concrete, Nice, France, 2000, ACI SP-195, V. M. Malhotra
(Ed.),pp 163-179.
Lewis J.A., Matsuyama H., Kirby G., Morissette S. and Young J.F., 2000,
"Polyelectrolyte effects on the rheological properties of concentrated cement
suspensions", JAm Ceram Soc 83, pp. 1905-13.

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too Flatt and Schober
Murata J., 1984, "Flow and deformation of fresh concrete", Mater. Constr. V. 17, No. 98,
pp. 117-129.
Pashias N., Boger D.V., Summers J., and Glenister D.J., 1996, "A fifty cent rheometer
for yield stress measurement". J. Rheol., V. 40, pp. 1179-1189.
Roussel N. and Coussot P., 2005, "Fifty-cent rheometer" for yield stress measurements:
from slump to spreading flow" J. Rhea/., V. 49, No. 3, pp. 705-718.
Roussel N., Stefani C. and Leroy R., 2005, "From mini cone test to Abrams cone test :
measurement of cement based materials yield stress using slump tests", Cern. Caner.
Res., V. 35, pp. 817-822.
Schober I. and Flatt R.J., 2006, "Optimizing Polycarboxylate Polymers", in Proc. 8th
CANMETIACI Conf on Superplasticizers and Other Chemical Admixtures, Sorrento, Ed.
Malhotra M., in press.
Yoshioka K., Sakai E. and Daimon M., 1997, "Role of steric hindrance in the
performance ofsuperplasticizers in concrete",J. Am. Ceram. Soc., pp. 2667-2671.
Zhou Z., Scales P.J. and Boger D.V., 2001, "Chemical and physical control of the
rhoelogy of concentrated metal oxide suspensions", Chern Eng Sci, 56, pp. 2901-2920.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
a)
1000~ -~~~-
- Rouluel approecllwtchoVI:IntartlelallaniiOfl
----- Rouatelapproachwwilt!IJ1terfaebdlllnlkln
'~ 100
......... Ermrwithod•urfaeatan&ion
100 t--. --r-- 75 [

'iii' c;-- c
0
!!:. ac
..... s
...I
10 50
I
1i
;: '- ~
.....-----...
/
25 !
0
10 15 20 25
Spread dlamatar [em]
b) o Combined data
7 • Data for regression 25
" relafive e1TOr
6 ....
15 2':.
'iii' 5 ""
!!,. " ~
" ~
"'"' 4
" 5
e-
~ 3 ..!l
!I " .5:
;E_2 """1:. " -5 E
_g
z 1
...... 1:.
A
6 -15 g
0- w
-1 -25
5 10 15 20 25
Spread diameter [em]
Figure 1. Interpolation between models in Eqs. (1) and (2), a) predictions of both
models, b) minimum yield predictions of both models as well as data selected for
the interpolation are shown as open and filled squares respectively. Open triangles
indicate the error from the interpolation.

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230~-------------------------.
210+---------------------
E 190 +-----------------,~07""~
.§.. 170 +-------------~~
i :E FE
~ 150 +------------:7"""'-----
----------1
1.0 1.2 1.4 1.6 1.8

Adsorption (mg polymer/g cement)
Figure 2. Linear dependence between polymer adsorption and diameter of paste
spreads. All points were obtained for a dosage of 3 mg polymer per gram of cement.
230~-------------------------.
210 y = 186.29Ln(x) + 101.56

e 19o R
2
= 0.9927
.§.. 170
~ 150
ii: 130
j
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
110
.... 90
70
50 -+-----..----r-----r-----1
1.0 1.2 1.4 1.6 1.8
Figure 3- Data from Figure 2 fitted with a logarithmic function (continuous line) and a
linear regression (discontinuous line).

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2.5
"".Ec
..
u
2
c."'
~
-.
.§. 1.5
E
0
1
-e0..
0.
"0
"0
. 0.5
< 0
0 2 4 6 8
Polymer in solution [mg/g cement]
Figure 4. Adsorption isotherms plotted as amount of polymer adsorbed versus

amount remaining in solution. The continuous lines are fits to the experimental data,
using the same values for the amount of irreversibly adsorbed polymer as well as
plateau adsorption. The circled data corresponds to the points in Figure 2.
230~------------------------.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
210
'E
.§. 170
19o
--- • ---------#
~ 150
Lt 130
-! 110
:. 90
70
50 +-----~~-----r------~----~
1.0 1.2 1.4 1.6 1.8
Figure 5· Data fitted the same amount of irreversibly adsorbed polymers for which
surface coverage is corrected.

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Flatt and Schober
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104

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Properties of New Polysaccharide as a

Thickener for Concrete
by T. Izumi, 5. Dikty, and H. Yamamuro
Synopsis: A new polysaccharide derivative (NPD) is a thickener that has ionic

functional groups and hydrophobic ones. This molecular structure generates unique
properties [1], [2]. Generally current common thickeners like cellulose derivatives
are much affected by variety and quantity of inorganic metallic ions dissolved from
cement. The solubility of thickeners tends to decrease due to metallic ions. Therefore,
under ion-exchanged water they add viscosity to water effectively, but the viscous
property would be reduced with increase of metallic ions.
On the other hand, NPD shows an opposite behaviour. As the concentration of
inorganic salt such as NaCl increases, the viscosity of NPD aqueous solution rises
significantly [1]. It is supposed that the formation of network structures generated
by associating hydrophobic groups in the presence of metallic ions would cause
excellent thickening ability.
It is expected that NPD will be utilized as a thickener for self-compacting concrete and
for anti-segregation in common concrete. Moreover, it is possible to make a so-called
two in one product that owns both dispersability and viscous ability, because NPD is
mixed with a superplasticizer easily without increasing solution viscosity.
Keywords: polysaccharide derivative; self-compacting concrete;

thickener

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106 Izumi et al.
Tatsuo Izumi is a technical manager of Kao Chemicals GmbH, Germany. His current
research interest is the mechanism of new superplasticizer from the molecular design
point of view. M.Eng.
Stefan Dikty is a research chemist of Kao Chemicals GmbH, Germany. He has worked
in the field of focussing on the development of new superplasticizer of polycarboxylate-
based polymer.
Hotaka Yamamuro is a manager of Performance Chemicals Research Laboratories, Kao

Corporation, Japan. His research field is the mechanism of concrete admixtures from
chemical design point of view. M.Eng.
INTRODUCTION
Various types of thickeners are used to give concrete anti-segregation properties.

Generally speaking, it is known that the characteristics of thickeners affect not only
concrete viscosity, but also dispersability.
For example, common thickeners, which are strongly adsorptive on cement
surface, cause flow decrease. This is why they form cross-linking among cement particles
They make cement particles coagulate and disturb distribution of particles. As a result,
dispersion state is spoiled. It was found that minimizing adsorption amount of thickeners
provide stable workability [3].
Since available thickeners like cellulose derivatives are said to be relatively little
affected by inorganic metallic salts, they are used in such fields as detergents, cosmetics
and food products. However, the ionic strength of the liquid phase in concrete is much
higher than that of other fields. It is reported that these thickeners are influenced by
variety and quantity of inorganic metallic ions dissolved from cement [1]. In a high
alkaline (pH) environment, the viscous properties decrease dramatically.
It is reported to modify starches in order to adjust to concrete requirements [4].
But when available thickeners are used in ordinary ready-mixed concrete plants, it is
necessary to provide either a dispenser or a pump for the thickeners, or to dose the
thickener powder into a mixer by hands.
In this study, the effects of inorganic metallic salts, which dissolve out from
cement particles, on the viscous behaviour of thickeners were examined. This led to the
development of a new polysaccharide derivative (NPD) that has low viscosity under low
ionic strength, but that shows higher viscosity under high ionic strength. The
development of a liquid-type admixture, which is a blend of NPD and
polycarboxylate-based superplasticizer, combining high dispersability with low setting
retardation is also described in this paper.
MATERIALS AND METHODS
Binding materials and chemical admixtures
Two different types of portland cement (CEM I 52.5R and CEM I 42.5R), that
had different strength properties, were used to establish the performance of

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Superptasticizers and Chemical Admixtures in Concrete 107
NPD. Superplasticizers used in this paper were polycarboxylate-based (PCE) with very
long side chains (more than 100 mole) of polyethylene oxide [5]. Three different
thickeners were used to establish the properties ofNPD as follows:
-NPD Mw ca. 800,000

-Methyl cellulose (MC) Mw ca. 700,000
- Hydroxyl ethyl cellulose (HEC) Mw ca. 1,500,000
- Xanthan gum (XG) Mw ca. 1,200,000
Mw: molecular weight
The chemical structure of NPD is shown in Fig. 1. This polymer has a bone
structure of cellulose principal chains with two functional groups of opposing natures,
ionic functional groups (X) and hydrophobic groups (R).
Viscosity measurement ofthickener aqueous solution
Supernatant liquid separated centrifugally from cement paste (w/c = 0.4) was
used to establish the behaviours of the thickeners. Thickener aqueous solutions were
prepared to dissolve with the required dilution of the above supernatant. The viscosity
was measured with a Type B viscometer (at 30 rpm).
Rheological characteristics of thickener aqueous solution (Hysteresis area)
A coaxial cylinder rheometer was used to establish rheological characteristics. It

has an inner cylinder rotational one with cfJ 27 mm of outer cylinder, cfJ 14 mm of inner
cylinder and 65 mm of height. The range of shear rate was from 0 sec- 1 to 100 sec·'
during 50· sec, and the apparent plastic viscosity at low shear rate ( 0-10 sec- 1) was
measured.
Mortar test
Cement, fine aggregate and water containing PCE and NPD were placed in a
mortar mixer at a w/c of0.5. Mixing was carried out for 2 min at 62 rpm. The fluidity of
mortar was evaluated by the spread measured when a truncate cone ( cf> 100 mm of lower,
cf> 70 mm of upper, 60 mm of height) filled with mortar was pulled up vertically. The
bleeding test was performed according to JIS A-1123 that defined the measurement of
bleeding amount. The exothermic curve of mortar at 25 oc was obtained using TAM Air
calorimeter manufactured by Thermometric. The hydration time was calculated from the
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second exothermic peak of cement hydration, which resulted mainly from C 3S hydration.
Concrete tests for SCC
A biaxial forced-mixing mixer with a capacity of 50 L was used to mix 40 L of

concrete. Cement and aggregates were placed in the mixer and mixed for 10 sec, and then

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108 Izumi et al.
water containing chemical admixtures was added and further mixed for 90 sec. The
temperature of concrete during testing and the laboratory co.ndition were held at 20 ± 5 oC
After the completion of mixing, slump flow, flow time to reach 500 mm of slump
flow, air content and V-funnel time (dimensions of discharge opening: 65 X 70 mm)
were measured. Both setting and compressive strength were performed according to JIS
A-6204 and JIS A-1108 respectively. The mortar viscosity was measured with mortar
sieved from concrete.
Concrete tests for a project of LNG storage tank
A biaxial forced-mixing mixer with a capacity of 60 L was used to mix 40 L of

concrete sample. Cement and fine aggregates were placed in the mixer and mixed for 10
sec, then water containing chemical admixtures was added and moreover mixed for 90
sec. Finally, coarse aggregate was placed into the mixer and furthermore mixed for 90
sec. Concrete was allowed to remain in the mixer for 5 min and then was mixed for 30
sec. After that slump flow, flow time to reach 500 mm of slump flow, air content and
self-compactability were measured. Compressive strength was performed according to
JIS A-1132 and JIS A-1108. Concrete properties such as slump flow, flow time, and air
content were carried out at every 30 min interval up to 90 min. The self-compactability of
concrete was determined with aU-test apparatus [6]. U-test was performed at 5 min and
60 min after preparing concrete.
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Chemical structure ofNPD
Conventional thickeners used in concrete generally undergo some chemical

modification dependent on purposes and requirements. The molecular structure ofNPD is
shown in Fig. 1. This polymer is characterized by a backbone of cellulose
chains with two different kinds of functional groups. Some are ionic (X) and others are
hydrophobic (R). The property ofNPD is controlled by the activities of both groups.
Viscous behaviour of thickener aqueous solution
The liquid phase in concrete contains a large number of inorganic metallic salts
dissolved from cement, including bivalent ions such as Ca2+ and a small amount of
trivalent such as Al 3+, additionally such monovalent as Na+ and K+. As pH is strongly
alkaline, the conditions are quite severe for thickeners. Fig. 2 shows the results of
viscosity of aqueous solution. Various thickeners were dissolved under three different
types of liquids; one was a cement supernatant liquid (pH 12.9), another was supernatant
diluted 7 times (pH 12.2), and the third was ion-exchanged water (pH 7 .0). The dosage of
each thickener were determined as the viscosity of solution dissolved with ion-exchanged
water adjusted to around l 000 mPa ·sec. The dosage of each thickener was described
below the name in Fig. 2.
The viscosity of both HEC and MC were gradually reduced with increase of ion
concentration. In the case of HEC, the molecular structure expanded with hydration in

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ion-exchanged water and showed high viscosity. However, under cement supernatant
liquid, aqueous molecules close to oxygen atom of HEC would be released due to
metallic ions around it and finally estimated to make HEC insoluble. Although XG
solution indicated the highest viscosity under supernatant solution diluted 7 times, the
viscosity of actual supernatant was dropped to 30 mPa ·sec dramatically.
On the other hand, NPD solution had a completely opposite effect. As ionic
strength was raised, the viscosity of its solution also increased. Under higher ionic
strength, it showed stable viscosity behaviour.
Rheological characteristics ofNPD
The rheology curves of both ascending and descending slopes are depicted in
Fig.3. Each sample was dissolved with cement supernatant liquid. From a rheology curve
point of view, the difference between ascending and descending slopes suggests
thixotropy of solution. With respect to the rheology curve of NPD, a bigger difference
was observed between both slopes. The hysteresis area enclosed with both slopes
of NPD is 174.5 Palsec and that of HEC is 28.0 Palsec. This indicates that NPD forms
twisted structures as networks under high ionic strength.
Fig. 4 shows the influence of metallic ion concentration on the hysteresis area of
NPD. As cement supernatant liquid is diluted, the hysteresis area ofNPD tends to reduce
and show a minimum at ion-exchanged water. Since the value of hysteresis area achieves
to zero, the twist ofNPD remains partly even if under ion-exchanged water.
From the experimental results, the behaviour of NPD in aqueous solution is
established as follows:
Under ion-exchanged water, NPD is supposed to be present with a small amount
of polymer twist due to the strong electrostatic repulsion of ionic function group in it as
shown in Fig. 5. As metallic ion concentration increased, electrostatic repulsion caused
by ionic function group would be weakened gradually. Therefore, each NPD polymer
shrank due to loss of internal stretch. Furthermore, the hydrophobic function groups
approached one another and accelerated to form twists and to cohere in aqueous solution.
This cohesion occurred not only in a polymer, but also among ones like cross linkages.
Finally, large network structures were formed in aqueous solution as shown in Fig. 6.
On the other hand, ordinary cellulose derivatives were also affected by metallic
ion and shrank in solution. Since they had no strong hydrophobic groups in themselves,
their molecules were held shrunk. This is why they showed lower viscosity under high
ionic strength condition.
To summarize the above results, conventional thickeners cannot efficiently
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realize their inherent viscous properties in the presence of salts, so these are added in
excessive amounts for concrete application. However, since NPD displays greater
viscosity under cement supernatant liquid, it can be used at a lower dosage. Moreover, it
may be possible to develop a so-called two-in-one product that possesses both
dispersability and viscous ability, because NPD can be mixed with a superplasticizer
easily without increasing solution viscosity.

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110 Izumi et al.
Mortar test for possibility as an anti-bleeding agent
The first application test was to study the possibility ofNPD as an anti-bleeding
agent. The mortar tests were performed under two different cement samples at a w/c of
0.5. The results are shown in Table 1 and 2. As expected, NPD indicated good anti-
bleeding performance at a low dosage. Further, low retardation of cement hydration is
also observed in both conditions. This effect appears to depend on the high viscosity of
liquid phase in mortar.
Concrete tests for SCC
The second application was to investigate the use of NPD in SCC. The mixture
proportions and test result are shown in Table 3 and 4, respectively. No segregation was
found at 600 ± 30 mm over 90 min. In comparison with HEC, similar viscosity was
observed in the concrete with NPD at half the dosage of HEC. Furthermore, the setting
time was 3 hours earlier than that of HEC. This suggests that NPD minimizes the
retardation of cement hydration due to a lower dosage.
Concrete tests for a project of LNG storage tank
Finally, the application of SCC in the wall of a LNG storage tank was undertaken
[2]. The mixture proportions and test result are shown in Table 5 and 6, respectively.
Belite-rich cement was used to reduce the heat amount of cement hydration. A liquid-
type admixture of NPD blended with PCE was prepared for this project. The self-
compactability required in this test was Rank 1 [7]. This R number indicates the level
of self-compactability. Required value and test condition are dependent on the R number.
The filling height has to be more than 300 mm when Rl (obstacle) is used.
Satisfactory flowability of concrete was obtained for 90 minutes. Good
segregation resistance was also observed due to the effect of NPD. Therefore, the
quantity of powder in the proportions could be reduced. Limestone powder having a
Blaine of 750 m2/kg was used for this project. If the quantity of limestone powder were
reduced without sacrificing the performance of fresh concrete, total concrete cost would
be reduced.
Even when the limestone powder content was reduced to 81 kg/m 3 , as shown in
mixture proportions No.2, good SCC was achieved. Furthermore, good self-
compactability was achieved, when the limestone powder was replaced by cement. The
PCE mixed with NPD indicates that it is not necessary to weigh the thickener separately.
CONCLUSIONS
1) NPD forms large network structures due to the cohesion among hydrophobic groups in
the presence of inorganic metallic ions, and as a result, exhibits high viscosity in
concrete.
2) NPD provides good anti-bleeding performance at low dosage. Furthermore, NPD can
be used to produce good self-compactability and to minimize retardation of cement
hydration due to its relatively low dosage.
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3) Utilizing the property ofNPD, it may be possible to develop a two-in-one product that
has both dispersability and viscous ability, because NPD can be mixed with a
superplasticizer easily without increasing solution viscosity.
ACKNOWLEDGEMENT
The authors would like to acknowledge the contributions of colleagues from

Kao Chemicals GmbH and Kao Corporation Japan. These were useful to improve the
work reported in this article.
REFERENCES
1. Yamamuro H., "Property of new polysaccharide derivative as a viscosity agent for

self-compacting concrete", 1st International RILEM Symposium on Self-Compacting
Concrete, 1999, pp. 449-459.
2. Yamamuro H., Hamada D., and Shounaka M., "Development of a liquid type
admixture for self-compacting concrete", 2"d International Symposium on Self-
Compacting Concrete, 2001, pp. 179-186.
3. Yamamuro H., Izumi T., and Mizunuma T., "Study of non-adsorptive viscosity
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agents applied to self-compacting concrete", 5th CANMET/ACI International
Conference on Superplasticizer and Other chemical Admixtures in Concrete, 1997,
pp. 427-444.
4. J.L.Wolf and J.Pera, "Study of Valorization of modified starch in mortars", 6th

CANMET/ACI International Conference on Superplasticizer and Other chemical
Admixtures in Concrete, 2000, pp. 43-60.
5. Hamada D., Sato T., Yamato F., Mizunuma T., " Development of new
superplasticizer and its application to self-compacting concrete", 6th CANMET/ACI
International Conference on Superplasticizer and Other chemical Admixtures in
Concrete, 2000, pp. 269-290.
6. Hayakawa, M., Matsuoka, andY., Shindoh, T., "Development and application of

super-workable concrete", Special Concretes, Proceedings 24, 1993, pp. 183-190.
7. Guidelines for High Plowable Concrete, Concrete Library, JSCE, 1998, No.93, July,
pp. 10-11.

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112 Izumi et at.
Table 1- Properties ofNPD under CEM I 52.5 R
PCB NPD Mortar flow (nun) Hydration

Bleeding
dosage dosage time
(%)
(Cx%) (Cx%) 2min 30min 60min 90min (h-min)
0.2 u 2()5 2S!S 24':1 225 18.9 11-23

0.2 0.0075 225 255 248 238 3.7 11-30
0.2 0,015 210 253 253 242 4.5 11-35
Table 2- Properties ofNPD under CEM I 42.5 R
PCB NPD Mortar flow (mm) Hydration

Bleeding
dosage dosage time
(%)
(Cx%) (Cx%) 2min 30min 60min 90min (h-min)
0.2 0 258 250 241 227 37.0 15-30

0.2 0.0075 244 239 238 224 8.6 15-53
0.2 0.015 230 235 236 233 4.0 16-07
Table 3 - Concrete mix proportions for SCC
W/C s/a Unit content (kg/m3) Air

(%) (%) w I c I s I G (%)
48.6 53 170 I 350 I 918 I 862 4.5±1.5
C (cement) Normal Portland cement (s.g.: 3.16)
S (Fine aggregate) Pit sand :River sand= 1 : l (s.g.: 2.57, FM: 2.57)
G (Coarse aggregate) Crushed limestone (s.g.: 2.72, FM: 6.61)
Superplasticizer Polycarboxylate-based with EO chains of 130 moles
New polysaccharide derivative (NPD)
Thickener
Hydroxy Ethyl cellurose (HEC)
sfa: percentage of sand of total aggregate by sohd volume
s.g.: specific gravity
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Table 4 - Concrete test result for SCC
Thickener Test Time after preparation (min) V-funnel Setting a1

time
(Cx%) Item (sec) (MPa)
0 30 60 90 (h-min)
SF 600 620 605 605 Omin Initial

NPD MV 3.52 - - 3.92 7.0 9-33
5.9
(0.03) FS 6.5 6.7 7.4 9.9 90min Final
Air 3.7 3.9 3.9 4.0 8.2 11-47
SF 605 620 615 590 Omin Initial
HEC MV 3.71 - - 4.15 10.0 12-21
3.9
(0.06) FS 7.1 7.2 8.9 13.5 90min Final
10.3 14-20
Air 3.5 3.8 3.7 3.5
SF: slump flow (mm), MV: mortar viscosity (Pa·sec)
FS: flowing time to SF 500 mrn (sec), Air: concrete air(%)
a1: compressive strength after 1 day
Table 5 - Concrete mix proportions for LNG storage tank
W/C s/a Unit content (kg/m3) Air

No.
(%) (%) w c LP s G (%)
1 38 51.6 160 421 135 832 813
2 38 53.1 160 421 81 884 813 4.5±1.5
3 34 53.1 160 471 41 884 813
C (cement) Belite-rich cement (s.g. : 3.24)
LP Limestone powder (s.g. : 2.70, B.V.: 750 m 2/k:g)
S (Fine aggregate) Pit sand (s.g. : 2.60, FM: 2.65)
G (Coarse aggregate) Crushed limestone (s.g.: 2.71, FM: 6.68)
Superplasticizer Polycarboxylate-based with EO chains of 130 moles
Thickener New polysaccharide derivative (NPD)
s/a: percentage of sand of total aggregate by sohd volume
s.g.: specific gravity, B.V.: Blaine specific surface area
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114 Izumi et al.
Table 6- Concrete test result for LNG storage tank
Compressive
Dosage Time after preparation (min.)
No. Test Strength (MPa)
(%)*
5 30 60 90 cr3 cr7
SF 665 680 690 660
LTA** FS 7.5 7.6 8.7 10.3
1 16.2 29.2
1.4 Air 3.3 --- --- ---
U-test 310 --- 310 ---
SF 670 690 680 670
LTA** FS 6.4 7.4 7.5 9.7
2 14.2 24.2
1.4 Air 4.3 --- --- ---
U-test 312 --- 309 ---
SF 670 675 685 670
LTA** FS 7.2 7.6 9.5 10
3
1.4 --- --- --- 29.8
Air 3.6 ---
U-test 310 308--- ---
*: app. dosage (CX %) **: LTA (hqUid type admixture)
SF: slump flow (mm), FS: flowing time to SF 500 mm (sec)
Air: concrete air(%), U-test: filling height (mm)
0
y X Ionic functional group
~ OH OH
0 ; '
/,•' --~ 0 7;?'o

o0 a····/
HO
0
\
OH ?
0
o~-R
OH Hydrophobic group
Fig. 1- Molecular structure of NPD
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NPD MC HEC XG
(1.3%) (1.4%) (1.2%) (1.0%)
Fig. 2- Influence of ionic strength on the viscosity behaviour
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,-.. 30
~
~ 20
j
<Zl 10
50 100
Shear rate (~ec· 1 )
Fig. 3- Rheology curves of NPD and HEC
Cement supernatant
diluted 2 times
Cement sup,emata:nt
diluted 7 times
0 50 100 150 200
Hysteresis area (Pa/sec)

Fig. 4- Effects of metallic ion concentration on hysteresis area of NPD

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116 Izumi et al.
IY Li
Fig. 5- Status of NPD under low metallic ion concentration
Fig. 6- Status of NPD under high metallic ion concentration
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Influence of High Volumes of Ultra-Fine
Additions on Self-Compacting Concrete
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by R. Cioffi, F. Colangelo, D. Caputo, and B. liguori
Synopsis: In this paper, the influence of high volumes of ultra-fine fly ash, raw fly
ash, silica fume and natural zeolites on the properties of self-compacting concrete
is evaluated. Three different samples of ultra-fine fly ash obtained after high energy
milling of raw material were employed. Concretes were prepared employing various
kinds of mineral additions as partial replacement (40%) of cement or in addition
to it. Fresh concretes prepared were submitted to technological characterization
through the determination of normal slump and J-ring slump flow values. The values
of the normal slump flow were found to range between 604 and 785 mm, while the
differences with the ]-ring slump flow were less than 30 mm.
Specimens were tested to evaluate the mechanical properties of the hardened
concrete after 7- and 28-day curing. Specifically, the modulus of elasticity and
compressive strength were determined. Significant strength increases were observed
for the concrete containing ultra-fine fly ash. Finally, no segregation phenomena
were observed in the case of cylindrical column specimens (30 x 150 em). All the
results obtained show that environmentally sustainable, high workability concrete
could be successfully prepared using large volumes of mineral additions.
Keywords: compressive strength; mineral addition; self-compacting

concrete; ultra-fine fly ash; workability

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118 Cioffi et al.
Raffaele Cioffi is full professor at the University of Naples "Parthenope" and teaches
Materials and Environmental Chemistry at the Faculty of Engineering at the same
University. His main research activities concern the stabilization/solidification of
industrial solid wastes and sediments and the preparation concrete made with coal fly
ashes, MSWI ashes, etc. All the above researches are proved by more than one hundred-
twenty papers.
Dr. Francesco Colangelo is a research civil engineer at the Department of Technologies at
the University of Naples "Parthenope", Italy . He is working in the area of recycling of
industrial waste in concrete and in geo-environmental applications. He has been and still
is member of several research projects with public and private societies. All the above
researches are proved by more than thirty papers.
Domenico Caputo, is Associate Professor of Materials Science and Technology at the
Engineering Faculty of the Federico II University of Naples, Italy. Research interests are
in the broad field of microporous and mesoporous materials with particular emphasis in
applications connected with their extensive surface. Research activity is proved by more
than eighty papers.
Barbara Liguori, is a researcher of Material Science and Technology at the Department of
Materials and Production Engineering, Federico II University of Naples, Italy. Her main
research interest is zeolite synthesis and natural zeolite characterization and application in
various fields of environmental and industrial relevance, including cement industry.
Research activity is proved by more than thirty papers.
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INTRODUCTION
As mineral additions affect the flow behaviour of concrete, it seems reasonable
to try to select them, in order to relate their properties to concrete characteristics, such as
workability and segregation. It is usually reported that, if the volume of solids is held
constant, the addition of a fine powdered mineral admixtures improves concrete
performance, such as durability or strength, but increases the water demand to attain
specific workability levels (1 ,2).
Furthermore, in some cases it is also reported that the use of fine mineral
addition can reduce water demand or increase the slump . Indeed, it has been found that,
when a very fine blast furnace slag is added, an optimum amount of mineral admixture
reduces the water demand for a specific flow (3). Furthermore, enhanced workability is
achieved when spherical shaped fine mineral admixtures are used, especially fly ash (4-
6).
Other authors have reported that in concrete containing alkali-activated ground
granulated slag, the workability was improved by replacing part of the binder with ultra-
fine materials (7). In other cases, some similar materials were not effective in improving
workability (8,9).
Considering these results, it is useful to outline that the dependence of concrete
fluidity on the composition, shape and average particle size of mineral additions must be
taken in to account. In the field of high workability concretes, self-compacting concretes
(SCCs) not only flow under their own weight but also fill the entire form and achieve
uniform consolidation without segregation. sec is used in structures with closely spaced
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120 Cioffi et at.
reinforcing bars and should be able to flow through and completely fill the form without
any external vibration (1 0-12).
It is important to outline that the properties of freshly mixed SCC are highly
dependent on the mixture proportioning. This is an important factor as the grain size
distribution, maximum dimension of aggregate, types of mineral addition and chemical
admixtures. Furthermore, since chemical admixtures are expensive, the use of mineral
additions is also important as they could increase the. flow behaviour of concrete but not
its cost.
Typically, the following types of mineral additions can be used: limestone
powder, fly ash, silica fume, blast furnace slag, etc. Moreover, the additions can lower the
price of concrete when they are industrial wastes and have a considerable influence on
the mechanical properties and durability of hardened sec (13-16).
In this paper, SCCs have been prepared in order to evaluate the influence of high
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volumes of ultra-fine fly ash, raw fly ash and natural zeolites on the normal slump and I-
ring slump flows of fresh concrete as well as the mechanical (compressive strength and
elastic modulus) properties of hardened concrete. Investigations have been carried out
employing amounts of each addition calculated as 40% by weight of cement content. This
amount was used as a partial replacement of either cement or natural aggregate in order
to prepare two different types of concrete.
Furthermore, a combined blend of silica fume and raw fly ash was also used at a
total dosage equal to 40% of cement content.

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Materials
A cement CEM IIIA-L 42.5 R (according to European Standards EN-197/1) and
a crushed limestone natural aggregates were used. Different kinds of pozzolanic
additions, such as fly ash (FA), silica fume (SF) and natural zeolites (NZ), were also used
in order to improve and maintain the cohesion and segregation resistance. The fly ash
employed came from a power plant located in Brindisi (Italy). Furthermore, in order to
investigate the influence of shape and particle size of ash on concrete properties, this raw
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material was subjected to wet high energy milling, carried out by means of Netzsch
Labstar equipment This is a grinding unit that allows exact scale-up to comparative
production mills.
During the experiments, the rotating speed, milling time, water-to-solid ratio,
and size of milling media were optimized in order to obtain powders with different
fineness and to reduce treatment costs. At the end of this phase, the operative parameters
were fixed as follows: rotating speed: 3500 rpm; milling time: 30 min; water to solid
ratio: 1.2; and size of milling media: 0.8 to 1.0 mm. The final product of the wet milling
treatment was a slurry with a 55% water content, which was taken into account during the
subsequent concrete mixture proportioning.
Three different size fractions of milled fly ash were produced. The samples
obtained as described above and marked FAI, FAil and FAIII presented 90% or more of
particles finer than 10, 20 and 30 ~m, respectively. The particle size distributions of raw
and milled fly ash are shown in Fig l.Two natural zeolites (NZI and NZII) were
employed. These were commercial products. The two materials selected were a

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122 Cioffi et al.
phillipsite-rich tuff (NZI) from Marano (Naples, Italy), and a clinoptinolite-rich tuff
(NZII) from Eski~ehir (Anatolia, Turkey). Their grading is reported in Table 1.
The silica fume used was a commercially available material. In particular, this
special addition was employed in order to enable a comparison with the ultra-fine fly ash
perfonnance. The chemical composition of the mineral additions employed, expressed in
terms of main oxides, is reported in Table 2. The superplasticizer (SP) used was an
acrylic base with 40% solid content and a specific gravity of 1.2 kg/dm 3 . It was used in
all SCC mixtures, and its amount was kept constant for each type of concrete. Even the
water content of the superplasticizer was considered during the mixture proportioning.
An inorganic viscosity modifying agent (VMA) was also used in mixtures to enhance
stability (I 1).
Mixture proportions
Two different types of SCC mixtures were proportioned and cast. Type A
concrete was prepared using each mineral addition as a partial replacement of the fine
fraction of natural aggregate and in addition to cement. While in type R, mineral
additions were employed as a partial substitution of cement. The amount of each addition
was calculated as 40% of cement content. The silica fume was blended with raw fly ash
in amounts of 10% and 30% of cement content, respectively. Considering the well known
characteristics of silica fume, such as the large specific surface, the high content of free
silica and its high cost, its content generally did not exceed 10-15% of the binders. A
control concrete not containing mineral addition was also made and marked as C
concrete.
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Table 3 shows the mixture proportions for all the specimens tested. In this table
the first part of the mixture code gives information on the type of concrete while the
second part indicates the mineral additions contained. The control concrete was prepared
with a cement content of 365 kg/m 3 . For each type of mixture a similar aggregate-to-
cement ratio was employed and the filler content of aggregate was taken in to account
during the mixture proportioning phase. The water-to-cement ratio was kept constant at
0.50 for all the concretes. The mix proportions were chosen to satisfY all performance
criteria for the concrete in both the fresh and hardened state.
Methodology used
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In order to manufacture concrete, a 90 dm3 capacity conventional concrete
mixer was used. After mixing, fresh concrete was used to determine normal and J-ring
slump flow according UNI 11041 and UNI 11045 Italian Standards, respectively. The
slump flow test measures the mean diameter of concrete spread after the removal of the
slump cone. A spread of at least 600 mm is required for SCC. Slump flow gives
information about the flowability of a fresh mixture in unconfined conditions. All the
mixtures prepared did not reveal any segregation phenomena, as shown in Fig. 2 (left).
The J-Ring slump flow equipment consists of a ring of reinforcing bars that fit
around the base of a standard slump cone. After the slump cone is lifted, the concrete
flows under its dead weight through the steel bars which simulate the flow through
reinforcement in a real formwork. J-Ring flow values give information about the
capacity of the fresh mixture to flow through confined spaces and narrow openings
(passing ability), as shown in Fig. 2 (right). The differences between the slump flow
values, measured with and without J-Ring, were also calculated.

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124 Cioffi et al.
To evaluate strength development, compressive tests were carried out after 7
and 28 days of water curing, according to UNI 6132 Italian Standard. Three specimens
(1 00-mm cube) were cast for each data point. The dynamic modulus of elasticity was
determined using cylinder specimens of 150-mm diameter x 300-mm height. The
dynamic modulus of elasticity was recorded by ultrasonic pulse velocity measurements.
This method, according to Rilem NDT 1 Standard, links the velocity with which an
ultrasonic pulse passes through a material, with its elastic modulus. The specimens were
tested at age of 28 days.
The ultrasonic pulse velocity measurement was also carried out to verify the
presence of segregation in the hardened concrete specimens. The specimens employed, as
shown in Fig. 3, were cylindrical columns of 30-cm diameter x 150-cm height. Sixteen
measurements of velocity were taken for each specimen at different heights and the
results were plotted as a function of the specimen height.
Table 4 shows the results of normal and J-ring slump flow measurements
carried out on type A concrete. The values reported were separately obtained
immediately after, and 30 minutes after the mixing of the concrete. The differences
between the two above values recorded, expressed in terms of percentage of slump loss,
are also shown. It is seen that the systems containing raw fly ash and silica fume show
slump flow values higher than those of the other mixtures. These results are clearly
affected by the particle shape and fineness of the additions and, in actual fact, the
spherical shape of samples is one of the main factors that improves the workability (4).
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On the contrary, the natural crushed aggregate is characterized by an irregular shape and
a lower fineness.
A relevant consideration can be drawn once the results for the systems FAI,
FAIT and FAIII are taken in to account. It is seen that the irregular (sharp) particle shape
of ground material and their high fineness do not significantly affect the flow behaviour
of concrete. Indeed, the slump flow values are fairly high, and equal to 722, 735 and 753
mm, respectively for the systems under consideration. These high values suggest that, in
the presence of 40 % ultra-fine fly ash, it is possible to manufacture self-compacting
concrete (about 600 mm of slump flow) reducing the amount of superplasticizer added.
Moreover, the role played by the two kinds of zeolites on the slump flow of mixtures is
clearly affected by their different fineness and the behaviour shown by the coarser sample
is worse than that of the finer one. This is due to the presence in sample NZII of a
significant content of particles with a diameter higher than 125 J-Lm.
Finally, analysing the results of the C mixtures makes it possible to draw the
conclusion that when the concrete is prepared without mineral addition the slump flow
value is lower than those of zeolites containing ones. As regards the slump flow
measurements carried out 30 minutes after mixing, it is clearly seen that the values of
slump loss found for all the mixtures tested in this study lay within the 5.4- 8.7% range.
This technological aspect is of great importance in the use of self compacting concrete at
a considerable distance from the production plant. The values observed for SF mixture
are higher, due to the chemical and physical characteristics of silica fume ( 16). Regarding
the J-ring slump flow values measured for the same type of mixtures described above, it
is seen that the differences between normal slump and J -ring slump values are between
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126 Cioffi et al.
10 and 30 mm for all the mixes tested. The observed values make it possible to say that
the self-compacting concrete prepared and studied in this work have a good passing
ability in terms of capacity to flow through confined spaces. Moreover, the data also give
information on the fact that no blocking phenomena are shown when the tests are carried
out 30 minutes after mixture preparation (Fig. 2 right).
Considering the important technological and economic factors such as the VMA
content, it is possible to say that, as reported in Table 3, all the mineral additions tested
are able to favour a reduction in comparison to the amounts required in the control
mixture. Table 5 shows the results of normal slump and J-ring slump flow test carried out
on type R concrete. It is possible to see that all the values measured are lower than those
found for the type A concrete, the reason being that the mixture proportioning is different
for the type R concrete, as shown in Table 3. The data show that the higher slump flow
values are found for the mixes containing silica fume while the lowest values are
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measured for the zeolite-containing mixtures. Furthermore, in the cases of the concrete
employing the raw and ultra fine fly ash, the slump flow values range between 671 and
635 mm. The latter value (F AI system) is lower than that found for the C mixture.
Finally, the values found carrying out the J-ring slump flow test confirm that all
the mixtures tested show a good behaviour in respect to their capacity to flow through
narrow openings (steel bars). As in the case of the type A systems, the differences
between normal and J-ring flow values are less than 30 mm and the workability loss after
30 minutes is low.

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Properties of hardened concrete
As far as the aggregate segregation is concerned, the ultrasonic pulse velocity
measurements carried out on concrete cylindrical columns show that almost all the
specimens manufactured with mineral additions are homogenous along their height (see
Fig. 3). The only exceptions were found for the C and NZII mixtures, in which ultrasonic
pulse velocity variation (5% and 8%, respectively) were measured. Therefore, the clearly
observable effect due to the use of large amounts of mineral additions is the absence of
segregation phenomena on real scale concrete specimens
The results of these real scale tests are of some interest when the amount of
chemical admixtures, such as viscosity modifying agent and superplasticizer, have to be
determined during the mixture proportioning phase. The compressive strength
development for type A and R concrete are shown in Figs. 4 and 5. Figure 4 indicates
that, after 28-day curing, all the mixtures give a strength higher than that of the control
concrete. In particular, the mixture containing silica fume shows a much greater
mechanical strength than the others (16). Moreover, for the mixtures containing fly ash,
the strength increases as the grain size become finer and strengths of 59.0, 59.4, 62.5 and
64.7 MPa have been found for the systems FA, FAIII, FAil and FAI, respectively. The
mixture NZI gives a strength (58.5 MPa) which is very close to that found in the case of
raw fly ash (59.0 MPa), while the mechanical behaviour of the NZII mixture is similar to
the control concrete (17).
As far as the type R systems are concerned, Fig. 5 shows that, after 28-day
curing, all the values are, as expected, lower than those for type A systems and, even for
this type of concrete, the higher strengths were found when the fineness of the additions
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128 Cioffi et al.
increased. The highest strength was found for concrete made with silica fume; which is
the only one that shows a higher value than the control mixture. In all the other cases, the
lowest value of strength loss is 5% for the F AI mixture, while the highest is 25% for the
mix containing coarser zeolite (NZII). Analysing all the above results, it can be said that
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the development of strength, up to 28-day curing, is not governed by chemistry but by the
specific surface of the additions.
The dynamic modulus of elasticity values are reported in Fig.6. After 28-day
curing type A concretes show a higher modulus value than concrete C, whereas the
values recorded for the type R mixtures are lower. These experiments confirm that, with
the exception of SF systems, the higher values of modulus are found for the finest
additions, such as FAI, as was the case for compressive strength.
CONCLUSIONS
All the experiments carried out m this investigation allow the following
conclusions to be drawn.
Two different types of high performance self-compacting concrete can be
prepared employing considerable amounts of mineral additions. The first type, containing
the additions as a partial replacement of the finer fraction of aggregate, showed slump
flow values higher than those for the other type in which the cement was replaced. For all
the mixtures investigated the behaviour was better or comparable to "standard" self
compacting concrete. When compared with concrete containing raw fly ash, the mixtures
prepared with high energy milled fly ash have shown a decrease in slump flow of less
than 8%. The flow data recorded for mixtures made with zeolite were found to be lower
than those for mixtures containing fly ash. In all cases, the particle-size distribution of the

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added materials played a more predominant role than the nature of materia:Js. The ultra-
fine fly ash tested are able to favour a reduction of the chemical admixtures content in
comparison to that required in the control mixture.
The compressive strength determined for the mixtures made with the finest
milled fly ash was found to be not much lower than those of the silica fume-concrete
specimens. This is true both for the two curing times investigated and for the two types of
concrete prepared. Significant differences were seen for the mixtures containing zeolite.
The modulus of elasticity values confirmed the trend observed for the
compressive strength. Finally, the absence of segregation phenomena on real scale
specimens were observed.
REFERENCES
1
V.S. Ramachandran, 1995, Concrete Admixtures Handbook; Properties, Science and
Technology, Noyes Publications.
2
C.F. Ferraris et a!., 2001 , "Fresh Concrete Rheology - Recent Developments",
Material Science of Concrete, Vol 6, pp. 215-241.
3
F. Lange, eta!., 1997, "Dense Packing of Cement Pastes and Resulting Consequences
on Mortar Properties", Cement and Concrete Research, Vol. 27, No.IO, pp. 1481-1488.
4
V.M. Malhotra, P.K. Mehta, 2002, "High-performance, high-volume fly ash concrete:
Materials, Mixture Proportioning, Properties, Construction Practice, and Case Histories",
Supplementary Cementing Materials for Sustainable Development, Inc. Ottawa, Canada.
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130 Cioffi et at.
5
M. Collepardi et al., 2004, "Combination of silica fume, fly ash and amorphous nano-
silca in superplasticized high-performance concretes", Innovative Materials and
Technologies for Construction and Restoration, Editors A. La Tegola, A. Nanni, Liguori,
Naples, Italy, pp. 459-468.
6
V. M Malhotra, 2002, "High-performance high-volume fly ash concrete. An
environmentally friendly solution to the infrastructure needs of developing countries",
Concrete International, Vol. 24, No.7, pp. 30-34.
7
F. Collins, J.G. Sanjayan, 1999, "Effects of ultra-fine materials on workability and
strength of concrete containing alkali-activated slag as the binder", Cement and Concrete
Research, Vol. 29, pp.459-462.
8
PK Mehta, 1999, "Advancements in Concrete Technology", Concrete International,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Vol. 21, No.6, pp. 69-76.
9
Bakharev T. et a!., 2000, "Effect of admixtures on properties of alkali-activated slag
concrete", Cement and Concrete Research, Vol. 30, No.9, pp. 1367-1374.
10
Collepardi, 2003, June, "Innovative concrete for Civil Engineering Structures: SCC,
HPC & RPC", Proc. of the Workshop on New Technologies and Material in Civil
Engineering, Milan, Italy.
11
J. Ambroise et al., 1999, Self-Levelling Concrete-Design and Properties, Concrete
Science and Engineering, Vol.l, pp.l40-147.

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12
Collepardi M., 2003, "Self-compacting concrete : what is new ?", Proc. of Seventh
CANMET/ACI International Conference on Superp/asticizers and Other Chemical
Admixtures In Concrete, Berlin, Germany, pp. 1-16.
13
F. Colangelo et al., 2004, "Influence of admixtures on the properties of Self-
Compacting Concrete", Innovative Materials and Technologies for Construction and
Restoration, Editors A. La Tegola, A. Nanni, Liguori, Naples, Italy, pp372- 380.
14
S.D Fossey et al., 2003, "Superclassified PFA for self-compacting concrete", Proc.
lith Int. Cong. on the Chern. of Cement, Durban, South Africa, pp.769- 779.
15
N.Bouzoubaa, M. Lachemi, , 2001 "Self-compacting concrete incorporating high
volumes of class F fly ash. Preliminary results", Cement and Concrete Research, Vol.Jl,
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pp. 413- 420.
16
ACI - SP233 CD, 2006, Workability of SCC: Roles ofIts Constituents and
Measurement Techniques, Editors C. Shi & K. H. Khayat, New York.
17
B. Liguori, D. Caputo, M. Marroccoli, C. Colella, 2004, Evaluation of zeolite-bearing
tuffs as pozzolanic addition for blended cements, Proceedings Eighth CANMETIACJ
International Conference on Fly Ash, Silica Fume, Slag and Natural Pozzolans in
Concrete, American Concrete Institute, Farmington Hills, MI, U.S.A., Editor: V.M.
Malhotra, p. 319-334.

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132 Cioffi et al.
Table I - Grading of natural zeolites
Oxide Fly ash Silica Zeolite I Zeolite II

fume
Si02 44.31 93.00 58.82 76.29
Al203 20.26 0.80 19.!0 12.78
Fe203 10.56 0.70 4.60 1.45
CaO 0.53 0.20 3.10 2.88
MgO 0.67 0.60 1.11 1.19
Na20 0.31 0.60 3.44 0.79
K20 8.13 1.00 9.39 4.46
l.o.i. 11.35
Table 2 - Chemical composition of the mineral additions, wt"/o
Composition, kg/m,
System CEM FA FAI FAll FAIII SF NZI NZII SP VMA Aggr.
c 365 5.20 1.92 2335
A-FA 365 146.0 7.26 1.20 2303
A-FAI 365 146 7.26 0.65 2309
A-FAIT 365 146 7.26 0.75 2306
A-FAIII 365 146 7.26 1.00 2305
A-SF 365 109.5 36.5 7.26 0.60 2285
A-NZI 365 146 7.26 1.40 2327
A-NZII 365 146 7.26 1.70 2322
R-FA 219 146.0 5.20 1.90 2279
R-FAI 219 146 5.20 1.80 2285
R-FAII 219 146 5.20 1.80 2282
R-FAIII 219 146 5.20 1.90 2280
R-SF 219 109.5 36.5 5.20 1.80 2266
R-NZI 219 146 5.20 1.90 2295
R-NZII 219 146 5.20 1.90 2291
Table 3. Concrete mixture proportions
Cumulative passinlt wt"/o

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Sieve size, NZI NZII

mm
125 98.5 87.5
90 94.0 74.0
63 82.5 58.5
38 57.0 27.0

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Table 4- Properties of type A fresh concrete
System Slum flow Slump flow Slump J-ring J-ring J-ring

t~o. t~30'. flow loss, t~ 0, t~ 30', loss,
em em % em em %
c 640 602 5.9 620 561 9.5
A-FA 785 739 5.9 774 716 7.5
A-FAl 722 681 5.7 692 631 8.8
A-FAil 735 689 6.3 707 640 9.5
A-FAlll 753 712 5.4 730 674 7.7
A-SF 761 695 8.7 749 672 10.3
A-NZI 704 653 7.2 677 605 10.6
A-NZII 667 628 5.8 649 591 8.9
Table 5 - Properties of type R fresh concrete
System Slum flow Slump flow Slump J-ring J-ring J-ring

t~O, t~30', flow loss, t=O, 1=30', loss,
mm mm % mm mm %
c
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
642 603 6.1 620 562 9.4

R-FA 671 632 5.8 650 600 7.7
R-FAI 635 577 9.1 606 527 1.0
R-FAII 651 608 6.6 627 566 9.7
R-FAlii 663 613 7.5 640 569 11.1
R-SF 682 623 8.7 672 604 10.1
R-NZI 614 567 7.7 587 519 11.6
R-NZII 604 562 7.0 574 515 10.3
100
.• ,
90 /
/ _l .... FA!
/, I
[!()
/;
I
i: I
--FAIT
I:
: I I
I / I
- .. FAIII
/
.,.
-
20
10 ~,..
0 -FA
0.1 10 100 1000
Sew,mm
Fig. 1- Particle size distributions of fly ash samples.

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134 Cioffi et al.
Fig. 2- Details of normal slump flow (left) and )-ring slump flow (right) tests.
150
140
130
120
110
100
90
e
:=" eo
·r:c 70
80
50
40
30
20
10
55 60 65
Vt'loeUy.J.Lt
Fig. 3- Real scale specimens for resistance to segregation test (left) and velocity of
ultrasonic pulse as function of height (right).
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mo.-----------------------------------,c7~
i /UO i!l28~
I ::
t::
8 :no
~ 10.0
M~~~~~~~~~~~~~
C A-FA A-FA! A-FAll A-FAll! ASF A-NZI A-NZII
Fig_ 4- Compressive strength of type A self-compacting concretes.
1 !,'
; I II I 7 r.<-
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Ii i .Iii I
c RooFA RooFAI RooFAn RooFAni RSF R<-NZI &NZII
--------------------------------~------~--~
Fig. 5- Compressive strength of type R self-compacting concretes.
,----
({)
~ r-;.
~
i IIII I~ I
f 50
f F
1 40
ll:l
~
1 III III
"a
I I
s :l) :\\:
1 3)
10
0
II: ~)~ ::j:J ~~j~ ~ m
Fig. 6- Dynamic modulus of elasticity of the self-compacting concretes.

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136 Cioffi et at.
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SP-239-10
Novel Slurry Rheology Modifier

for Materials of Civil Engineering
and Construction
by H. Yamamuro, K. Koyanagi, and T. Kojima
Synopsis: A novel slurry rheology modifier (Vl) has been developed for slurry,
mortar and concrete using an inorganic powder such as cement. This chemical
admixture mainly consists of cationic and anionic surfactants. VT can efficiently
exhibit unique viscoelasticity in spite of low molecular weight when the cationic and
anionic surfactants coexist in slurry at the same time. This technology gives very good
segregation resistance to cement slurry and concrete under several conditions, e.g.,
water, vibration, and high water-cement ratio and without setting retardation. The
viscoelasticity mechanism ofVT is caused by the formation of higher-order structure
of surfactants in slurry. Controlling the viscoelasticity ofVT is an effective method
to prevent segregation for cement slurry, various grouts for repair and ground
improvement. VT has various potential abilities in civil engineering and construction
fields because of unique viscoelastic behavior.
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Keywords: cement; concrete; segregation resistance; slurry rheology

modifier; surfactants; viscoelasticity

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138 Yamamuro et al.
Hotaka Yamamuro, Senior Research Chemist, Performance Chemicals Research
Laboratories, Kao Corporation, Japan.
Koji Koyanagi, Research Chemist, Performance Chemicals Research Laboratories, Kao

Corporation, Japan.
Toshiharu Kojima, Research Chemist, Performance Chemicals Research Laboratories,

Kao Corporation, Japan.
INTRODUCTION
Surfactants have been extensively made available for our daily life and industrial
activity such as detergents, for cosmetics, medicinal products, agricultural chemicals,
food products, construction and civil engineering. The main functions of surfactants are
detergency, emulsification, dispersibility, wettability and so on. In recent years, the
higher-order structure formed by molecule association of surfactants has been
investigated by academic chemists and industrial scientists. The technology development
utilizing the functions derived from higher-order structure has been expected in the
various fields. The authors applied the higher-order structure of surfactants to the
viscosity agents of concrete and developed a novel slurry rheology modifier (VT) for
cement slurry, mortar and concrete.
There have been many studies on the properties of viscosity agents for concrete
[1,2]. The most typical viscosity agents are water-soluble polymers, e.g., cellulose
derivatives [3], fermentation polysaccharide [4,5,6] and various types of synthetic
polymer [7], and are added to prevent segregation of concrete. However these viscosity
agents have several problems; for example, the dissolution rate of viscosity agent's
powder is slow due to the very high molecular weight, and handling and workability
become worse in the case of dissolving viscosity agents in water and setting retardation.
In contrast, VT gives excellent segregation resistance to concrete in spite of very low
molecular weight. Furthermore, since VT dose not inhibit the hydration of cement;
setting retardation is very small compared to conventional viscosity agents.
This paper reports the general properties ofVT in cement slurry and concrete.
The mixture proportions adopted for laboratory testing purposes in this study and
the specifications of the materials used are listed in Table 1.
Slurry test: Cement slurry was prepared by mixing cement together with water containing
viscosity agent and/or superplasticizer at a water-to-cement ratio of 0.5-6.0. In this
connection, the water-to-cement ratio of 0.49-0.55 in Table 1 was selected to get the
required compressive strength (more than 24.5MPa at 28 days). The slurry was mixed
with a hand mixer for 1.5 minutes. In the case of VT, mixing was carried out for 1.0
minute with the addition of compound A and then for 0.5 minutes with.the addition of
compound B.
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Rheology measurement:
• Static viscosity: The viscosity was measured with rotation viscometer(RION Co., LTD).
The rotation speed was 63.5rpm.
• Dynamic viscoelasticity: The viscoelastic property was evaluated by measuring the
storage modulus G' value at 20°C. ARES viscoelasticity measuring instrument and cone
plate( i/> 50mm, angle:0.0398, Gap: 0.0508mm)were used (Rheometric Scientific); the
measuring range was from 0.0628 to 62.8rad/s at strain 1.0%.
Hydration property: Using the slurry prepared as a sample, exothermic curve of hydration
was obtained with TCC2-6 calorimeter. Hydration property was evaluated by measuring
the second exothermic peak time of C3S hydration.
Direct observation of higher-order structure: Blast-furnace slag slurry containing VT was

iced on the copper plate and then the higher-order structure of surfactants in coexistence
with the blast-furnace slag powder was observed by using the field-emission scanning
electron microscope with Cryo-unit S4000.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Concrete tests: A biaxial forced-mixing mixer with a capacity of 50 liters was used to mix
40 liters of concrete sample. To prepare the sample, the cement and both coarse and fine
aggregates were placed in the mixer and mixed for 10 seconds; then water containing the
superplasticizer and the viscosity agent was added, and mixing continued for a further 90
seconds. The temperature of the concrete during testing, and also the laboratory ambient
temperature, were held at 20.0 ±0.5°C. After the completion of mixing, the slump flow
value, underwater segregation resistance, air volume were measured in accordance with
JIS AllOl and 1128. Self-compactability of the concrete was determined by using the
Box-type test apparatus (2]. The compressive strength test was determined according to
JIS A-1132 and ns A-1108.
The molecular structure of VT is shown in Fig. 1. VT is supplied as two kinds of

liquid (compound A and compound B). Compound A, which consists mainly of alkyl
allylsulfonate, is anionic surfactant and compound B, which contains alkylammonium
salt in major proportions, is cationic surfactant.
Figure 2 shows the viscosity behavior of viscosity agents in water. lt is clear that
the viscosity of methylcellulose (MC) solution increases strikingly with increasing
concentration. On the other hand, the viscosity of compound A and B solution do not
almost change with increasing concentration, because both compound A and compound B
are not polymer but monomer of a few hundred of molecular weight as shown in Fig.!.
The viscosities of solutions are less than 20mPa · s at 20°C. This indicates that compound
A and compound B solution are very easy to handle.
The results for the viscosity of cement slurry (water-to-cement ratio of 0.7)
containing VT are shown in Fig.3. Compound A and compound B did not exhibit
viscosity individually. However, they could exhibit excellent viscosity in cement slurry

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140 Yamamuro et al.
when compound A and compound B coexist in slurry at the same time. The
viscoelasticity mechanism of VT was caused by the higher-order structure formed by
molecule association of compound A and compound B.
Figure 4 shows the effect of molar ratio of compound Ncompound B on the

viscosity of cement slurry. VT exhibited the maximum viscosity at a 1:1 mohtr ratio.
The viscosities of cement slurry vs. the VT dosage of plots for cement slurry with
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
different water-to-cement ratio are shown in Fig.5. A desired viscosity value can be
obtained for slurries of various water-to-cement ratios by adjusting the dosage ofVT.
Figure 6 shows the fluidity aspect of cement slurry having ditierent concentration
of VT at same water-to-cement ratio of 0. 7. The flowable viscous slurry and gumlike
viscoelastic slurry were manufactured by changing the concentration of VT.
Figure 7 shows the angular frequency dependence of G' (G' is called as storage
modulus and defined as G'( w )= G ( w )I y 0 (t=O) w :angular frequency, G :strain,
y :stress, t: time) of VT solution and MC solution. The MC solution has the frequency
dependence of typical flexible polymer solution. On the other hand, the VT solution has
what is called a Maxwell-type frequency dependence. The G' ofVT solution was higher
than that of MC solution at a broad range of angular frequency. This indicates that VT is
effective to avoid the segregation of slurry and thus to obtain the homogeneous slurry.
The rheological property of the CaC03 slurry ofVT was compared to that ofMC in
Fig. 8. The CaC03 powder was used to prevent the influence of hydration reaction on
rheological property during the measurement of lhr. The results of slurry were reflected
in the aqueous solution experiments, that is, the G' of VT slurry was extremely high
compared to that of MC slurry at the slurry viscosity 800mPa · s. Additionally, the fresh
behavior of CaC0 3 slurry was very similar to that of cement slurry.
Figure 9 shows the picture of the VT in coexistence with the blast-furnace slag
powder by using Cryo-SEM, VT of0.05 mol/1. The higher-order structure of30-50 nm in
diameter spreads homogeneously around the powder particle. This structure could give
the slurry the unique viscoelasticity, so that the cement slurry containing VT had
excellent segregation resistance in water, as shown in Figure 10.
The second exothermic peak time of C3S hydration was measured to investigate the
influence of viscosity agents on the hydration of cement (Fig.!!). In the case· of MC, the
hydration was strikingly inhibited compared to the control. In contrast, though VT slurry
was about the same viscosity as MC slurry, retardation of VT was within 1 hour.
Moreover, the VT slurry showed the retardation of mere 2 hours regardless of triple
viscosity 15,000mPa · s for MC. This suggests that water molecule used in hydration can
get through the higher-order structure and then get around to the surface of cement
particles.
The cement slurry at water-to-cement ratio of > 1.0 was prepared without

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segregation and retardation, so that the test specimens had the extraordinary low-strength
and a high water-absorbing property (Table 2 and Table 3). The hydrate crystals
photomicrographs of water-to-cement ratio of 2.0 are shown in Figure 12 and they were
taken by using FE-SEM. It is thought VT inhibited the sedimentation of cement particles
and maintained the dispersion of cement until hardening, so that the test specimen had
very porous structure.
Figure 13 shows an example of applications to civil engineering. This cement

slurry containing VT (water-to-cement ratio of 1.25) was used for the grout of bored
precast pile method in Japan. Although the cement-bentonite slurry is normally used, the
conventional slurry infiltrated into sand or gravel ground and could not remain around the
concrete pile. On the other hand, in the case of VT slurry, no infiltration was observed.
Moreover, even if a lot of water exists under ground such as groundwater and flux and
reflux of the tide, VT slurry is not diluted with water and not washed away.
The interaction between the VT and superplasticizers was shown in Fig.l4. In the
case of Polyether-based superplasticizer (PE)[8)NT, the viscosity of slurry did not
significantly change with increasing dosage of PE. In contrast, the viscosity of
naphthalene-based superplasticizer (NS)NT slurry decreased with increasing dosage of
NF. It was thought that the phenomenon of NSNT was caused by inhibiting the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
formation of high-order structure due to the pi electron of naphthalene ring. It is clear that
PE was more suitable for VT slurry.
The underwater concrete was examined for self-compactability and good hardening
property by utilizing the feature of VT. The results of concrete tests are shown in Table 4
and Table 5. In the case of MC/Melamine-based superplasticizer (ML), the
self-compactability was not observed because MC/ML concrete could not get the
sufficient fluidity in spite of increasing dosage of ML. In contrast, VT/PE concrete had
good self-compactability with segregation resistance in water at some mixture
proportions. Additionally, the strength ofVT/PE concrete was more than 5N/mm2 in 24 hr
However, MC/ML concrete did not harden in 24 hr. It was confirmed that good hardening
property was compatible with self-compactability and underwater segregation resistance
by usingVT.
In summary, the high-order structure of VT that consists of cationic and anionic

surfactants is formed in cement slurry and concrete. It can exhibit unique viscoelasticity
efficiently and can give very good segregation resistance to cement slurry and possibly
concrete. Controlling the slurry viscoelasticity by VT is an effective method to prevent
segregation for water-inorganic powder slurries. VT has various potential applications
and can be applied to the materials for civil engineering and construction fields such as
cement slurry, mortar, concrete, various grouts for repair, reinforcement and ground
improvement and much more.
CONCLUSIONS
1. A novel slurry rheology modifier VT can efficiently exhibit unique viscoelasticity in

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142 Yamamuro et at.
spite of low molecular weight, and can give very good segregation resistance to cement
slurry and concrete without setting retardation.
2. The viscoelasticity ofVT is exhibited when the cationic and anionic surfactants coexist
in slurry at the same time, and the viscosity of each surfactant solutions is very low.
3. VTexhibited the maximum viscosity at a 1:1 molar ratio.
4. The viscoelasticity mechanism of VT was caused by the formation of higher-order

structure of surfactants.
5. A cement slurry was produced at water-to-cement ratio of> 1.0 without segregation and
retardation by adding VT and the test pieces had extraordinary low-strength and a high
water-absorbing property.
6. Polyether-based superplasticizer (PE) was suitable for VT slurry.
REFERENCES
[1] Izumi, T., Tadokoro, T., Mizunuma, T. and Kawai, T., 'Characterization of
thickener's adsorption in view of mortar flow', Proceedings of the
Japan Concrete Institute, Vol.l7, No.I, 1995, pp. 63-68
[2] Hibino, M., 'Effect of Viscosity Enhancing Agent on Self-Compactability of
Fresh Concrete', Sixth CANMET/ACI, 2000, pp. 305-320
[3] Yamamuro, H., Hamada, D. and Shonaka, M., 'Development of a liquid type
admixture for self-compacting concrete' 2nd Symposium on Self-Compacting
Concrete, Oct. 2001, pp. 179-186
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
[4] Kang, K.S. and Pettitt, D.J., 'Industrial gums third edition'
(R.L. Whistler, J .N .Bemller edition), Academic Press, pp354-, 1993
[5] Shindoh, T., Matsuoka, Y. and Sornnuk T.,' Fundamental study on properties of
super wakable concrete ' Proceedings of the Japan Concrete Institute , Vol.l3,
No.1, 1991, pp. 179-184
[6] Khayat, K.H. and Saric-Coric, M., 'Effect of Welan Gum-Superplasticizer
Combinations on Properties of Cement Grouts', Sixth CANMET/ACI, 2000,
pp. 249-268
[7] Yamamuro, H., Izumi, T., Mizunuma, T. and Kawai, T., 'A research on high
flowable concrete with non-adsorptive thickeners', Proceedings of the
JapanConcreteinstitute, Vol.17, No.I, 1995, pp.99-104
[8] Mizunuma, T., Izumi, T., Kanzaki, S. and Iizuka., 'Properties of high range
water reducing concrete with new high range water reducing agent(AE type)'
Proceedings of the Japan Concrete Institute, Vol.l4, No.1, 1992, pp. 33 7-342

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```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
11a ble 1 -- . ls t:or l ab oratory tes t
Mixtureproportionsan d matena
Unit content (kglm3 ) VTdosage
Mix. W/C s/a Air
No. (%) (%) Water Fine Coarse (Water X%) (%)
Cement
agg. agg.
1 55.0 40.0 220 400 627 964 2.5 4.0
2 49.0 45.0 210 429 707 886 2.5 4.0
3 49.0 44.0 200 408 712 925 2.5 4.0
Cement Normal portland cement (s.g. : 3.16 ,B.V.:3380)
Fine aggregate Chinese river sand (s.g. : 2.56, FM: 2.57)
Coarse aggregate Crushed stone (s.g. : 2.62, FM: 6.61)
Superplasticizer Polyether-based (PE) (M.w : 45000)
Melamine-based (ML)
Naphthalene-based (NS)
Viscosity agent Slurry rheology modifier (VT): Compound A, B
Methyl cellulose (MC)
s.g. : Spec1fic grav1ty
FM : Fineness modulus
B.V : Specific surface area of cement by Blaine method
Table 2-- Relationship between dosage of VT and strength

Dosage (W x %) Strength 28d
W/C
Compound A CompoundB (MPa)
0.50 0.50 0.50 41.9
0.75 1.00 1.00 10.3
1.00 1.00 1.00 5.8
1.25 1.00 1.00 3.1
1.50 1.00 1.00 1.4
2.00 1.00 1.00 1.0
3.00 1.00 1.00 0.3
6.00 1.00 1.00 ----
Table 3- Relationship between water to cement ratio and water absorption
W/C Density Water absorption

(g/cm3) (%)
1.00 0.85 68.0
2.00 0.50 137.0
3.00 0.39 205.0
6.00 0.26 270.0

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144 Yamamuro et at.
Table 4-- The result of concrete test
Mix. Visco. SP Slump flow (mm) Air Filling SR test
No. Agent (CX%) 5min lOmin (%) hight-Rl(cm) (pH)
MC ML2.5 495 520 3.3 10.5 10.71
l
VT PE 1.2 530 600 3.1 25.5 10.59
2 VT PE 1.5 590 650 3.7 33.0 10.72
VT PE 1.5 570 620 3.7 32.5 10.61
3
MC MIA.O 450 460 3.9 16.0 10.96
Note: dosage of V1SCOStty agent: MC 2.5kg!m3, VT WX2.5%
SR-test{pH): segregation resistance test in water
Table 5 -- The resu lt of compresstve stren2t h

Mix. Visco. SP Compressive strength (MPa) days
No. Agent (CX%) I 2 5 7 28
MC ML2.5 0.0 7.8 17.1 23.9 34.4
I
VT PE 1.2 5.0 12.4 19.0 23.6 37.7
2 VT PE 1.5 6.5 14.9 23.7 31.5 41.0
VT PE 1.5 6.2 14.2 22.8 30.6 39.2
3
MC ML4.0 0.0 6.3 23.4 29.8 38.5
Compound A CompoundB
R4
R 0 S0 3 Na
I
R - N -R
1 I 2
oX
R3
Fig. 1-Chemical structure ofVT
~- -o- I
i-;;- 40000
~
30000
Compound A
.....__ Compound B
_._ Methyj cellulose
~ 20000 II
't
.t'
8"'
.~
_
10000
i---'1'-------======>i
..' r:ote;:~ ;;1
Viscosity of Compound AlB
are less than 20mPa ·s ~\)~
> o .::.- L_______o--e--'~-o-•-
0 5 10 15 20 25
Concentration of viscosity agent (%)
Fig. 2-Relationship between viscosity of solution and concentration of

viscosity agents
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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10000 , . . - - - - - - - - - - - - - - - ,
dosage (WX%) 1.0
~
0.7
~
~
'7il 1000
"""0
c
·;;;
0.5
0
u
0 2.1 2.1
>"'
too~~~--~----~--~~~~
additive-free A B AB AB AB
Fig. 3-Relationship between viscosity of slurry and concentration of VT
100000 , - - - - - - - - - - - - - - - - - - - ,
~ 10000- -
f
"""0
.£'
"'
0
~
> 100~---.~--~--~----~--~
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction of Compound A (NA+B)
Fig. 4-lnfluence of mole fraction of compound A on viscosity of slurry
9000
W/C
r-. 0.70
;;"'
} 6000
""'"'0
0 3000
·:;;
0
()
.;!l
>
0
0 1.0 2.0 3.0 4.0 5.0 6.0
Dosage of Compound A+B (WX%)
Fig. s-Relationship between viscosity of slurry and concentration of VT at each

water-cement ratio
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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146 Yamamuro et at.
W/C=0.70, dos.O.S%, 5000 mPa 'S
Fig. 6-Fluidity of cement slurry having different concentration ofVT at

water-cement ratio of 0.70
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
I 0,000 mPa · s
0.1
0.01 0.1 10 100
Angular rate w (rad/s)
Fig. 7-Frequency dependence of G' ofVT and MC solution

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10000
';' VT~
i
0..
G' 1000
~
1100
& 10 WIP~ 1OO%(CaC03)

s
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
rrJ 800 mPa·s
1 ~--~----~----~--~
O.Dl 0.1 10 100

Angular rate w (rad/s)
Fig. 8-Frequency dependence of G' ofVT and MC solution
Fig. 9-Cryo-SEM ofVT in slurry
Fig. to-Photographs of cement slurry with and without VT in water

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148 Yamamuro et al.
I I ! I
MC i 5,000
I : mPa·s
I J:
i I
[15,000 mPa·s( 4.0)
I (1.5)
VIS
I I I
VIS I 6,550 mPa·s (2.0)
additive
I
-free (dosage%)
0 5 10 15 20 25 30
Secondary exothermic peak time (h)
Fig. 11-lnfluence of viscosity agents on hydration of cement
Fig. 12-Hydrate crystals photomicrographs with VT at water-cement ratios of 2.0 (FE-

SEM)
without
VT
Fig. 13-Test of grout with and without VT for bored precast pile method at
sand ground
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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";;;' 5000
"'
~ 4000 -- ~
PE
w3000 '\ '-'
Vi
'0 2000 '\
.€
8 1000 ~NS
~ 0 .~
0 0.2 0.4 0.6 0.8 1 1.2
Dosage of superplasticizer (CX%)
Fig. 14-lnteractions between VT and superplasticizers
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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150 Yamamuro et al.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-11
Influence of Three Types

of Superplasticizers on
Tricalciumaluminate Hydration in
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Presence of Gypsum
by S. Pourchet, C. Comparet, A. Nonat, and P. Maitrasse
~\fnopsi~ Different types of superplasticizers have been widely used over the past
few decades in order to produce a more fluid or very high strength and durable
concrete. These chemical admixtures interfere with the various physico-chemical
processes occurring in early cement paste.
In this paper we present results from a study on the influence of superplasticizers
on pure tricalciumaluminate hydration in presence of gypsum. The suspensions
hydration has been investigated by conductimetry, isothermal calorimetry and total
organic carbon analysis of the liquid phase.
The time taken for ettringite formation has been determined without superplasticizer
and in presence of three different types of superplasticizers: polynaphtalene
sultanates (PNS), polycarboxylate-polyox (PCP) and diphosphonate terminated
polyoxyethylene.
Whereas diphosphonate terminated polyoxyethylene does not seem to modify
tricalcium aluminate hydration carried out in presence of gypsum, PCP and even
more PNS slow down ettringite formation. This effect seems to be largely due to a
decrease of the C3A dissolution rate and might be connected to an adsorption of
PCP. or PNS observed from the early C3A hydration. Such an adsorption does not
happen with diphosphonate terminated polyoxyethylene superplasticizer. Moreover
the presence of PCP superplasticizer causes a decrease in the size of the ettringite
crystals formed.
Keywords: hydration; superplasticizer; tricalcium aluminate

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152 Pourchet et al.
Sylvie Pourchet: sylvie.pourchet@u-bourgogne.fr
Universite de Bourgogne, Dijon FRANCE
Sylvie Pourchet is an assitant professor at the University of Bourgogne (France). Her
current research is based on the reactivity of cement with special interest in studying the
relation the mechanisms of hydration reactions in presence of organic admixtures.
Cedric Comparet: cedric.comparet@pole-technologique.lafarge.com

Lafarge,L.C.R., St Quentin Fallavier FRANCE
Cedric Comparet worked for Chryso during his Ph.D on interactions between
superplasticizers and hydraulic cement phases. He works for Lafarge (L.C.R.) as research
engineer on organa-mineral interactions.
Andre Nonat: andre.nonat@u-bourgogne.fr

Universite de Bourgogne, Dijon FRANCE
Andre Nonat is a research director in C.N.R.S. at the University of Bourgogne (France).
His research is based on the reactivity of cement with special interest in studying the
mechanisms of hydration reactions, the thermodynamical and microstructure of hydrates
and the mechanism of the setting.
Philippe Maitrasse: philippe.maitrasse@chryso-online.com

Chryso, Sermaises du Loiret, FRANCE
Philippe Maitrasse is a research manager of Chryso. He's mainly concerned by
superplasticizers research, development and relationship with concrete properties.
INTRODUCTION
Superplasticizers are polymers which added to concrete, increase the fluidity at

early age without affecting the setting and hardening behaviour of concrete. For that
purpose different polymers are used. Whereas polynaphtalene sulfonates (PNS) are often
reported to act on cement particles dispersion by electrostatic repulsion, polycarboxylate
with polyoxyethylene graft chains (PCP) or diphosphonate terminated monofunctional
polyoxyethylene polymer are given to disperse cement particles because of the steric
hindrance effect resulting from the extension of their graft chains away from the surface
of cement particles [ 1, 2]
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Moreover it is reported that the type of superplasticizer (SP) and the mixing
method as preparations conditions or the surrounding environment of concrete could
significantly affect the fluidity of the paste [3-14].
The main purpose of our study was to investigate the influence of the chemical
structure of various SPs on the interaction with early cement hydration products in order
to have a better understanding of the paste fluidity evolution.
Portland cement mainly consists of four mineral phases: the most abundant
phases are tricalcium silicate (C 3S, alite) and bicalcium silicate (C 2 S, belite) and the other
phases are tricalcium aluminate, Ca3A]z0 6 (C 3A) and calcium aluminoferrite
Ca4A[zFez0 10 (C 4AF, celite). Moreover gypsum CaS0 4 • 2H20 is added to clinker to
regulate the reactivity of the aluminate phases. When cement is mixed with water, it
undergoes a dissolution reaction generating calcium ions, hydroxyde, silicate, aluminate

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and sulfate anions in the interstitial solution. Very soon, new hydrates of low solubility
precipitate from the initially dissolved phases and these hydrates modify the fluidity of
the paste and then, give rise to the hardening of concrete. Because of the very high
reactivity of the aluminate phase in presence of water, the fluidity of the paste at the early
age will be governed by early hydration reactions of aluminate phase. Consequently, in
order to control the fluidity of the cement paste at early age in presence of
superplasticizers it is useful to study the hydration reactions of aluminate phase in
presence ofthe different superplasticizers.
Previous studies [ 15, 16] showed C3A hydration leads to same hydrates when
C3A hydrations are carried out in paste or in suspension. Furthermore hydrates formed in
a lime saturated solution are mainly the same as those obtained in water. Therefore, due
to the experimental methods used, C 3A hydration was studied in suspension. Because
adsorption of polymers largely depends on the chemical composition of the solution, C3A
hydration was studied in a lime saturated solution in order to mimic the pore solution.
Moreover early C3A hydration is known to depend on the type of calcium sulfate [17]. In
this paper we will focus on C3A hydration carried out in presence of gypsum.
Materials
Three types of superplasticizers were investigated for this study. Their chemical
structures and molecular weights are described in Table 1. The pH of these additives was
adjusted to 9.60 by adding 1M NaOH in order to neutralise all the acidic functions
present in the additive. Since adsorption mechanisms are governed by the concentration
of the additive in the solution, the superplasticizer dosages were calculated in order to
have the same concentration in solution as in the pore solution of a typical concrete. The
three superplasticizers were:
A polycarboxylate-type superplasticizer with a polyoxyethylene graft chain
(PCP) produced by Chryso. The main carboxylic and grafted polyoxyethylene chain
lengths are reported in Table 1. --`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
A polynaphtalenesulfonate polymer (PNS) produced by Handy Chemical

(Dysal) was also used.
A diphosphonate terminated monofunctional polyoxyethylene polymer
synthesized by Chryso and with a very well defined chemical structure reported in Table
1.
C3A was synthesized by Lafarge by mixing and pulverizing in accordance with
stoechiometric equation using calcium carbonate and alumina, and repeating the process
to calcine them at 1400°C for 3 hours in an electric furnace twice. C 3A obtained was
analysed by XRD.
As calcium sulfate, pure gypsum (R.P. Normapur prolabo) was used. The molar
ratio gypsum/C3A was adjusted to 0.2 by mixing 7.3 mmol of pure gypsum (1.25g) with
37mmol ofC 3A (10 grammes).

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154 Pourchet et al.
Experimental methods
The C3 A-gypsum mixture was hydrated at 25°C in dilute lime saturated suspensions with
a liquid/solid ratio equal to 25 under inert atmosphere in order to avoid carbonation. The
suspension was continuously subjected to mechanical stirring. The chemical evolution
was followed by isothermal calorimetry (Tian-Calvet Setaram) and by electric
conductivity measured with an XE 150 electrode (Tacussel).
To determine concentrations of species in solution ([Ca 2+], [Ae+], [SO{]) or the polymer
adsorption during the C 3A hydration reactions, small portions of the suspensions were
removed , filtered through 0.3 !Jill millipore filters and acidified to avoid carbonation. A
carbon analyser, model TOC 5050 (Shimadzu) was used to determine the evolution of
the adsorption of the polymer during the C 3A hydration. Atomic Absorption
Spectrometry (Perkin Elmer) was used for the calcium and aluminium concentrations
and ionic chromatography (Dionex) equipped with a conductivity cell was used to
determine sulfate concentration.
In order to analyse the effect of the different superplasticizers on the C 3A

hydration in presence of gypsum, the hydration of C 3A-gypsum mixture was first carried
out without superplasticizer in a lime saturated solution.
C3A-gypsum hydration without superplasticizer
The reference experiment was carried out by adding 37mmol of C3A and
7 .25mmol of gypsum to 250mL of lime saturated solution. The evolution of the sulfate,
calcium and aluminium ions concentrations and the heat flow deduced from the
isothermal calorimetry are reported in Fig. I. The Fig. 1 shows two parts.
During the first part, sulfate ions are still present in the solution and they are consumed to
precipitate a hydrate. That is the situation during the workability period. The second part
begins when the sulfate concentration becomes equal to zero.
First part-- When C3 A-gypsum mixture is introduced in a lime saturated solution without
additive, it undergoes dissolution reactions generating calcium ions, hydroxyde,
aluminate and sulfate anions in the interstitial solution according to the dissolution
reactions:
Ca3Ah06 + 6 HzO -:) 3 Ca2+ + 2 AI 3+ + 12 OR (I)

CaS04, 2 H20 -:) Ca2+ + SO/ + 2 H 20 (II)
The suspension very quickly becomes supersaturated with respect to ettringite and AFm.
Previous studies have clearly showvn that although ettringite is the more stable hydrate,
AFm phase precipitates at the very beginning of the C3A hydration and the early AFm
precipitation depends on different factors as for example the sulfate type used, C 3A
granularity or superplasticizer presence (18, 19]. Consequently the exothermic peak
obtained at the beginning of the first part expressed the very high reactivity of the system
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
and this peak results from the exothermic C3A dissolution and AFm and/or ettringite
precipitation.
This peak is followed by a period of a low thermic activity. Under the experimental
conditions, there is still solid gypsum at the beginning of the C 3A hydration giving rise to
the sulfate concentration plateau, because of the limited solubility of gypsum in lime
saturated solution which is equal to l2.5mmoVL.
Since aluminium concentration remains constant and very low so that it is not detectable,
we can deduce all the aluminium ions liberated by the dissolution are consumed by
ettringite precipitation. Namely, under these conditions, the supersaturation level is the
highest for ettringite which is then the more stable phase. Ettringite precipitates according
to the reaction :
Ettringite precipitation consumes calcium, aluminium and sulfate ions which causes
further C3A and gypsum dissolution. A stationary state is then established resulting
from dissolution reactions and from ettringite precipitation reaction. When gypsum is
totally dissolved, ettringite precipitation rate can be deduced from the decrease of
sulfate ions concentration. As usually reported and observed in these systems, the
average rate of ettringite precipitation from C3A and gypsum, is decreasing according
to time. For instance Fig.1 shows that 70 minutes (duration of the "sulfate plateau") are
needed to precipitate 1.4 mmo1 of ettringite from 4.2 mmol of gypsum and 1.4 mmol
of C3A (according to reactions I, II and III), while 140 minutes are needed to "convert"
the last 3 mmol of sulfate into I mmol of ettringite. Moreover, because sulfate
concentration decrease is linear, we assume ettringite precipitation is quite constant
during this period. Such an evolution on the rate of ettringite precipitation from C3A
and gypsum has already been reported [18]. The average rate of ettringite precipitation
clearly depends on the C3A granularity but also on other parameters as sulfate
concentration.
Second Part.--This part begins when sulfate concentration becomes equal to zero. C3A
hydration without sulfate leads to a metastable calcium hydroaluminate precipitation
according to the reaction:
The exothermic peak appearing at the beginning of this period is attributed to C3A
dissolution which is going on faster and C4AH 13 precipitation. Due to C3A dissolution (I)
and C4AH 13 precipitation (IV), calcium ions concentration decreases and consequently
conductivity too, whereas aluminium ions concentration increases.
In the same time monosulfoaluminate(3Ca0 AbOJ.CaS04 ,12H2 0) becomes more stable
than ettringite and consequently precipitates by using sulfate ions liberated by ettringite
dissolution. This last reaction is very slow and ettringite is still present two days later.
Finally, all these reactions give rise to a stationnary state.

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
156 Pourchet et al.
Consequently, the conductivity curve allows us to determine the duration of the
first step which corresponds to the precipitation of 2.4 mmol of ettringite under our
conditions from C3A and gypsum. Moreover, the evolution of sulfate ions concentration
allows us to determine the time needed to precipitate total ettringite and also the first 1.4
mmol.
Effect of the superplasticizers on the reactivity of the C1A-gypsum system in a lime

saturated solution
The evolution of the electric conductivity during the hydration of a C3A-gypsum

system in a lime saturated solution and in presence of 0.5g of superplasticizer that is to
say 5% with respect to the C3A weight is represented in Fig.2. From these curves it
appears that the diphosphonate doesn't modify the duration of ettringite precipitation
whereas both PNS and PCP decrease the rate of ettringite formation. Next Figures
(Fig.3,4,6) represent the evolution of the ionic concentrations during the C3A-gypsum
system hydration in presence of the different superplasticizers.
Diphosphonate.--The C3A-gypsum mixture was introduced in a lime saturated solution

containing 5% of diphosphonate with respect to the C3A weight. The results are presented
in Fig.3. The reference experiment was carried out with the same C 3A sample. As we can
see In fig.2 the diphosphonate doesn't modify the duration needed to precipitate ettringite
from gypsum and C3A. The same experiment was also carried out with higher levels of
gypsum (2 and 2.5g of gypsum) and again, the time needed to precipitate the ettringite is
the same with or without the diphosphonate, as reported in Fig.3. The only noticeable
difference is relative to the initial conductivity. The slight increase observed in presence
of the diphosphonate can be attributed to the ability of the diphosphonate to form a
complex with calcium ions and consequently increases the solubility oflime. [20]
PNS.--The average rate of ettringite precipitation is drastically decreased in the presence

of PNS; the time needed is approximately multiplied by four in the experimental
conditions (Fig.2). The decrease of the rate depends on the PNS dosage as shown in the
Fig.4. Moreover Fig.4 shows the decrease of the precipitation rate when the sulfate
concentration is at the plateau level and also when it decreases. Figure 5 suggests that the
time needed to precipitate ettringite in the presence of PNS could be correlated with the
initial adsorption level ofPNS. The slowing down ofthe ettringite precipitation is maybe
linked to a decrease of C3A dissolution rate.
PCP.--Figure 2 shows a slowing down of ettringite precipitation as a result of the PCP

presence. Under the experiment conditions the time needed to precipitate the ettringite is
multiplied by 1.5 in presence of 5% of PCP. Moreover an increase of the PCP amount (5
to 6 % ) leads to higher duration (Fig. 7). As the slope of the sulfate concentration
decrease is linked to the rate of ettringite precipitation we conclude that PCP slows down
the rate of ettringite precipitation.
Nevertheless it appears that the rate of ettringite precipitation is not affected when the
sulfate concentration is high enough and at the "plateau" value (Fig.7). In the same time,
the size of ettringite crystals precipitated in the presence of PCP during this period, is

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smaller than usually. Indeed in order to determine concentrations of species in solution
during the C3A hydration reactions, small portions of the suspensions were removed, and
as usually filtered through 0.3 11m millipore filters. However in the presence of PCP,
aluminium, calcium and sulfate concentrations proved that ettringite crystals were present.
in the filtered solution (Fig.8). In this case a new filtration was done using O.l)lm filters
in order to prevent ettringite from going through. SEM images of the solid collected on
the O.l)lm filter one hour after the beginning of the C3A-gypsum hydration in saturated
lime solution in the presence of PCP are presented in Fig.9. PCP clearly decreases the
size of the ettringite crystals formed.
Consequently, the presence of PCP induced a slowing down of the rate of ettringite
precipitation and a decrease of the size of ettringite crystals. The PCP may act on
ettringite precipitation by decreasing its growth rate. Previous studies already showed
such a decrease of the growth rate or a modification of the ettringite morphology as a
result of a polymer adsorption [21-25]. However the average rate of ettringite
precipitation is not affected when the sulfate concentration is high enough and at the
"plateau" level Namely when the sulfate concentration is high enough and at the plateau
level, ettringite nucleation might take place and by this way the rate of ettringite
precipitation would not be decreased during this period.
Study of the adsorption:
Preliminary adsorption isotherms were established on pure ettringite, mosulfoaluminate

and C3AH 6 for each superplasticizer in saturated lime solution and with a liquid to solid
ratio adjusted to 25. They are reported in Fig.l 0.
The specific surface area determined by B.E.T. using nitrogen are reported in Table 2. As
expected, the adsorption level mainly depends on the specific area of the hydrate and
consequently the adsorption level on monosulfoaluminate and ettringite is similar and
larger than that on C3AH 6 phase. Therefore the adsorption should be larger again on
platey hexagonal C4AH 13 crystals. Moreover PNS and PCP show larger ability to adsorb
than the diphosphonate. By using these informations we are able to approximately
determine the amount of each superplasticizer likely to be adsorbed on 2.4 mmol of
ettringite that is to say on ettringite which will precipitate during C3A hydration under our
conditions. By this way about 9mg of diphosphonate and 30 mg of PNS or PCP should
adsorb on ettringite as represented in the Fig.l2.
The evolution of the superplasticizer adsorption during the C3A-gypsum hydration is
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
reported in Fig.ll. An initial adsorption is only observed for both PCP and PNS. In the
case of the PNS, a large part of the superplasticizer, about 150mg ( 30%), is adsorbed
during the first minutes. The initial adsorption could happen on the anhydrous phases but
also on the AFm formed at the very begining of the C3 A hydration, because of its
important specific surface area.
In a second time, a quite linear increase of adsorption is observed during the ettringite
precipitation with all superplasticizers. Nevertheless, whereas about lOOmg of PCP or
PNS are adsorbed on ettringite, only 1Omg of diphosphonate seems to be adsorbed on
ettringite. These amounts are larger than the values previously calculated for the PCP and
PNS (~30mg for PNS and PCP). These values are reported infFig.12. These differences
can result from the adsorption of other phases which could also be formed (AFm for

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158 Pourchet et al.
example). Furthermore, we also can suspect a modification of ettringite morphology due
to the adsorption of superpasticizer on ettringite giving rise to an increase of ettringite
specific surface area. Namely, the previous observations made on the effect of PCP on
the size of ettringite crystals lead us to conclude that the superplasticizer adsorption
should be higher because of the increase of the specific area of the ettringite formed in
this case.
At least, when there is no more sulfate ions in solution, hydroaluminate begins to
precipitate, giving rise to a large adsorption of the superplasticizers. The adsorption level
gets fastly maximum, all the superplasticizer able to be adsorbed are adsorbed.
CONCLUSIONS
The interaction of superplasticizers with C 3A when hydration occurs in presence of

gypsum was studied with three types of superplasticizers.
Diphosphonate does not modify the average rate of ettringite precipitation. No adsorption
happens during the first minutes and the adsorption level of the polymer on ettringite is
low.
The PNS slows down the ettringite precipitation. The decrease of the average rate of
ettringite precipitation is higher with higher PNS dosages. Moreover, the time needed to
precipitate ettringite varies as a function of the initial PNS adsorption level. PNS may act
on C 3A hydration by decreasing its dissolution rate, in consequence of its strong initial
adsorption. By using PNS delayed addition, the strong initial adsorption on the aluminate
phases can be avoided and consequently more PNS can act efficiently on silicate phases
in slowing down its hydration and delaying setting.
PCP also slows down ettringite precipitation, but the decrease of ettringite precipitation is
less strong than with PNS. Whereas PCP may decrease the C3A dissolution rate, it mainly
acts on ettringite growth giving rise to smaller size of ettringite crystals.
REFERENCES
1. Uchikawa, H., Hydration of cement and structure formation and properties of

cement paste in the presence of organic admixture. in Conference in tribute to
Micheline Moranville-Regourd. Importance of Recent Microstructural
Developments in Cement and Concrete. 1994. Sherbrooke, Canada, E.C.
Canada, Editor. p. 63-117.
2. Uchikawa, H., S. Hanehara, and D. Sawaki, The role ofsteric repulsive force in
the dispersion ofcement paricles in fresh paste prepared with organic
admixture. Cement and Concrete Research, 1997. 27(1): p. 37-50.
3. Tagnit-Hamou A., A.P.C., Cement and superplasticizer compatibility. World
Cement Research and Development, 1993. 24(8): p. 38-42.
4. Hanehara, S. and K. Yamada, interaction between cement and chemical
admixture from the point of cement hydration, absorption behaviour of
admixture, and paste rheology. Cement and Concrete Research, 1999. 29: p.
1159-1165.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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5. Altcin, P.-C., C. Jolicoeur, and J.G. MacGregor, Superplasticizers: how they
work and why they occasionally don't. Concrete International. 16(5): p. 45-52.
6. Yamaguchi, 0., H. Nakajima, and M. Takahashi, The effect ofpaste and mortar
containing various type of water-reducing agents. JCA Proceedings of cement
and concrete, 1995. 49: p. 216-221.
7. Kato, H., K. Yoshioka, and M. Ushiyama, Influence of sulfate ion on steric
hindrance in the performance ofsuperplasticizers. JCA Proceedings of cement
and concrete, 1997. 51(258-263).
8. Jiang, S., B.-G. Kim, and P.-C. Altcin, Importance of adequate soluble alkali
content to ensure cementlsuperplasticizer compatibility. Cement and Concrete
Research, 1999.29: p. 71-78.
9. Okamura, T., H. Harada, and M. Daimon, Influence of calcium sulfate in belite-
rich cement on the change in fluidity of mortar with time. Cement and Concrete
Research, 1998. 28(9): p. 1297-1308.
10. Nawa, T., H. lchiboji, and M. Kinoshita. Influence of temperature on fluidity of
cement paste containing superplasticizer with polyethylene oxide graft chains. in
Superplasticizers and other chemical admixtures in concrete. Proceedings Sixth
International Conference CANMET SP-195. 2000. Nice, France: ACI
International, V.M. Malhotra, Editor. p. 195-210.
II. Jolicoeur, C. and M.-A. Simard, Chemical admixture-cement interactions:
phenomenology and physico-chemical concepts. Cement & Concrete
Composites, 1998. 20: p. 87-101.
12. Bonen, D. and S.-L. Sarkar, The superplasticizer adsorption capacity of cement
pastes, pore solution composition, and parameters affecting flow loss. Cement
and Concrete Research, 1995. 25(7): p. 1423-1434.
13. Coppola, L., Troli, R.,Zaffaroni, P.,Collepardi, M.Injluence of the sulfate level
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
in the clinker phase on pe1jormance of superplasticized concretes. in

Proceedings of the fourth CANMETIA.C.I.Inter. Symp. on advances in concrete
technology SP-179 (Recent Advances in Concrete Technology). 1998. Michigan:
American Concrete Institute. p. 271-281.
14. Jolicoeur, C.S., J.; Otis N.; Lebel A.; Simard, M.A.;Page, M. The influence of
temperature on the rheological properties ofsuperplasticizered cement pastes.
in Fifth CANMET! A CIInternational Conference on Superplasticizers and other
Chemical Admixture in Concrete. 1997, V.M. Malhotra, Editor. p. 3 79 -405.
15. Breval, E., C~ hydration. Cement and Concerte Research, 1976.6: p. 129-138.
16. Taylor, H.F .W., Cement chemistry (2nd edition). 1997: Thomas Telford edition.
17. Tang, F.J. and E.M. Gartner, Influence ofsulphate source on Portland cement
hydratation. Advances in Cement Research, 1988.1(2): p. 67-74.
18. Minard, H., Etude integree des processus d'hydratation, de coagulation, de
rigidification et de prise pour un systeme C3S-C;A-sulfates-alcalins. 2003,
Thesis: Dijon France. Universite de Bourgogne.
19. Sakai, E., J.K. Kang, and M. Daimon, Influence ofsuperplasticizers on the very
early hydration ofCa~l206 in the presence ofgypsum, CaS0 4 0.5H20 and
CaO Cement Science and Concrete Technology, 2002. 56: p. 36-41.

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20. Comparet, C., etude des interactions entre les phases mode!es representatives
d'un ciment portland et des superplastifiants du beton. Thesis Universite de
Bourgogne Dijon France, 2004.
21. Simard, M.A. and P .-C. Aile in, Calorimetry, rheology and compressive strength
ofsuperplasticized cement pastes. Cement and Concrete Research, 1993. 23(4):
p. 919-9:'i0.
22. Hekal, E.E. and E.A. Kishar, Effect of sodium salt of naphtalene-formaldehyde
polycondensate on ettringiteformation. Cement and Concrete Research, 1999.
29: p. 1535-1540.
23. Afridi, M.U.K., et al., Effects ofpolymer modification on the formation of high
su!foaluminate or ettringite-type AFt crystals in polymer-modified mortars.
Cement and Concrete Research, 1994. 24(8): p. 1492-1494.
24. Sakai, E., eta!., Influence ofsodium aromatic sulphonates in the hydration of
tricalcium aluminate with or without gypsum. Cement and Concrete Research,
1980. 10(3): p. 311-319.
25. Slanicka, S. Influence of water soluble melamine formaldehyde resin in
hydration ofC3S, C;A+CaS04.2 H 2 0. in International Congress on the Cement
Chemistry. 1980. Paris, France: Septima. p. 161-166.
Table )--Chemical structures of the different Superplasticizers
SPname Chemical formula
/ CH2-PO/, 2Na+
Diphosphonate CH3 -[0-C~-CH2Jn-N+-H
' CH2-PO{, 2Na+
PCP
t CH2-t cj~ c~)
too t=o
CH2-t -
6
Na+ n p q
( tH2CH20)m
n-0.4 p-0.6 m-15
~~_.'
PNS
S03Na
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Table 2--Specific area of different hydrates fonned during C3A-Gypsum hydration
Hydrogarnet Monosulfo
Cornpmmd c3~ ettringite aluminate
BET Specific 3.5 1.1 1.2

surface area
Jmz/g)
Part1 Part2
- ( b ) heat flow mW/g of C3A
o (c) [calcium] mmoi/L
- ... - (a) [aluminium] mmoi/L
- ( d ) Conductivity mS/cm
20
o~~~~~~~~~~--~---=~==~~==~o
0 100 200 300 400 500 600 700
llme(min)
Fig. 1-- Evolution of heat flow, electric conductivity and ions concentration during C A
3
hydration (10g) in saturated lime solution in presence of 1.25g of gypsum. The liquid
to solid ratio was adjusted to 25
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
200 400 600 600 1000 1200

time (min)
Fig. 2·- Evolution of electric conductivity during C3A hydration (10g) in saturated lime
solution in presence of 1.25g of gypsum and in presence of o.5g of superplasticizer.
The liquid to solid ratio was adjusted to 25.

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
162 Pourchet et al.
14 - - - - - - - - - - - - - - - - - - - - - - ,
12
·--···(a) reference, 1.25g gypsum - (a15%diphoaphonate, 1.25g gypsum

······(b) reference,2g gypaum - (b15%dlphosphonate,2g gypwm
-- -(c)reference.2.5g gypsum - (c') 5%Ctphospnonate,2.5g gypsum
200 400 600 BOO 1000 1200 1400

Time(min)
Fig. 3 -- Evolution of the electric conductivity during C3A hydration (tog) in a lime
saturated solution with or without o.5g of diphosphonate and in presence of different
quantities of gypsum. liquid/solid= 25.
-{a)conductlvlly relaranca
- -(b) conductlvttyPNS 2%
······ (c)oonductiYity PNS 5%
--[sulfate] mmoVL reference
"""'!'l •[sulfate]mmolll PNS 2%
- .. -[sulfate] mmolll.. PNS 5%
'
\
200 400 600 800 1000 1200

r~me(min)
Fig. 4-- Evolution of the electric conductivity during C3A hydration (tog) in a lime
saturated solution in presence of t.25g of gypsum and in presence of different
amounts of PNS. The liquid to solid ratio was adjusted to 25.

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!lOO
'C' sao .a.

i
!
700
- 600
~
;sao
.
.
~
=
'!i
400
300
.a.
.a.
j 200
i!,
.. 100
4 10 12 14 16
PNS lniUally adsorbed rnglg OfC3A
Fig. s-- Evolution of the duration of ettringite precipitation versus initial adsorption
level of the PNS. tog of C A were hydrated in zsoml of a lime saturated solution and
3
in presence of 1.25g of gypsum.
14 ---------------------------------------,100
••• 90
• r~-------------.--:~::::~=o···- 80
70 §
•
! ...._(aluminium] mmoi/L
aoJ
so'lil
o o o o
•
•
t
I
o [PCP3S%] adsorbed %
o (calcium] mmoL'L
401B
o oo o o o • o f
~0 --------------------f~-
o.!.·'o 20
0 0 <t....-"' ..
~~,! __ 1>.,_!.---~---~--~.--------.. • 0 0 10
~-.~~~~~~~. .~~~-------,~----~~----+0
0 100 200 300 400 500 600
Time(min)
Fig. 6-- Evolution of the electric conductivity and ions concentration during C A
3
hydration (wg) in a lime saturated solution in presence of 1.25g of gypsum and o.sg
of PCP. The liquid to solid ratio was adjusted to 25.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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164 Pourchet et al.
0 100 200 300 400 500 600

Time(min)
Fig. 7 ·-:Evolution of the electric conductivity and the sulphate concentration during
C A hydration (10g) in a lime saturated solution in presence of 1.25g of gypsum and in
3
presence of different amounts of PCP.
- • - [calduml mmolll
---[suffate]mrnol/1..
--[ahJminiuml mmo\f\.
opan ayrnbola =filler 0.3f.1m
turraymbola,..fllter01J!m
100 200 300 4()0 500 600

T1me(min)
Fig. 8-- Evolution of the aluminium, calcium and sulfate concentrations of the
solution filtered through 0.3 11m or o.liJm millipore filters during the C3A-Gypsum
hydration in presence of s%PCP.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
3 JliD
Fig. 9-- Typical SEM images of ettringite obtained 1 hour after the beginning
of the Cl-gypsum mixture hydration in presence of s% of PCP or without
superplasticizer (down).

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166 Pourchet et al.
0 0.5 1.5 2 2.5 3

[diphosphonate) giL
20 , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .
18
16
1,,,""
--------------------------
Fig.b
~ 14 I
,
I
I
12 -C3AH6
10 - •· ettringite
......,...... m on oau lfoafum in ate
!I 8
if"' 6
0.5 1.5 2.5

[PNS[ giL
20 .--------------------------------------------,
18 Fig.c
-----------·
.
;,.' .·•· · · ~---=--
•· · · · · · · · · · • .
16
"'14 ------- -•-C3AH6
E /,- ··+·· ettring ite
-g 12
.,..
€ 10
n.
0
n.
0
6
8 ,. /
"'
.......-monosulfoaluminate
~-J
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
4
2 .......__._...,!/
---------------_
0
0 0.5 1 .5 2 2.5 3
[PCP] giL
Fig. 10 a,b,c.-- Adsorption of the diphosphonate (a), PNS (b) and PCP (c) on aluminate
phases: ClH 6 , ettringite and monosulfoaluminate in a lime saturated solution and
with a liquid-to-solid ratio adjusted to 25.

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120
~100
€
0
~ 80
.r-··-·-
~
:il 60 ( . ·············•······-··········•··················· ........................... .
0
.!!!
~40
a.
r.-----~;
' i
.
""'
~ 20
__.. .•..-!: ......-""' · ·- · ·% diphosphonate adsorbed
-%PNS adsorbed
0
.............. -
..'
- •% PCP adsorbed
0 200 400 600 BOO 1000

time (min)
Fig. 11--Evolution of the fraction of superplasticizer adsorbed during C3A-gypsum

hydration in a lime saturated solution. o.sg of superplasticizer was added to 10g of
C3A and 1.25g of gypsum.The liquid to solid ratio was adjusted to 25.
120
a; II experimental adsorption Ill adsorption calculated from isotherm curves
!:?
gtoo
~c
.
~
<=
0
80
~
60
.0
II)
'0
c.. 40
en
'0
E 20
~"
«J
0
PCP PNS Diphosphonate
Fig. 12--Comparison between the amount of superplasticizer adsorbed during the

ettringite precipitation deduced from the adsorption measurements (Fig. 11) and
the amount of superplasticizer adsorbed on ettringite calculated from isotherm
adsorption curves represented on the Fig. 10.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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168 Pourchet et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-12
Optimizing Polycaboxylate Polymers
by I. Schober and R.J. Flatt
Synopsis: Polycarboxylate polymers as superplasticizers have revolutionized

concrete technology in the past years. Today most of sec and high performance or
ultra high strength concrete is produced with this new kind of polymers. Their comb·
like structure consisting of an ionic backbone and non-ionic polyalkylene glycol
side chains offers a huge "playground" for polymer design. Polymers with different
side chain chemistry, length, grafting density as well as with different backbone
ionic content, structure and length are on the market, which offers the customer an
almost confusing range of superplasticizers. Different concrete applications often
require different and chemically optimized superplasticizers. The universal admixture
is still a challenge for the researchers. In order to better understand the structure-
performance relationship of polycarboxylates, systematic variations of comb type
superplasticizers were produced in the laboratory and the influence of the changes
in polymer structure on the performance in cement paste, mortar and concrete was
studied. Clear effects of the structural changes on the performance regarding water
reduction, flow improvement and slump retention can be shown. They stress the
importance of a good adsorption and adequate surface coverage to achieve good
dispersion. All can be directly influenced by the polymer design depending on the
desired properties of the superplasticizer.
Keywords: adsorption; concrete; flow retention; mortar; paste flow;

polycarboxylate ether; polymer structure; SCC; superplasticizer
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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170 Schober and Flatt
Irene Schober received her PhD in chemistry from the Technical University of Vienna.
She is head of the Polymer Synthesis Department of Corporate Research at Sika
Technology AG (Ztirich, Switzerland).
Robert J. Flatt is head of inorganic chemistry in Corporate Research at Sika Technology

AG (ZUrich, Switzerland). He has a PhD (1999) in materials science and a chemical
engineering diploma from the Swiss Federal Institute of Technology in Lausanne (EPFL).
In 2003, he was awarded the RILEM Robert L'Herrnite Medal in recognition of his
contributions to the understanding of admixture behaviour in cement and concrete.
INTRODUCTION
The newest generation of superplasticizers, the polycarboxylate-ethers, offer a

wide variety of modifications that influence the performance and make specially
designed polymers for special applications possible. However, constantly increasing
performance requirements like extreme high water reduction or strongly extended slump
retention can eventually lead to more sensitive systems. This means, that the performance
of the admixtures is more sensitive to the production conditions like cement type, W/C,
mixing time and aggregates. This leads to a large variety of polycarboxylate-ethers on the
market with basically the same chemistry but large differences in behaviour, targeted
applications and performance.
BACKGROUND
To produce a homogeneous concrete with low water content and good

workability the cement particles must be well dispersed in the system. Well dispersed
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
means, that the portion of flocculated cement particles in the system is low. The cement
particles flocculation is due to attractive interparticle forces which can he of van der
Waals or electrostatic origin. The magnitude of these forces increases as the interparticle
distance decreases. This may happen at rest and over the time and lead to the system
showing a slump loss. The stronger the attractive interparticle forces are, the larger is the
yield stress related to the slump loss. However, not only the interparticle forces but also
their number influence yield stress. High volume fractions increase the number of
interparticle contacts and thereby the interparticle forces.
Thus, in order to increase the fluidity of the system one can attempt either reduce
the number of possible interparticle contacts (by increasing the water content) or by
decreasing the magnitude of the attractive interparticle forces (adding a superplasticizer).
We also note that mixing will have temporarily reduce the number of particles in close
contact and have an effect on both the number of particles in close contact as well as on
the magnitude of the interparticle forces.
Increasing the W/C or reducing the cement content in the concrete at a given
amount of water unfortunately leads to reduced strength of the hardened material and to
reduced durability. Therefore superplasticizers or high performance water reducers
should be preferred. These substances adsorb on the cement particles. If particles come in

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closer contact the adsorbed superplasticizers induce repulsive forces with either
electrostatic and/or steric origin. At high ionic strength, like in cement suspensions,
electrostatic repulsion is usually of insufficient range to outweigh the van der Waals
attraction. The superplasticizers based on polycarboxylate ethers act via electrosteric
stabilisation of the system with focus on the steric stabilization 1· 3 • The polymers consist
of an anionic backbone and non-ionic side chains (Fig. 1). They adsorb on the cement via
the backbone with the side chains, which do not adsorb, dangling into the solution more
or less coiled, depending on the polymer structure. If two polymer-covered particle
surfaces come close to each other, en tropic effects that unfavour the mixing of the
polymer chains dangling into the solution (reduction of the entropy of freedom) prohibit
the aggregation ofthe particles, thus leading to a well dispersed system (Fig. 2). The
chemistry of the backbone (number and type of anionic groups, length ofthe chain) as
well as that of the side chains (length, type, number) can be varied to a large degree
offering the chemists a wide field of innovation. The performance of the polymer as a
dispersing agent in cement depends on its adsorption parameters like the amount of
adsorbed molecules, the layer thickness of the polymer layer and the degree of surface
coverage. Each change of the polymer influences these parameters and therefore the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
performance as plasticizer with respect to flow, flow retention, setting time and
sensitivity to changes in the cement solution 4·6 . The adsorption of a polymer also depends
on the substrate, in this case on the type of cement and the solution chemistr/· 8 .
Therefore in some cement-superplasticizer combinations unsatisfying fluidizing
properties or fast stiffening occur which are described as cement-superplasticizer
incompatibility.
EXPERIMENTAL
Materials
Polycarboxylate-ethers--In the first series (PEI-PE4) only the ratio of
methacrylic acid to polyalkylene glycol methacrylate was varied keeping the length of the
side chains the same. In the second series (PE5-PE10) the length of the side chains was
varied too (Table 1). For the use in mortar or concrete the polymer solutions were
defoamed with a commercial defoaming agent.
Cements--The composition ofthe cements is given in Table 2. NPCl and NPC2

are commercially available Swiss cements. NPC I is a standard cement whereas NPC2 is
a sulphate resistant cement with low content of C 3A. NPC3, NPC 4 and NPC 5 are
European Type I 42.5 cements. NPC3 is a standard cement, NPC4 is a high C3A cement
and NPC5 is a low alkali cement. All three cements were ground without a grinding aid.
Methods
Adsorption tests--200 g cement and 100 g water containing the polymer are
blended with a mechanical stirrer. After the defined time part of the slurry is taken and
the liquid phase is separated from the cement by centrifugation with 8000 rpm for 8
minutes. The amount of polymer in the supernatant phase is determined by HPLC with a
light scattering detector. The difference in the polymer concentration in the liquid before
and after adsorption is calculated as adsorbed polymer.

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`````,,,,```,-`-`,,`,,`,`,,`---
Paste-flow test--In a 500 ml blending cup 250 g cement and tap water containing
the superplasticizer are blended by hand at a W/C of0.23 for 2 minutes. The paste is
filled in a cylinder of 50 mm inner diameter and height of 51 mm placed on a dry glass
plate. This cylinder is described in JASS 15M 103 and is used to evaluate the
performance of superp1asticizers (8, 15). The cylinder is lifted and the spread diameter of
the cement cake is taken as the flow value.
Mortar test--Mortar with aggregates from 0-8 mm is used (Table 3). The cement
is mixed with the sand in a Hobart blender for 1 minute. Then the water containing the
superplasticizer is added and the mortar is blended for an additional 3 minutes. A flow
cone of 100 mm lower and 70 mm upper diameter and a height of 60 mm is filled with
the mortar and lifted. The flow table spread is the diameter of the mortar cake produced
when the flow table is dropped 15 times from a height of 20 mm. The measurement of the
flow is repeated after 30 and 60 minutes with a re-mix of 30 seconds.
SCC--The mixture proportion of SCC is given in Table 4. The fly ash is added to
avoid bleeding and segregation. The mixing is done according to EN 480-1. Aggregate,
sand and filler are placed first in the mixer. Half of the mixing water is added and all is
mixed for 2 minutes. The mixer is stopped and after 2 minutes of rest the cement and the
fly ash are added and all is mixed for 30 seconds. Next the remaining water containing
the superplasticizer is added within 30 seconds and the concrete is mixed for another 2
minutes. A flow cone of 200 mm lower and 100 mm upper diameter and a height of 300
mm is filled with the concrete and lifted. The spread of the cement cake is measured
when the concrete stops flowing and this value is called "slump flow". The measurement
is repeated after 30, 60, 90 and 120 minutes with 15 seconds re-mixing.
Concrete test--Concrete with a grading according to EN 480-1 is produced

(Table 5). Filler, sand, aggregate and cement are blended dry for 30 seconds. The mixer
is started and all the water including the superplasticizer is added within 30 seconds and
the concrete is mixed for another 30 seconds. The total wet mixing time is 1 minute. The
plasticity of the concrete is determined by the flow table test according to EN12350-5. A
flow cone of200 mm lower and 130 mm upper diameter and a height of200 mm is filled
with the concrete and lifted. The flow table spread is the diameter of the concrete cake
produced when the flow table is dropped 15 times from a height of 40 mm. This
measurement is repeated after 30, 60, 90 and 120 minutes with 15 seconds of remixing.
Adsorption of polymers on cement

The adsorption of PEl to PE4, all polymers with the same structure but varying
ratio ofmethacrylic acid to methacrylic ester, on cements NPCl and NPC2 was
measured. The dosage was 2 and 4 mg solid polymer per g of cement. The adsorption
was generally low, from about 15% to about 50% of the added polymer. PE4 adsorbs
most, PEl to the least. This confirms previous data 6• 9 that the higher the content of
methacrylic acid groups in the polymer backbone (higher ratio of acid to ester), the
higher is the adsorption. NPC2, the cement with the low content of C3A shows low

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`---
adsorption for all polymers. This is not astonishing, since C3A is the most reactive phase
of the cement that adsorbs or consumes the polymers 4' 10 •
The adsorption after 30 minutes of PE5 to PEIO was measured on NPC3, NPC4
and NPC5 (Fig. 4) . With increasing dosage, the amount of adsorbed polymer increases
but stops at a certain level. This dosage where no more adsorption takes place when
polymer is added is the so called dosage of surface saturation which is dependent on the
structure of the polymer and the type of cement. Again NPC4, the cement with the
highest content ofC 3A, adsorbs/consumes the highest amount of polymer. The adsorption
on NPC3 and NPC5 is comparable. When we compare the polymers with the same
(short) length of the side chains (PE5, PE6 and PE7) we see, that the polymer with the
high amount of methacrylic acid and with the longer backbone (PE6) adsorbs most,
whereas a low amount of methacrylic acid, as seen before, results in poor adsorption
(PE7). This is also confirmed by the high adsorption ofPE8 with it's high content of
methacrylic acid in the backbone and medium length of the side chains. Increase of the
side chain length by keeping the amount of methacrylic acid in the backbone, as done for
PE9 in comparison to PE8, reduces the adsorption. A high degree of adsorption with low
amount of methacrylic acid in the backbone can be reached with a combination of very
short and medium length of the side chains (PEIO).
Effect of adsorbed polymer on the flow of a cement paste

The importance of polymer adsorption on the performance of the polymers
regarding water reduction and improvement of the flow of a cement paste has been
shown before 6 ' 9 . Figure 5 shows the flow of a cement paste ofNPC3 in dependence of
polymer type and dosage. If we draw the amount of adsorbed polymer after 30 minutes
for a dosage of 3 mg per g of cement against the flow of the cement paste after 30
minutes with the same polymer dosage we find a linear correlation (Fig. 6). This result
indicates the importance of the good adsorption of these polycarboxylic ether polymers to
act as a superplasticizer.
Polymer performance in mortar

Although the linear correlation of adsorbed amount of polymer with the flow of
the cement paste was shown before, no correlation with the flow of the mortar can be
seen. The reason can be either the adsorption of polymer on the limestone filler and I or
the treatment of the mortar with 15 shocks on the shocking table before measuring the
spread. The influence of the shocks is dependent on the mortar density and possibly
plastic viscosity and not only on the yield value, whereas the flow of the cement paste is
directly correlated to the yield value 11 • 12 .
Mortar tests with PE 1 to PE4 with NPC 1 and NPC2 (Fig. 7 ) and the mortar tests
ofPE5 to PEIO with NPC3, 4 and 5 (Fig. 8) show, that not only each cement has it's
optimum superplasticizer but that also different W/C show different optimal polymers. In
the first mortar series (Fig. 7) the best superplasticizer for NPC 1 at higher W/C and lower
polymer dosage is PEl, the polymer with the lowest amount ofmethacrylic acid in the
backbone. The flow table spread decreases from PEl to PE4 in which the content of
methacrylic acid in the backbone of the polymer increases (Fig. 7 a), but when we reduce

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```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
the W/C ratio and increase the polymer dosage, PE3 is the optimum polymer (Fig. 7 b).
For NPC2 the difference in polymer performance is lower, possibly due to the low
content ofC 3A which makes the cement more "robust". If we increase the content of
methacrylic acid in the backbone (from PEl to PE4) we increase the flow of the mortar at
low dosage and higher W/C but when theW/Cis decreased PEl to PE3 have about equal
performance and PE4 is poorer (Fig. 7 c and d).
Another mortar series with PES, PE6, PE8 and PE9 was tested. PE7 and PEl 0
could not be measured at the same time therefore PES was tested again in order to be able
to compare the performance ofall6 polymers (Fig. 8). Again no correlation of the mortar
flow with the amount of adsorbed polymer is found. The polymer dosage and Wle as
well as the type of cement influence which polymer is the best performing regarding the
flow of the mortar. Polymers with high adsorption like P£8, for example, show poorer
relative flow than PES at low dosage and higher W/e whereas better relative flow at
lowerW/e and higher dosage with NPCl. Whereas PE7, that has low adsorption rate, is
better at lower dosage and higher W/C than at higher dosage and lower W/C.
There is no trivial link between polymer adsorption and flow table spread of
mortars, which we attribute to the nature of this test. We infer that a similar conclusion
would be drawn for vibrated concrete.
Polymer performance in self-compacting concrete (SCC)

sec is not vibrated, therefore in this case, the mass of adsorbed polymer should
be a measure for the slump flow of sec which is directly correlated with the yield stress
of the concrete. This was shown by the good correlation of adsorbed amount of polymer
on calcium carbonate and the flow in non vibrated concrete9 and by the correlation of the
paste flow with the concrete slump flow 13 .
To determine the different effects of the polymers in SCC we chose polymer

PE7 and polymer PElO, the cement used was NPCS. Polymer PElO is a polymer with
high adsorption and thus a high flow in the cement paste. Polymer PE7 adsorbs only to a
limited extent and the flow in the cement paste is lower than that of PE 10 (Fig. 5). SCC
was produced by adding fly ash to the cement to avoid bleeding and segregation. The
adsorption of the PE polymers on fly ash and standard cement is very similar as shown in
Fig. 9. Therefore we can compare the adsorptions on the pure cement to predict the
performance in the fly ash blend too but of course only with respect to the slump flow
(yield stress) ofthe concrete. As expected, the necessary dosage ofPE7 is higher than
that ofPElO to reach the desired slump flow of about 75 em (Fig. 10). On the other hand
the slump flow retention of the SCC with PElO is very poor, whereas the slump flow
retention of sec with PE7 is not bad. If we further increase the dosage of PE7 we get a
constant high slump flow over 2 hours. This increase ofthe slump flow retention with
dosage indicates, that the slump flow retention is somehow correlated with the necessary
polymer dosage to reach surface saturation. Figure 11 shows the adsorption curves on
NPCS after 30 minutes of the two polymers with a maximum adsorption level of about
l.S mg/g for PElO and about 1.0 mg/g for PE7 and the dosage for surface saturation of
about 2.4 mg/g cement ofPE7 and about 3.0 mg/g cement ofPEIO. The graph indicates,

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that polymer PE7 reaches the surface saturation at lower polymer dosage than polymer
PEIO. So, at the dosage of2.l mg per g binder PEIO is under dosed with respect to the
surface saturation, but PE7 with a dosage of 2.6 mg per g binder has already reached it.
Other authors have correlated good slump flow retention with time to the amount of
dispersant remaining in the solution 14 or poor slump flow retention to the increase of
surface area with time and thus reduction of the amount of adsorbed polymer per surface
13
area • All these theories show the same background as is the dependence of the slump
flow retention on the degree of surface coverage. With increasing dosage, the polymer
adsorbs on the cement surface or is consumed by C 3A forming organa-aluminate
phases 10 • The higher the polymer dosage the higher is the degree of surface saturation.
The necessary dosage when this surface saturation is reached is dependent on the
polymer structure. If the surface is not saturated with the polymer, space is left for
contact of two non-occupied parts of different cement grains or one occupied part with
one non-occupied part leading to aggregation that eventually causes the stiffening of the
cement paste. The number of formed aggregates is dependent on the number of possible
contacts of non-polymer covered surfaces and this number of contacts is higher at lower
W/C, higher temperature, and elapsed time. Therefore stiffening is more pronounced at
higher packing density (low W /C), elapsed time and increased temperature.
The effect of the surface saturation on the slump retention can also be seen in
standard concrete where we measure the flow with 15 shocks on the flow table. Concrete
with a target flow of 45 +/- 2 em was produced at 3 fixed W/C ratios and NPC5. The
dosage of polymers PE 10 and PE7 was adapted to reach the desired initial flow value.
The change of the flow within 2 hours was determined. Figure 12 shows again the
increase of flow retention with polymer dosage. At a W/C of0.39 the dosage of PElO
with 0.18% (=1.8 mg /g cement) is far below the saturation level of about 3.0 mg/g,
therefore we find fast stiffening of the concrete. The 0.21% (2.1 mg/g cement) dosage of
PE7 is close to the saturation level (about 2.4 mg/g) and therefore only moderate
stiffening with time is recorded. Reducing the W/C to 0.36 and increasing the polymer
dosages to 0.28% and 0.53% for PEIO and PE7 respectively (Fig. 12 b) the saturation
level of the polymers is nearly reached or overreached leading to almost constant flow
over 2 hours. These tests again indicate, that the flow retention is correlated with the
degree of surface saturation.
CONCLUSIONS
In the work presented here and before 6 we were able to demonstrate the
importance of the adsorption of polycarboxylate ether polymers on the cement in order to
behave as high range water reducer or superplasticizer. The higher the adsorbed amount
of polymer the higher was the flow in the cement paste. Since the paste flow and the yield
12
stress are directly correlated"' , increasing the amount of adsorbed polymer reduces the
yield stress of a cement paste. The degree of adsorption is dependent on the polymer
structure and the cement. Higher ionic content in the polymer backbone and increased
backbone length increase the adsorption. The length of the side chains influences the
adsorption in as much as it influences the overall ionic content of the polymer and is
15
more important when very low W/C ratios are used 13 • •
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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On the other hand, the amount of adsorbed polymer has no direct correlation to
the flow of the mortar when it is shocked for 15 times on the flow table. Here we find,
that polymers with low adsorption show good performance at higher W/C but fail to work
at lower W/C ratio whereas polymers with longer side chains are better at lower W/C. In
mortar the choice of the optimum polymer depends on the type of cement used and on the
desired W/C ratio.
We could further demonstrate that the degree of surface saturation is important

for the flow retention not only of a cement paste but also for self compacting concrete.
Polymer dosages in the range to reach surface saturation produce concrete with good
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
f1ow retention, whereas dosages far below this surface saturation show fast stiffening. In
general, polymers with a high adsorption level reach this value only at comparably high
dosages compared to polymers with low adsorption rate. Polymers that show high
adsorption usually are already very good plasticizers at dosages far beyond this level of
surface saturation and are mainly used for precast conrete. They are in most applications
under dosed with respect to the surface saturation and therefore can give problems with
faster stiffening. Polymers with lower adsorption are generally dosed higher to give the
desired flow and they reach the surface saturation already at lower dosages compared to
polymers with high adsorption. These polymers are therefore usually very good in
applications where long slump retention is desired like in ready-mixed concretes.
ACKNOWLEDGEMENTS
This work received funding from the Swiss Federal Office for Education and Science
(contract No 00.0273-2) and was part of a project funded by the 5th European Framework
Programme (Contract G5RD-CT -200 1-00435).
We want to thank our collaborators, Domenico Larosa and Jabbar AIShemari for their
help in producing the polymers and performing most of the application tests and our
colleagues from the Materials Testing Department for performing all concrete tests.
REFERENCES
1. Uchikawa, H., Hanehara S. and Sawaki, D.:"The Role ofSteric Repulsive Force
in the Dispersion of Cement Particles in Fresh Paste Prepared with Organic
Admixture", Cern. Concr. Res. 27 (1997), pp 37-50.
2. Yoshioka, K., Sakai, E., Daimon M. and Kitahara, A.: "Role ofSteric Hindrance
in the Performance ofSuperplasticizers for Concrete", J. Am. Ceram. Soc., 80,
(1997), pp 2667-1671.
3. Flatt, R.J., Houst, Y.F., Bowen, P. and Hofmann, H.: "Eiectrosteric Repulsion
Induced by Superplasticizers between Cement Particles - an Overlooked
Mechanism?", Proc 6 1h CANMET/ACI Int Conf on Superplasticizers and Other

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Chemical Admixtures, Ed. V.M. Malhotra, Nice, France, 2000, ACI SP-195, pp
29-42.
4. Yoshioka, K., Tazawa, E., Kawai, K. and Enohata, T.: "Adsorption

Characteristics of Superplasticizers on Cement Component Materials", Cern.
Concr. Res. 32 (2002), pp 1507-1513.
5. Ohta, A., Sugiyama, T. and Tanaka, Y.: "Fluidizing Mechanism and Application
ofPolycarboxylate-Based Superplasticizers", Proc 5th CANMET/ACI Int Conf
on Superplasticizers and Other Chemical Admixtures, Ed. V.M. Malhotra,
Rome, Italy, 1997, ACI SP-173, pp 359-378.
6. Schober, I. and Mader, U.: "Compatibility ofPolycarboxylate Superplasticizers

with Cements and Cementitious Blends", Proc 7th CANMET/ACI Int Confon
Superplasticizers and Other Chemical Admixtures, Ed. V.M. Malhotra, Berlin,
Germany, Oct 2003, ACI SP-217, pp 453-468.
7. Hanehara, S. and Yamada, K.: "Interaction between Cement and Chemical

Admixture from the Point of Cement Hydration, Absorption Behaviour of
Admixture, and Paste Rheology", Cern. Concr. Res. 29 (1999), pp 1159-1165.
8. Yamada, K., Ogawa, S. and Hanehara, S.: "Controlling of the Adsorption and
Dispersion Force of Polycarboxylate-Type Superplasticizer by Sulfate Ion
Concentration in Aqueous Phase", Cern. Concr. Res. 31 (2001), pp 375-383.
9. Comparet, C., Nonat, A., Pourchet, S., Mosquet, M. and Maitrasse, P.: "The
Molecular Parameters and the Effect of Comb-Type Superplasticizers on Self-
Compacting Concrete: A Comparison of Comb-Type Superplasticizer
Adsorption onto a Basic Calcium Carbonate Medium in the Presence of Sodium
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Sulphate", Proc 7th CANMET/ACI Int Conf on Superplasticizers and Other

Chemical Admixtures, Ed. V.M. Malhotra, Berlin, Germany, Oct 2003, ACI SP-
217, pp 195-209.
10. Flatt, R.J. and Houst, Y.F.: "A Simplified View on Chemical Effects Perturbing
the Action ofSuperplasticizers", Cern. Concr. Res. 31 (2001) pp 1169-1176.
11. Roussel, N., Stefani, C., Leroy, R.: "From Mini-Cone Test to Abrams Cone
Test: Measurement of Cement-Based Materials Yield Stress Using Slump
Tests", Cern. Concr. Res. 35 (2005), pp 817-822.
12. Flatt, R.J., Larosa, D. and Roussel, N.: "Linking Yield Stress Measurement:
Spead Test Versus Viskomat", Cern. Concr. Res. 36 (2006), pp 99-109.
13. Yamada, K. and Hanehara, S.: "Working Mechanism ofPolycarboxylate

Superplasticizer Considering the Chemical Structure and Cement

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Characteristics", Proc 11 1h Int Congr on the Chemistry of Cement (ICCC), May
2003 Durban, South Africa, pp 538-549.
14. Vickers, Th.M., Jr., Farrington, S.A., Bury, J.R and Brower, L.E.: "Influence of
Dispersant Structure and Mixing Speed on Concrete Slump Retention", Cern.
Concr. Res. 35, (2005), pp 1882-1890.
15. Yamada, K., Takahashi, T., Hanehara S. and Matsuhisa M.: "Effects ofthe
Chemical Structure on the Properties ofPolycarboxylate-Type
Superplasticizers", Cern. Concr. Res. 30 (2000), pp 197-207.
Table 1 - Comoosition of the oolvcarhoxvlate etbe!'ll

Ratio of acid Relative side Molecular weight Mw!Mn•
to ester chain length
PEl 2.0 2 15'000 3.0
PE2 3.0 2 13'000 2.7
PE3 3.5 2 12'000 2.8
PE4 4.0 2 11'000 2.4
PES 3.1 2 23'000 1.8
PE6 3.1 2 113'000 2.5
PE7 2.3 2 32'000 2.0
PE8 6.4 4 25'000 1.4
PE9 6.7 10 60'000 2.3
PEIO 2.9 I and6 48'000 1.6
• Mw!Mn ts the polydtsperstty mdex
Table 2 - Cement composition

NPC1 NPC2 NPC3 NPC4 NPC5
c3s 66.3 67.5 49.5 48.5 53.5
c2s 10.8 5.7 22.0 22.0 17.5
C3A 6.4 1.2 S.G 11.5 8.0
C..Af 8.2 21.3 9.G 6.5 10.5
Na2 0-equivalent n.a. n.a. 0.4~ 0.44 0.36
Specific surface area (m2/g) 1.59* 1.23* 1.20*" 1.3** I.o••
* laser granulometry •• BET N2 adsorp!ton
-
T a ble 3 M'IXture proportions of mortar
Series 1 Series 2
Cement 750 g 880 g
Limestone filler ISO g 320 g
Quartz sand 0.08-3.2 mrn 2700 g
Limestone 0-1.2 mm 950 g
Limestone 1.2-4 mm 800 g
Limestone 4-8 mm 1250 g
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Table 4- Mixture proportions ofSCC (calculated with 2% air content)
Cement 8.75 kg 357 kglm'
FJy_ ash 2.50 kg I 02 kg/m'
Limestone filler 2.61 kg I 06 kg, m'
Limestone sand 0-1 mm 7.83 kg 319 kg,m'
Limestone sand 1-4 mm 11.75 kg 479 kg/m'
Limestone aggregate 4-8 mm 8.27 k~ 337 kg/m'
Limestone aggregate 8-16 mm 13.05 kg 532 kj!lm'
Water (Water/Binder- 0.34) 3.83 kg 156 kglm'
Table 5- Mixture proPOrtions of standard concrete (calculated witb 2% air content)

Cement 9.1 kg 354 kgfm'
Limestone filler 1.5 kg 58 kg!m'
Limestone 0-8 mm (rounded) 22.5 kg 876 kglm'
Limestone 8-32 mm (rounded) 26.0kg 1013 kglm'
Water for W/C- 0.39 3.55 kg 138 kg/m'
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
non-ionic polyether side
chains (non-adsorbing)
anionic backbone
(adsorbing)
Figure 1- Schema of a polycarboxylic ether polymer
2L Layer thickness = 3nm

40
It ot-----~~--------~
0
6 8 10 12 14
Separation [run]
Figure 2- Action of steric stabilization of comb-like polymers

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i 2.5 ..,.-----,.-.,-----,--, i 2.5 ,---,...-,.----,---,
~ 2.0
10
~ 2.0
NPC2
"' • 2 mglg cement
t"' 1.5 +---t--+ t 1.5 •4mglgcement
.5 1.0 .5 1.0
i 0.5 i 0.5
!
0
0.0
PE1 PE2 PE3 PE4
i o.o
PE1 PE2 PE3 PE4
Figure 3- Adsorption of polymer PE1 to PE4 on NPC1 and NPC2 at dosages of 2 and
4 mg solid polymer per g of cement after 30 minutes adsorption time
t)
A. 2.0 +----1---+---i
~
"'
.§. 1.5 +---±:;.,.,.."':,;;.....~;:......o
1:
e.
0
1.0 -t----u.......~~-t.,J--"-'"-=--'f
t)
2.5
NPC4 ........
~ II.
~ 0.5 -t--BJ---t-----+-----1 z 2.0
~
0.0 r l f - - - - 1 - - - - + - - - - - l g 1.5
0.0 1.5 3.0 4.5
2.5 ,..---..,.----,---....,
"0
= 1.0
e-
t) NPCS
~ 2.0 +---+---+---:-.......~
..
0
'0
4:
0.5
~
0.0
_!1.5-l---\--;-?;.::::l!:;:::;;:::::i~
0.0 1.5 3.0 4.5
c:
~ 1.0 -t---b~::Y-=---n--~~""1.,1 Dosage (mg/g cement)
e0 -+-PES --PE6 • D ·PET
~ 0.5 • 0. ·PES • 0 • PE9 _.,_PE10
0.0 1.5 3.0 4.5

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Dosage (mglg cement)
Figure 4- Adsorption of PEs to PElo on cements NPC3, NPC4 and NPCs at different
dosages and after 30 minutes adsorption time
250 -+-PES
--PE6
• D • PE7 -----j~;:;:o"~~
• 0.• PES
• O• PE9
0.0 1.5 3.0 4.5

mg polymer 1 g cement
Figure 5- Flow of the cement paste with cement NPC3 at a W/C of 0.23 after
30 minutes

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e
230
210
190
p.:>r
?-:::. PE&-
-5. 170 _........ PE 10 -'-=------
~ 150
~ PE9
U::1l0
~ 110 ~E5
PE7
a.. 90
70
50
~0 L2 1A 1~ 1~
Adsorption (mg polymerlg cement)
Figure 6- Correlation of flow of the cement paste with adsorbed amount of

polymer; polymer dosage 3 mg/g cement (NPC3); W/C = 0.23 for flow test,
all data after 30 minutes
a) b)
220 -,---.,..--....-----,----. 220 ,---...,----..---.---,
NPC1 i
i
-
200 e NPC1
2oo -t-- ~-~~+-~~~·~---+-~···---~-!----- -1
;: 180 s 180 -1---+••---+---+---1
~ 160 1 160
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
1&.
~140
0
~ 140 +--+111: 1-+11111--+11
2 120 +a;:-~ :i 120 +=J,:.+BI:'• t-a-•1··
100 +-"--..._....,..c..;...-o:....-....,_...,.L..f 100 -1-"""--+"'"'-"""4-"..,.4-'llll:..dl~
PE1 PE2 PE3 PE4 PE1 PE2 PE3 PE4
c) d)
220 ,...--...,.----,---,---, 220 .---.---.-~--..,
~ 200 NPC~---l-1&---!'-llo,...-1 e 2oo NPC2
i' 180 s 180 +-11111---HII---HII----+--1

~ 160 +111=.-+111--+111-:---~ 1 160 ~.
1&.
~ 140 +JI:•f--11.,,-f-. ~ 140
:i 120 :i 120
100 +-~-+-- ....4-"''"'-'-4-'..,_,.Ll 100 -1-""o..:..-4-"IL.:IIL.j-.IR:.J-+-.c-_,
PE1 PE2 PE3 PE4 PE1 PE2 PE3 PE4
Figure 7- Flow of mortar with polymers PE1 to PE4; a) W/C 0-47. polymer dosage
0.18% solids, b) W/C 0.38, polymer dosage 0.35%, c) W/C 0-40, polymer dosage
0.18% and d) W/C 0.39. polymer dosage 0.35%

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240
220
200
e.E. 180
~ 160
140
120
100
PE5 PE6 PE8 PE9 PES PE10 PE7 PE6 PES PES PE9 PES PE10 PE7
240
220
200
e
,E_180
~ 160
li:
140
120
100
PES PES PES PE9 PE5 PE10 PE7 PES PES PES PES PES PE10 PE7
240
220
200
1180
£160
140
120
100
PES PE6 PE8 PE9 PES PE1D PE7 PE5 PES PES PE9 PE5 PE10 PE7
Rgure 8- Flow of mortar with polymer dosages of 0.15% (a, c, e) and 0.30% (b, d, f). --`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
TheW /C was 0-40 and 0.42 for a, 0.35 and 0.38 forb, 0-43 and 0.44 for c, 0.38 and
0.39 ford, 0.40 and 0-42 fore and 0.34 and 0.35 for f.

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-;::- 2.0 . - - - - r - - - , . . . - - - - ,
<U
"0
li 1.5 +----1----:;:!oiit-~......--
~
0)
.§. 1.0 +---~'ft--

c:
0
~ 0.5 • ·!!.· Blend of

"0
"' NPC5
<( 0.0 n:----+----t----1
0.0 1.5 3.0 4.5
Polymer dosage (mg/g binder)
Figure 9- Adsorption of PE10 on NPCs and on a blend of NPCs with fly ash in the ratio
of6o/4o
70
e
.2.60
;:
£50
ll.
§ 40
u;
30
20
PE10 (0.21%) PE7 (0.26%) PE7 (0.35%)
Figure 10- Slump-flow of sec with PE10 and PE7 at W/B 0.34 with a blend of NPCs
and fly ash in the ratio of 78/22
.t.PE10 : NPCS
[
z I .5
~
•PE7
····:·' , -+-,-~-.r,· •
~r···
E
:i"t.o ! )···~
e- '.· v:
T
l 0.5 . . ; '
4 /:
0.0 '
0.0 1.0 z.o 3.0 4.0 s.o
Dosage (mglg cementl
Figure 11- Adsorption and estimated dosage for surface saturation of PE10 and PE7
on NPCs after 30 minutes adsorption time
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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60 .--------.-----. , - - - - - - - . - - - - . ,
-
55
50 +----t-t.-----1
!iio;- ·
l4s '•30'
1111160'
~ 40
!o90'
u:: 35
~120'
30
25
PE10 PE7 PE10 PE7
Figure 12- Concrete flow with PEto and PE7. a: W/C 0.39 and 0.18% PEto, 0.21% PE7;
b: W/C 0.36 and 0.25% PE10, 0.53% PE7
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-13
Effect of High-Range Water-Reducing

Admixture Type on Performance of
Self-Consolidating Concrete
by K.H. Khayat and S.-D. Hwang
Synopsis: The workability characteristics of self-consolidating concrete (SCC) and
performance of the hardened concrete depend on the type of high-range water
reducing admixture (HRWRA) in use. An experimental investigation was undertaken
to evaluate the effect of HRWRA type on key performance aspects of SCC, including
workability, mechanical properties, transport properties, frost resistance, de-icing
salt scaling resistance, and restrained shrinkage. The evaluated mixtures were
proportioned with water-to-cementitious materials ratio of 0-42 using two types
of blended cements. Two different types of polycarboxylate (PCP)-based HRWRAs,
a polynaphthalene sulfonate (PNS)-based HRWRA, and three types of viscosity-
enhancing admixtures (VEAs) that are compatible with the various HRWRAs were
used in this investigation. The SCC mixtures had initial slump flow of 66o :t 20 mm
and air volume of 6.5 :t 1.5%. As expected, the concrete made with PNS-based HRWRA
had significantly higher HRWRA demand compared to similar concrete prepared with
PCP-based HRWRA. For the selected binder type (Bt binder), the SCC proportioned
with PNS-based HRWRA had higher maximum settlement values of 0-44% compared
to 0.16% to 0-44% obtained in the case of similar SCC made with PCP-based HRWRA.
Despite some spreads in mechanical properties, sec mixtures made with either type
of HRWRA exhibited excellent frost durability and chloride-ion impermeability. Higher
resistance to shrinkage cracking was observed for the concrete made with PNS-based
HRWRA than that with PCP- based HRWRA, despite the lower compressive strength
and higher drying shrinkage of the former concrete. This can be due to relatively
greater tensile creep coefficient and stress relaxation in tension for the Bt-PNS
mixture, thus reducing tensile stress by restrained shrinkage.
In addition to the concrete investigation, concrete-equivalent mortars (CEMs) based
on the tested sec mixtures were prepared to evaluate the effect of HRWRA type on
the minimum water content needed to initiate flow and the relative water demand
required to increase fluidity. These parameters are closely related to packing density
and robustness of the mixture, respectively. Flow characteristics of CEM made with
different HRWRA types indicate that CEM made with PNS-based HRWRA exhibits
higher relative water demand and greater robustness than CEM prepared with PCP-
based HRWRA.
Keywords: concrete-equivalent mortar; high-range water-reducing
admixture; PCP; PNS; restrained shrinkage; self-consolidating
concrete; workability
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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186 Khayat and Hwang
Kamal H. Khayat, FACI, is a Professor of Civil engineering at the Universite de
Sherbrooke. He is a member of ACI committees 234, Silica Fume in Concrete; 236,
Material Science of Concrete; 237, Self-Consolidating Concrete; and 552, Geotechnical
Cement Grouting. His research interests include self-consolidating concrete, rheology,
and concrete repair.
Soo-Duck Hwang is a PhD candidate at the Universite de Sherbrooke, Quebec, Canada.

His research interests include workability, transport property, and visco-elastic property
of self-consolidating concrete.
INTRODUCTION
Self-consolidating concrete (SCC) has been used to facilitate construction operations,

including cast-in-place concrete in areas presenting special difficulties to casting and
vibration. The use of SCC has gained wide acceptance both in the precast and cast-in-
place construction. Since 1997, the Quebec Department of Transport has employed SCC
in the repair of bridge structures, including overhead girders and beams, pier caps, and
bridge abutments (1). Such repair necessitates the use of highly flowable concrete given
the complexity of the cast elements, degree of restriction by the reinforcement, difficult
access to ensure proper consolidation, and in some cases special requirements to provide
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
architectural quality surface. Similarly, the City of Montreal has successfully used SCC
for the rehabilitation of bridge abutments and parapet walls since 2000 (2).
sec used for the repair of concrete infrastructure should have high deformability,
passing ability, and resistance to segregation. The workability characteristics of SCC and
the performance of the hardened concrete, as well as the technical and economical
advantages of using sec can vary with a number of parameters, including mixture
proportioning, chemical admixture combinations, binder type, and fiber reinforcement. In
particular, the high-range water reducing admixture (HRWRA) type is shown to have
significant effect on workability and hardened properties. The use of polycarboxylate
(PCP)-based HRWRA can lead to high early compressive strength. Concrete subjected to
prolonged mixing or agitation after the introduction of PCP-based HRWRA could lead to
increase in air volume, without necessary refinement in the size of the air bubbles.
Polynaphthalene sulfonate (PNS)-based HRWRA is also used in SCC, especially in the
case of ready-mix concrete and in applications, including repair applications.
Recently, both PNS-based and PCP-based HRWRAs were used successfully in

proportioning SCC for the repair of a retaining wall in Montreal (3). The SCC made with
PCP-based HRWRA was employed in relatively cold weather to promote early-age
development of mechanical properties, while a similar SCC made with PNS-based
HRWRA was used in relatively warm weather to limit early-age strength development,
thermal shrinkage, and cracking of the repair material (3). The two SCC mixtures had the
same mixture proportioning with water-to-cementitious materials ratio (wlcm) of 0.40
and incorporated a synthetic fiber at 0.25% by volume. In the case of the PNS mixture,
the ambient temperature varied between 10 and 21 °C between the time of casting and

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beginning of hardening. This temperature ranged between 4 and l4°C in the case of the
PCP mixture. The mixtures developed similar peak in-situ temperatures of 25 to 30°C.
In order to better comprehend the influence ofHRWRA type on the performance ofSCC
used in cast-in place applications, an experimental work was undertaken to evaluate the
effect of PNS-based and PCP-based HRWRAs on key properties of the plastic and
hardened concrete. The study included the evaluation of HRWRA demand, mixture
robustness, passing ability, stability, mechanical properties, restrained shrinkage,
transport properties, frost durability, and scaling resistance.
EXPERIMENTAL PROGRAM
Materials and mixture proportioning
The SCC mixtures were prepared with wlcm of 0.42, two different types of PCP-based
HRWRAs (PCP! and PCP2), and a PNS-based HRWRA. For each type of HRWRA,
compatible viscosity-enhancing admixture (YEA) and air-entraining admixture (AEA)
supplied by the same admixture manufacturer were incorporated, as presented in Table I.
A lignosulfonate-based water-reducing admixture (WRA) and a set-retarding agent
(SRA) were used in mixtures proportioned with the PNS and PCP2 HRWRAs to enhance
fluidity retention. This was not required for the mixtures made with the PCPI HRWRA,
since the sec exhibited adequate fluidity retention.
Two commercially available blended cements that are often used in repair applications in
Quebec were employed. The Bl cement (CSA Type GUb-F/SF) contains approximately
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
25% Class F fly ash and 5% silica fume, by mass of cementitious materials, and the B2
cement (CSA Type GUb-S/SF) contains approximately 25% slag and 5% silica fume.
Continuously-graded crushed limestone aggregate with a maximum size of 10 mm and
well-graded siliceous sand were employed. The particle-size distribution of the aggregate
lies well within CSA A23.1 recommendations. The coarse aggregate and sand have
fineness moduli of 6.4 and 2.5, bulk specific gravities of 2.73 and 2.64, and absorption
values of0.5% and 1.2%, respectively.
All of the SCC mixtures were prepared with 4 75 kg/m3 of cementitious materials, which
is typically used in SCC for repair applications. The sand-to-coarse aggregate ratio (by
volume) was fixed at 1.0. The HRWRA and AEA concentrations were adjusted to secure
initial target slump flow consistency of 660 ± 20 mm and air volume of 6.5 ± 1.5%.
Three types ofHRWRAs (PNS, PCP!, and PCP2) were used with the Bl blended cement
The PNS and PCP! HRWRAs were incorporated to mixtures prepared with the B2
blended cement. The mixture proportioning is presented in Table 2. The targeted
minimum 56-d compressive strength of the evaluated mixtures is 35 MPa. This could be
easily achieved in air-entrained concrete made with w!cm of 0.42, regardless of the
HRWRA and binder types.

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Flow characteristics of concrete-equivalent mortar
Concrete-equivalent mortar (CEM) mixtures were used to evaluate the influence of

HRWRA type on the minimum water content and relative water demand. In the design of
the CEM, additional content of sand is used to provide an equivalent surface area of the
coarse aggregate that is not employed in the CEM formulation. For a given binder type
(B1 binder), three CEM mixtures were prepared with various types of HRWRAs (Table
2). The HRWRAs included PNS-based HRWRA (PNS) and two PCP-based HRWRAs
(PCPI and PCP2). The dosage rate of the HRWRA was fixed at 0.2% solid content, by
mass of cementitious materials, to eliminate the effect of different HRWRA dosages on
the flow characteristics. The CEM was prepared in 2-L batches using an epicyclic type
mixer of4.73-L capacity, in compliance with ASTM C 305.
The mortar flow test was used to evaluate the flow characteristics of CEM. The test
consists of determining the variations of fluidity of a given mortar with changes in water-
to-powder ratio (VwNp), by volume. As indicated in Fig. 1, the intercept of the curve
with the ordinates axe (VwNp) and the slope of the curve represent the minimum water
content that is needed to initiate flow and the relative water demand required to increase a
given fluidity, respectively. The reduction of minimum water content corresponds to an
increase in packing density and, for the same cementitious materials, can lead to decrease
in HRWRA demand. As indicated in Fig. 1, for a given increase in water content (ilW), a
CEM that has higher relative water demand would exhibit smaller increase in fluidity
compared to that of similar mixture with lower relative water demand. This indicates that
the former mixture has greater tolerance to undergo same addition of water with limited
increase in fluidity; this would lead to greater robustness.
Test methods for SCC
Workability ofSCC was evaluated using the slump flow, V-funnel, L-box, caisson filling
capacity, and surface settlement tests. Detail descriptions of these tests are elaborated in
reference 4. The apparent yield stress (g) and torque plastic viscosity (h) were evaluated
using a modified two-point workability rheometer. The workability testing was carried
out within 20 min after the end of mixing.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
A number of I 00 x 200 mm cylinders were cast to determine compressive strength

(ASTM C 39) and modulus of elasticity (ASTM C 469) at 28 and 56 days of moist curing
Prisms measuring 75 x 75 x 355 mm were prepared to evaluate frost durability (ASTM C
666, A). The prisms were moist-cured for 56 days before starting freeze-thaw testing
given the fact that concrete containing high volume of supplementary cementitious
materials necessitates curing period longer than 28 days to develop its mechanical
properties and durability. Samples of 280 x 230 x 75 mm were cast to evaluate the
scaling resistance (ASTM C 672). The samples were moist-cured for 42 days, then stored
at 50% relative humidity at 23 ± 1 °C for 14 days before frost testing. The air-void
system of the hardened concrete was determined in accordance with ASTM C 457.
Rapid chloride-ion permeability (RCP) testing (ASTM C 1202) was carried out after 56
days of moist curing. The chloride-ion diffusion coefficient was evaluated using steady

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state migration test similar to the setup used by True et al. (5). Relatively low electrical
potential of 12 Volt was applied to reduce the effect of temperature rise given the high
voltage used during the testing. The alkaline solution of 20 L was used as non-chloride
solution in this migration test. Such high volume can mitigate chloride concentration
increase in the downstream solution (anode). This can help keep the chloride ion flux
constant during the testing. A chloride solution made with NaCl (0.338 maUL), NaOH
(0.025 molfL) and KOH (0.083 mol/L) was used for the upstream (cathode). Diffusion
coefficient was determined from changes in chloride-ion concentration with time (5).
Prismatic concrete samples measuring 76 x 76 x 285 mm were used to evaluate drying

shrinkage (ASTM C 157). The samples were immersed in water for 7 days after casting
then were stored at 23 ± I °C and 50% relative humidity for 56 days. Drying shrinkage
was monitored between 7 and 63 days using a digital-type extensometer. An
instrumented ring test similar to the setup used by See et al. (6) was performed to
determine restrained shrinkage cracking of concrete. As shown in Fig. 2, concrete ring
specimens are dried from only outer circumferential surface with the top surface sealed.
Concrete was moist-cured for 24 hours under wet burlap after casting before demolding
and thereafter for additional 2 days before initiating the drying process at 23 ± I °C and
50% relative humidity. A sudden increase in steel strain corresponds to cracking of the
concrete ring specimen. Detail procedures of the ring test can be found in reference 6.
TEST RESULTS AND DISCUSSION
Effect of HRWRA type on flow characteristics of concrete-equivalent mortar
In general, the SCC made with PNS-based HRWRA exhibited higher HRWRA demand
compared to that prepared with PCP-based HRWRA. Similar findings were obtained for
the flow characteristics of CEM, as shown in Fig. 3. For a given HRWRA concentration,
CEM made with PNS-based HRWRA exhibited higher MWC to initiate flow compared
to similar mixture prepared with PCP-based HRWRA (1.23 versus 0.86 and 0.81). This
can be due to lower packing density of the CEM made with PNS-based HRWRA --`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
compared to that prepared with PCP-based HRWRA. Furthermore, it may be attributed to

the relatively lower dispersing force of the PNS-based HRWRA. It is worthy to note that
CEM proportioned with PNS-based HRWRA developed significantly higher RWD to
increase a given fluidity than the other mixtures made with PCP-based HRWRA (0.15
versus 0.05 and 0.06). Therefore, for a given change in water content (~W), the CEM
mixture made with PNS-based HRWRA exhibited smaller increase in fluidity, which
reflects the greater robustness than mixtures made with PCP-based HRWRA. The CEM
mixtures exhibited similar MWC and RWD values when PCP-based HRWRAs were
used.
Effect of HRWRA type on workability responses of SCC
Fresh properties of SCC mixtures are summarized in Table 3. Regardless of the HRWRA
and binder types, the targeted air content of 5% to 8% was achieved because AEA dosage
was adjusted to secure the targeted value. Regardless of the binder type, concrete made

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with PNS-based HRWRA exhibited much higher AEA demand of 350 to 400 mL/m 3
compared to 20 to 90 mL!m 3 for the other mixtures prepared with PCP-based HRWRA.
The HRWRA demand of the evaluated concrete varied from 1.7 to 7.0 Llm 3 , depending
on HRWRA-binder combination. As presented in Table 3, concrete made with PNS-
based HRWRA had a significantly higher HRWRA demand of7.0 and 5.8 Llm3 when the
Bl and B2 binders were used. The HRWRA demand ranged from 1.7 to 3.8 !Jm3 for
mixtures made with PCP-based HRWRA. Regardless of the HRWRA, all of the
optimized mixtures exhibited high passing ability with L-box blocking ratio (h2/h 1)
greater than 0. 70, high filling capacity with caisson filling capacity greater than 80%, and
adequate static stability with maximum surface settlement lower than 0.5%. The slump
flow loss of the sec after one hour of occasional agitation was limited to 50 mm.
The effect of HRWRA type on surface settlement varied with the binder type. In the case
of SCC made with the B 1 blended cement, the PNS mixture exhibited higher settlement
value of 0.44% compared to 0.16% and 0.21% obtained for SCC prepared with PCP-
based HRWRA, as presented in Fig. 4. This is attributed to the retarding effect of the
PNS incorporated at relatively high concentration. On the other hand, SCC mixtures
made with the B2 blended cement and two types ofHRWRAs exhibited the same surface
settlement of 0.49%. It is important to note that, regardless of the binder and HRWRA
types, maximum settlement values of the evaluated mixtures are lower than 0.5%, which
is recommended by Hwang eta!. (7).
Effect of HRWRA tvpe on mechanical and visco-elastic properties of SCC
Compressive strength, modulus of elasticity, drying shrinkage, and restrained shrinkage

cracking results of the evaluated mixtures are summarized in Table 4. In general, the two
SCC mixtures proportioned with PNS-based HRWRA developed lower I-d compressive
strength of approximately 4 and II MPa compared to I4 to 16 MPa for the three similar
mixtures made with PCP-based HRWRA. This can be due to the relatively longer setting
time of the PNS mixtures (Table 3). As presented in Table 4, the former SCC exhibited
lower 56-d compressive strength of 40 to 45 MPa compared to 40 and 53 MPa for the
SCC made with PCP-based HRWRA. Similarly, mixtures made with PNS-based
HRWRA and the Bl binder had lower 56-d elastic modulus of28.5 GPa compared to 30
to 35 GPa for similar mixtures prepared with PCP-based HRWRA and the same binder
type (Bl).
For a given HRWRA type (PNS), SCC made with the B2 binder developed higher 1-d
compressive strength of I0.6 MPa compared to 3.7 MPa for the concrete prepared with
the B I binder. Similarly, the former concrete had higher 28- and 56-d compressive
strength than the SCC made with the B l binder. This can be in part due to the relatively
high reactivity of blast-furnace slag in the B2 binder compared to fly ash in the BI binder
and lower air content of 5.8% for the B2 mixture compared to 7.0% for the SCC
containing the B I binder.
In general, SCC proportioned with PNS-based HRWRA and the Bl binder exhibited
higher drying shrinkage after 56 days of drying compared to similar concrete made with
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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PCP-based HRWRA. For example, mixtures made with PNS HRWRA had higher
shrinkage values of 660 !!Strains compared to 615 and 555 !!Strains for those prepared
with PCPl and PCP2 HRWRAs, respectively, when the Bl blended cement was used.
However, for a given binder type (Bl), SCC made with PNS-based HRWRA had
significantly longer time to cracking of 17.2 days (restrained ring test) compared to 6.3
and 8.8 days for similar SCC prepared with PCPl and PCP2 HRWRAs, respectively,
despite the lower compressive strength and higher drying shrinkage values of the former
concrete (Fig. 5). This is in part due to the relatively low elastic modulus of the PNS
mixture, thus leading to greater tensile creep coefficient. Similarly, SCC proportioned
with PNS HRWRA and B2 binder had longer time to cracking of 4.5 days compared to
2.8 days for the SCC made with PCPl HRWRA and the same binder.
For a given HRWRA type, SCC made with the Bl binder exhibited longer time to
cracking than similar SCC prepared with the B2 binder. For example, the Bl-PNS
mixture developed longer time to cracking of 17.2 days compared to 4.5 days for the B2-
PNS mixture. As presented in Fig. 5, this spread is mainly due to relatively greater tensile
creep coefficient and stress relaxation in tension for the Bl-PNS mixture, thus reducing
tensile stress by restrained shrinkage. On the average, at a given time, the B 1-PNS
mixture had approximately 60% lower tensile stress compared to the B2-PNS mixture.
Similarly, the 81-PCPI mixture exhibited relatively long time to cracking of 6.3 days
compared to 2.8 days for the SCC made with the B2 binder and the same HRWRA
(PCP!).
Effect of HRWRA type on transport properties and frost durability of SCC
The results of the transport properties, air-void system, frost durability, and resistance to
de-icing salt scaling are summarized in Table 5. The mean 56-d RCP and chloride-
diffusion coefficient values are compared in Fig. 6. For a given binder type, the SCC
mixtures made with PNS-based HRWRA exhibited slightly lower diffusion coefficients
of2.2 and 2.6 X 10- 12 m2/s compared to the sec made with PCP-based HRWRA that had
values of 2.6 to 3.5 x 10- 12 m2/s. On the other hand, no significant spread was found in
the RCP results of mixtures made with PNS- and PCP-based HRWRA. The B2-PCP1
concrete had the highest diffusion coefficient of 3.5 x 10- 12 m2/s and RCP value of 905
coulomb. The remaining mixtures had 56-d ·ReP values ranging between 505 to 620
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
coulomb.
The results of frost durability and de-icing scaling resistance of the mixtures made with
various HRWRAs and different binder types are compared in Fig. 7. Regardless of the
HRWRA, the optimized SCC exhibited excellent frost durability with durability
coefficient greater than 94%. All mixtures had spacing factor lower than 200 !liD, except
for the B 1-PCP2 concrete that had a spacing factor of 260 !!ill. The optimized SCC
mixtures had excellent resistance to de-icing salt scaling with cumulative mass loss after
50 freeze-thaw cycles less than 80 g/m 2, regardless of the HRWRA type. This is in
exception of the B l-PCP2 concrete that had a scaling value of 375 g/m 2, given its higher
spacing factor value of 260 !liD and lower hardened air content of 3. 7% (Table 5).

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The effect of the HRWRA type on the performance of hardened SCC is discussed in Fig.
8. The octagon plots are used to represent the data of eight response types determined for
the five optimized SCC mixtures developed for repair applications. The responses include
56-d compressive strength, 56-d modulus of elasticity, drying shrinkage after 56 days of
drying, time to cracking by restrained shrinkage (tc,), 56-d chloride-diffusion coefficient,
56-d RCP, frost durability coefficient, and cumulative mass of scaling residues. Each
branch of the octagon plot represents a response with the test value indicated at the
extremity of that branch. The scale of each branch varies from the minimum result
obtained for the five tested mixtures at the center of the plot, to the maximum value
indicated at the extremity. Frost durability coefficient of 80% was used for the minimum
value. For the drying shrinkage, elastic modulus, diffusion coefficient, RCP, and mass of
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
scaling residue values are expressed in the opposite direction. This is done to maintain a
representation whereby a broader plot would correspond to better performance.
For a given binder type, SCC made with PNS-based HRWRA exhibited relatively higher
"closed-loop area" values of 15,660 and 17,600 compared to 8,720 to 14,600 for similar
concrete prepared with PCP-based HRWRA, indicating superior performance of the
former set of mixtures. The main difference between the performance of the hardened
SCC made with PNS- and PCP-based HRWRAs lies in the time to cracking by restrained
shrinkage that was longer for the forrner set of mixtures compared to similar mixtures
made with PCP-based HRWRA. As presented in Fig. 8, the SCC mixtures made with
PNS-based HRWRA had relatively longer time to cracking of 4.2 and 17.2 days
compared to 2.8 to 8.8 days in the case of similar SCC mixtures prepared with PCP-based
HRWRA. This is despite the relatively lower compressive strength and higher drying
shrinkage of the SCC made with PNS-based HRWRA.
For a given HRWRA type, SCC proportioned with the B2 binder exhibited higher
compressive strength, lower drying shrinkage, higher frost durability, and higher
resistance to de-icing salt scaling. As presented in Fig. 8, mixtures proportioned with the
B2 binder and the PNS- and PCP-based HRWRAs exhibited greater "closed-loop area"
values of 17,600 and 14,600, respectively, compared to 15,660 and 8,720 for similar
mixtures made with the Bl binder and the same HRWRA. SCC proportioned with Bl
binder exhibited higher resistance to restrained shrinkage cracking than similar concrete
made with B2 binder.
CONCLUSIONS
Given the testing program presented in this paper to evaluate the performance of SCC
mixtures for repair of concrete infrastructures that were proportioned with 0.42 wlcm and
two different types of ternary cements, the following conclusions can be made:
I. CEM and SCC mixtures proportioned with PNS-based HRWRA necessitated higher
values of minimum water content to initiate flow and higher HRWRA demand,
respectively, compared to mixtures prepared with PCP-based HRWRA. The CEM
proportioned with PNS-based HR WRA exhibited higher relative water demand

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values indicating lower sensibility of the mixtures made with PNS-based IIRWRA to
a given variation in water content than those made with PCP-based HRWRA.
2. For the selected binder type (B 1 binder), the SCC proportioned with PNS-based
HRWRA had greater maximum settlement values of 0.44% compared to 0.16% to
0.44% obtained in the case of similar SCC made with PCP-based HRWRA.
3. Concrete proportioned with PNS-based HRWRA and the Bl binder exhibited

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
slightly higher drying shrinkage compared to similar concrete made with PCP-based
HRWRA and the same binder (660 J..!Strains versus 555 to 615 J..!Strains). However,
the PNS mixture developed longer time before cracking due to restrained shrinkage
of 17.2 days compared to 6.3 to 8.8 days for similar SCC prepared with PCP-based
HRWRA.
4. The HRWRA type does not seem to have any significant effect on transport
properties, frost durability, and de-icing salt scaling resistance for the optimized sec
made with the same cement and wlcm. Optimized SCC mixtures exhibited 56-d RCP
values lower than 900 coulomb, frost durability coefficients higher than 90%, and
cumulative mass of scaling residues lower than 400 g/m2, regardless of the HRWRA
and binder type.
ACKNOWLEDGEMENTS
The authors wish to thank the Natural Sciences and Engineering Research Council of
Canada (NSERC) as well as the industrial partners participating in the NSERC-Industry
Coop project involving the development of high-performance SCC for repair
applications: Axim, Chryso, Ciment Quebec, City of Montreal, De gus sa, Euclid Canada,
Handy Chemicals, Lafarge Canada, Ministry of Transport of Quebec, St-Laurence
Cement, and W.R. Grace. The assistance of Olivier Bonneau and Boualem Abdi in
conducting the experimental work is especially acknowledged.
REFERENCES
1. Hovington, A., "The Experience of the Quebec Ministry of Transports with Self-
Consolidating Concrete (1997-2000)," (in French), Proceedings, Annual ACI
Quebec and Eastern Ontario Annual Meeting, Quebec, Canada, 2000, 8 p.
2. Morin, R., and Khayat, K.H., "Performance of Self-Consolidating Concrete Used to
Repair Parapet Wall in Montreal," Proceedings, 1st North American Conference on
the Design and Use of Self-Consolidating Concrete, Chicago, USA, 2002, pp. 475-
481.
3. Khayat, K.H., Petrov, N., Morin, R., and Thibault, M., "Rehabilitation Strategies
and Material Performance of SCC Used for the Repair of the Jarry/Querbes
Underpass in Montreal," Proceeding, International Conference on Concrete Repair,
Rehabilitation, and Retrofitting, Ed. by Alexander, Capetown, South Africa, 2006,
pp. 1009-1013.

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4. Hwang, S.-D., Khayat, K.H., Bonneau, 0., and Mayen-Reyna, D., "Workability
Requirements of Self-Consolidating Concrete Used in Casting Highly Restricted
Structural Sections," Proceedings, 4th International Conference on Concrete Under
Severe Conditions (CONSEC 04), Edited by Oh, B.H, Seoul, Korea, June 2004, pp.
1321-1328.
5. True, 0., Ollivier, J.P., and Carcasses, M., "A New Way for Detennining the
Chloride Diffusion Coefficient in Concrete from Steady State Migration Test,"
Cement and Concrete Research, Vol. 30, 2000, pp. 217-226.
6. See, H.T., Attiogbe, E.K., and Miltenberger, M.A., "Shrinkage Cracking
Characteristics of Concrete Using Ring Specimens," ACI Materials Journal, Vol.
100, No.3, 2003, pp. 239-245.
7. Hwang, S.-D., Khayat, K.H., and Bonneau, 0., "Performance-Based Specifications
ofSCC Used in Structural Applications," ACI Materials Journal, 2005, V. 103, No.2,
Mar.-Apr. 2006, pp. 121-129.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 1 -Characteristics of chemical admixtures supplied by three different
suppliers
Admixture Solid Specific Manufacturer recommended range of

codification content(%) gravity additions
PNS 40.5 1.21 400- 4000 mL I I 00 kg of binder
WRA3' 28.5 1.15 Up to 200 mL I 100 kg of binder
VEA3 42.5 1.21 1100-2700 mLIJOO L of water
AEA3 10.5 1.00 30- 100 rnUlOO k2 of cement
PCP1 27.1 1.09 260- 780 m.LI 100 kg of binder
VEAl 39.1 1.12 130-920 mL I 100 kg of binder
AEAl 10 1.01 8- 98 mLI 100 kg of cement
PCP2 20 1.06 325- 1300 rnUJ 00 kg of binder
VEA2 50 1.35 Unknown
AEA2 19.3 1.02 30 - 320 mLil 00 kg of cement
SRA" 49.3 1.23 130- 520 mL I I 00 kg of binder
'WRA =Water-reducing admixture, "SRA =Set-retarding agent

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Table 2 -Mixture proportioning of SCC and CEM mixtures (kglm')
Binder Coarse HRWRA VEA AEA

Mixture Water Sand
(type) agg. Llm3 (type) L!m 3 (type) mLfm 3 (type)
475 7.0 3.7 400
Bl-PNS' 200 800 774
(Bl) (PNS) (VEA3) (AEA3)
475 2.9 1.6 90
Bl-PCPl 200 800 774
(Bl) (PCP!) (VEAl) (AEAI)
475 3.8 0.2 20
Bl-PCP2" 200 800 774
(Bl) (PCP2) (VEA2) (AEA2)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
475 5.8 3.3 350
B2-PNS' 200 811 785
(B2) (PNS) (VEA3) (AEA3)
475 1.7 2.0 45
B2-PCPI 200 811 785
(B2) (PCP!) (VEAl) (AEAI)
475 0.2%···
CEM-PNS
(Bl)
200 - 828
(PNS)
- -
475 0.2%
CEM-PCPl
(Bl)
200 - 828
(PCP!) - -
475 0.2%
CEM-PCP2
(Bl)
200 - 828
(PCP2)
- -
' Bl-PNS and B2-PNS were incorporated with a water-reducing admixture
" B t-PCP2 was proportioned with a set-retarding admixture
'" 0.2% solid content by mass of cemeotitious materials
Table 3 -Fresh properties of SCC made witb various HRWRA and binder types
wlcm=0.42
Bl-PNS Bl-PCPl B1-PCP2 B2-PNS B2-PCP1
HRWRA demand, Lfm3 7.0 2.9 3.8 5.8 1.7
!Omin 650 670 665 675 670
Slump flow, mm
70min 600 640 650 635 630
!Omin 94 88 91 94 93
Filling capacity,%
70min 85 94 96 82 83
!Omin 4.0 2.7 3.0 4.4 3.1
V-funnel flow time, sec
70min 4.3 2.8 3.2 4.4 4.0
L-box blocking ratio, !Omin 0.83 0.78 0.80 0.82 0.75
hv'b, 70min 0.72 0.87 0.74 0.73 0.67
10 min 0.6 0.4 0.2 0.4 0.7
1i g,N.m
70min 0.6 0.4 0.3 0.6 0.9
i!
~""
h,N.m.s
!Omin
70min
6.0
7.3
4.0
4.6
5.2
4.9
8.1
10.6
4.6
7.0
10min 6.2 7.2 6.4 6.8 7.1
Air volume, %
70min 5.0 7.0 5.7 5.0 7.4
Max. surface settlement, % 0.44 0.21 0.16 0.49 0.49
Rate of settlement at 30 min, o/ofh 0.14 0.08 0.07 0.15 0.16
Initial setting time, hour 13.5 9.2 8.7 9.7 8.0
Final setting time, hour 15.0 11.0 10.0 11.0 10.3

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,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 4 -Mechanical and visco-elastic properties of SCC made with various
BRWRA and binder types
Bl- Bl- Bl- B2- B2-

PNS PCP! PCP2 PNS PCP!
Compressive strength, MPa I d 3.7 14.8 15.7 10.6 16.1
28d 34.7 29.8 46.1 42.2 46.0
56d 40.2 40.0 52.9 45.1 51.8
Modulus of elasticity, GPa 28d 27.0 28.0 32.0 28.5 29.5
56d 28.5 30.0 35.0 29.5 31.0
Drying shrinkage @ 56 d of drying,
660 615 555 560 560
~strain (after 1 d of water curing)
Time to cracking, d 17.2 6.3 8.8 4.5 2.8
Table 5- Transport properties, air-void system, frost durability, and de-icing salt
scaling of SCC made with various HRWRA and binder types (at 56 days)
Bl- Bl- Bl- B2- B2-

PNS PCP! PCP2 PNS PCP!
Rapid chloride-ion permeability, Coulomb 620 505 575 615 905
Chloride-diffusion coefficient, w-12m% 2.6 3.4 2.6 2.2 3.5
Air-void system
Hardened air volume, % 8.0 8.2 3.7 5.8 7.5
Specific volume, a, mm· 1 29.1 27.7 24.7 26.0 31.2
Spacing factor, L , ~ 155 145 260 200 145
Frost durability and de-icing salt scaling
Elongation after 3 00 cycles, 4L/L, J.un/m 80 125 130 60 185
Durability coefficient after 300 cycles, % 98 94 98 98 100
Scaling residue after 50 cycles, g/m2 80 30 375 35 30
Higher relative water demand,

a given increase in water content (C. W)
leads to smaller increase in fluidity
(more robust)
AW
Relative flow
Fig. 1- Variations in relative flow of concrete-equivalent mortar (CEM) and

water-to-powder ratio

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3DD m m
blood base
coven=d w:ilh
325 am tafbn sheet
~DD mm
Fig. 2- Dimensions of ring setup used for restrained shrinkage testing
1.6 =Mwc 0,16
~
~ 1.2
l8
t 0.8
~
§
.§ 0.4 0.05 0.04 1
~ ~
B1·PNS B1-PCP1 B1· PCPZ
Fig. 3- Effect of HRWRA type on flow characteristics of CEM
0,6
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
D-3
0 Maximum settlement ;?
• Rate of settle meat ~
~
~
0.5
0.49 0.49 e..
e.. 0.44 .se;
5 OA O.i' 0
""'';!
f~
0.3
0.21
5
§
.§
1.1
0.2 Dol
i
....
;:;: 0.1 0
~
,.:
B1· ~NS B1·PCP1 B1-PCPZ BZ-PNS B2·PCP1
Fig. 4- Comparison of static stability of sec made with various HRWRA and
binder types

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20 = Time to cracking
--- 56-d elastic: modulus
~ 16
~
.!l 31.0
.soil 12
""'~ 28.5 ,....,

6.8
llJiLI I D
B
4.5
,..."
.§ 4 2.8
0 D
B1-PNS B1·PCP1 B1·PCP2 B2·PNS B2-PCP1
Fig. 5- Comparison of restrained shrinkage cracking of sec made with various

HRWRA and binder types
:2 1000 =RCP
e ~Diffusion coefficient 3.5
..!2
0=
-;;-
~ 800 N-s
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
3 N
$
.g
g
600
5" 2
5
·a
!E...
"'" 400
8
.,·.:-~
l ·~"
..!2 200 @
"fl iS
:s!
§- 620 505 575 615 905
~
B1-PNS B1-PCP1 B1- PCP2 B2·PNS B2-PCP1
Fig. 6- Diffusion coefficient and RCP values of sec made with various HRWRA and
binder types determined at s6 days
100 D Durabilily coefficient

• Mus of scaling residue
l 500
98
~...
~
400
~
·ail
96
=
"0
..
300
-~
!50 94
"
-~
:;::
-e 92
200
1
.....
0
0= lDD ~
90 ::E
88
B1-PNS B1-PCP1 81- PCP2 B2· PNS B2-PCP1
Fig. 7- Frost durability coefficient and scaling resistance of sec made with various
HRWRA and binder types

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Blbinder B2binder
40.2 AREA-17600 45.1
80 660 35 560
29.5
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
2.6
ARKA~sno AREA= 14600 51.8

40.0
30 615
30.0
2.8
905
3.4 3.5
AREA~ 11270 51.9 Legend 56-d. fc'
Mus of Shrinkage
Du~m: Rsm~ ~I/_&,::~:~

eoeflideat
Rcr n .....
@56d
575 cracking, let
DiiTWJioD
2.6 coefficient@ 56 d
Fig. 8- Summary of overall performance of the hardened evaluated sec mixtures

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Intercalation of Polycarboxylate
Superplasticizers into C3A
Hydrate Phases
by J. Plank, Z. Dai, N. Zouaoui, and D. Vlad
Synopsis: Pure C A hydrates under formation of layered phases (e.g. C AH, and
3 4 9
C2AH 8) which quickly convert to the cubic phase C3AH 6 • In presence of polycarboxylate
(PC) superplasticizers during C A hydration, intercalation of the PC molecule into
the layered calcium aluminum hydrate occurs. The resulting organa mineral phases
Ca-Al-PC-LDHs are very stable. They were characterized by powder XRD, elemental
analysis, IR spectroscopy and TEM microscopy. XRD patterns show that with
increasing side chain length (nw) of PC, the distance (basal spacing) between the
[Ca 2AI(OH) 6]+ layers increases. PCs with side chain lengths up to 45 ethylene oxide
(EO) units intercalate well whereas a PC with 111 EO units no longer intercalates.
Calculations indicate that the PC side chains mostly are compressed or tilted to fit in
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
between the inorganic layers.
Keywords: cement hydration; intercalation; polycarboxylate;

superplasticizer; tricalcium aluminate

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202 Plank et al.
Johann Plank is Professor at the Institute of Inorganic Chemistry at University of
Technology in Munich, Germany. He holds a Chair for Construction Chemicals. His
research interests include cement chemistry, CaS0 4 binders, polymer admixtures (e.g.
superplasticizers, water retention agents, retarders, biopolymers), organic-inorganic
composite and nano materials, and studies on interaction between admixtures and
inorganic binrlers
Dr. Zhimin Dai is a post-doc researcher at the Chair for Construction Chemicals in
Munich, Germany. Previously, she worked at the State Key Laboratory for Inorganic
Chemistry at Jilin University in China. Her research focused on the synthesis of hybrid
organic-inorganic materials.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
M. Sc. Nadia Zouaoui studied chemistry at University of Technology in Munich,

Germany. Currently, she is a Ph.D. student at the Chair for Construction Chemicals in
Munich. Her research focus is on polycarboxylate chemistry and CaS04 binder-
admixture interaction.
Dr. Dorina Vlad studied chemistry and physics at the University in Bucharest, Romania,
before joining the Chair for Construction Chemicals in Munich, Germany. In her Ph. D.
thesis, she studied the sulfate effect on polycarboxylate superplasticizers and their
interaction with binder surfaces.
INTRODUCTION
Polycarboxylate-based superplasticizers (PCs) are recognized as important admixtures for

use in modem concrete technology [1]. They allow to produce a highly flowable concrete
or to reduce the water/cement ratio of concrete, resulting in higher compressive strength.
For this application, it is essential to profoundly understand the interaction between the
PCs and the mineral compounds formed during cement hydration. One type of such
mineral phase is [C~Ah(OH),z](S0 4)"6H 2 0 (AFm) which possesses a layered structure. It
results from hydration of the tricalcium aluminate phase (C 3A) with sulfate present in
cement. It has been generally accepted that the high-range water-reduction and the high
fluidity of concrete containing PC is attributed to the PCs adsorbing onto the surface of
cement hydrate phases [2]. In this way, a steric repulsive layer leading to the dispersion
of the cement particle is formed [3-6]. Besides adsorption, intercalation (absorption) of
the PCs into newly formed mineral phases, particularly of AFm type, is also possible. Up
to date, only intercalation of beta-naphthalene sulfonate (BNS) formaldehyde condensate,
a superplasticizer with linear structure, has been studied [7]. In comparison, from the
point of steric size, PC type superplasticizers are much larger molecules because of their
side chains. This makes their intercalation more difficult.
Hydration of the pure aluminate phase (C3A) first produces minerals with layered
structure, e.g. C4AH 19 and C2AH 8 [8]. At room temperature, these metastable phases
quickly transform into the more stable cubic phase C3AH 6 • Under heat of hydration from
C3A, the conversion is almost instantaneous. The structure of the layered phases derives
from brucite Mg(OH 2), in which some Mg 2+ cations are replaced by a trivalent cation.

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This substitution results in an excess of positive charge in the main layer which is
compensated by anions situated in between these cationic layers. Such compounds are
generally called layered double hydroxides (LDHs). Their general composition can be
expressed by the formula
with Mil= Ca 2+ Mg2+ Zn 2+ Co 2+ Ni2+ Cu2+ Mn 2+. M m = Ae+ Cr3+ Fe3+ Co3+ N?+
Mn3+; X = inte~l~yer 'anion: e.g. 'oR", 'cr, N0 3-, Clo:-, cot, 'so/ and ~any 'other
anions.
Layered double hydroxides consist of positively charged layers separated by anionic

counterions x•· and water molecules. During hydration of pure C3A (no sulfate present),
layered calcium aluminum hydroxide hydrate is formed initially. A schematic of its
lamellar structure is shown in Fig. 1. Its positively charged main layer consists of
[Ca2Al(OH) 6t units. The counteranion x•· is OR". If sulfate is present during C3A
hydration, then soi· anions instead of oH· intercalate in between the [Ca2Al(OH)6t
layers, resulting in calcium aluminate monosulfate hydrate [Cl4Alz(OHb](S04)"6H20,
AFm.
Several authors have shown that not only inorganic, but also organic guest anions can
intercalate into the layered calcium aluminate structure. Meyn et al. [9], for example,
confirmed the intercalation of citrate, diglycolate, phthalate and aryl/alkyl sulfonates such
as dodecylbenzenesulfonate. Others showed that also polymers such as puly(ethylene
oxide) derivatives [10], poly(u,~-aspartate) (11], poly(acrylic acid), poly(vinylsulfonate)
and poly(styrene sulfonate) [12] intercalate into LDH phases. With respect to concrete
applications, Fernon et al. (7] demonstrated the successful intercalation of BNS polymer
into the Ca-Al-LDH structure. These articles generally show that the steric size of the
intercalated anion determines the interlayer distance as expressed by the gallery height or
the basal spacing (see Fig. 1). Sterically very large anions are more difficult to
intercalate.
In this work, we have investigated the potential intercalation of polycarboxylate

superplasticizers into Ca-Al-LDH obtained from C3A hydration. To avoid competition
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
between the polycarboxylate and the sot anion which supposedly has a high tendency
to intercalate, pure C 3A clinker without sulfate was used. Several synthetic routes for the
incorporation of PC were studied, among them direct anion-exchange with Ca-AI-OH-
LDH as precursor, coprecipitation of calcium and aluminum nitrate in aqueous PC
solution at pH value of 11.7, and rehydration of calcined C3A in aqueous PC solution.
The rehydration method produced particularly good results and was selected for all
syntheses. Polycarboxylates with increasing poly( ethylene oxide) side chain length (nEO =
4.5 to 45) were used to study the steric influence of molecule size.

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204 Plank et al.
EXPERIMENTAL
Preparation of ClA clinker
Tricalcium aluminate was prepared via a sol-gel process as precursor before calcination.
Aqueous colloidal alumina (VP disp. W630, Degussa, Hanau, Germany) containing 29.7
wt.-% Alz03 with a medium particle diameter of about 200 nm was mixed with
stoichiometric amounts of neutral Ca(N0 3)z solution, which was freshly prepared from
CaC0 3 and HN0 3 (p.a. Merck, Darmstadt, Germany). The mixture was heated at 70°C
and stirred at pH 8 for 10 to 12 h until gel formation. The gel was transferred into
platinum crucibles and slowly heated to 900°C. Water evaporated and Ca(N03) 2
decomposed to the metal oxide. Finally, the sample was heated at l350°C for 9 h with
two intermediate grindings. Investigations by X-Ray powder diffraction confirmed the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
resulting product to be pure tricalcium aluminate.
Preparation of Polycarboxylate Superplasticizers
The chemical structure of the synthesized polycarboxylates is shown in Fig. 2.

Methacrylic acid and ffi-methoxypoly(ethylene oxide)methacrylate (MPEG) ester with
average nEO = 4.5; 8.5; 17 and 45 were copolymerized in aqueous solution initiated by
NaS 20 8 in presence of sodium methallylsulfonate as chain transfer agent. Polymerization
was carried out by charging a 2L-three neck vessel with water, monomers at a molar ratio
of 6:1 (MA acid:ester) and chain transfer agent, heating at 60°C and feeding in an
aqueous solution of the starter over l hr while the mixture is allowed to reach 80°C. After
stirring for one more hour at 80°C, the polymer solution is cooled to ambient and
neutralized with aqueous NaOH. The resulting copolymers were characterized by
aqueous GPC (eluent 0.1 M NaN0 3 adjusted to pH=l2; Waters Alliance 2695; pre
column PL aquagel-OH; columns ultrahydrogel 120, 250 and 500; Wyatt Dawn EOS
dynamic light scattering detector) and charge density titration in cement pore solution
using poly(DADMAC) as cationic titrator.
Preparation of Ca-AI-PC-LDH
A typical synthesis of a PCn-LDH (n denotes the number of EO units in the side chain) is
described as follows: polymer PCn=1.s (Mn=14, 000 Da; Mw=67,460 Da) was dissolved in
100 ml of deionized water at a concentration of 2.5 wt. %. 1.5 g of C3A was added to the
PC solution (pH ~ 12). The system was stirred under argon flow at 75°C for 48 h. The
precipitated intercalate was separated by centrifugation and washed with deionized water
in order to remove residual polymer. The resulting solids were dried at 65°C under high
vacuum (10-2 ~ 10-3 mbar) for 12 hours. Similar routes were used to prepare the other
three PC-LDHs, the number of EO units being 8.5, 17 and 45. Ca-Al-OH-LDH was
prepared by reacting monocalcium aluminate (CA) in deionized water [13].
Compositions of the organomineral compounds were determined by X-ray powder
diffraction, elemental analysis, IR spectroscopy and transmission electron microscopy
(TEM).

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Results and Discussion
Properties of PC superplasticizers
Properties of the synthesized Ca-Al-PC copolymers are shown in Table I. As expected,

molar masses (Mw, Mn) of the PCs increase with increasing number of ethylene oxide
units in the side chain.
The molecular conformation of the PC molecules was determined as shown in Table 2:

First, the molar mass of a hypothetical unit (Mu) comprising of 6 mols of methacrylic
acid and one mol ofMPEG methacrylate ester was calculated by adding the masses of all
atoms in the unit; next, the repeat number n of the hypothetical unit in each copolymer
was determined by dividing Mn by Mu. The main chain length was obtained by
multiplying the average backbone length of Mu which is 7 x 0.252 nm with the repeat
number n. This calculation is based on a C-C-C length of 0.252 nm and assumes that the
polymer chain is ideally stretched. Our GPC data (RgfRh ratio) indicate that, at this molar
ratio, this is almost the case. The side chain lengths were determined based on previous
work by Ohta et al. [11 reporting a distance of 1.95 nm for 7 ethylene oxide units with
helical orientation.
From the data of Table 2, a schematic of the molecular size and conformation of the PC
copolymers was developed (see Fig. 3). It shows that 4.5PC and 8.5PC are worm
molecules while 17PC and 45PC are polymer brushes. It also gives one the idea that PC
molecules with longer side chain will not easily intercalate into Ca-Al-LDH.
X-ray powder diffraction ofPC-Ca-Al-LDH intercalates
Tn spite of the large size of the PC molecules, all synthesized copolymers intercalated
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
easily into the lamellar calcium aluminum hydroxide structure. Incorporation was evident
from X-ray powder diffractograms developed on Bruker axs D9 instrument. The basal
spacing for each intercalate was taken from the (001) reflections and is shown in Fig. 4.
As can be seen, the increasing side chain length of PC as expressed by increasing nw
causes a considerable widening of the inter layer distance. The basal spacing d increases
from 1.15 nm for 4.5PC-Ca-Al-LDH to 4.27 nm for 45PC-Ca-Al-LDH (see Table 3). In
comparison, Femon et al. [7) report a gallery height of approx. 1.5 nm for the BNS-Ca-
Al-LDH.
Infrared Spectroscopy
IR spectra of all synthesized intercalates were taken between 4000 and 400 cm· 1 (see
Fig. 5).
At 3600 cm- 1, all spectra show valence vibrations for the -OH groups in the cationic
inorganic layers. The absorption of the interlayer water appears around 3400 em·I. The
asymmetric and symmetric valence vibrations of the carboxylate group appear around
1560 and 1455 cm· 1• They confirm the presence ofpolycarboxylates in the mineral phase.

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206 Plank et al.
The CHz-O-CH 2 vibrations at 2790 cm- 1 and 1100 cm- 1, resp., can be attributed to the
polyethylene oxide side chains. Typical lattice vibrations of the LDH structure appear at
421 cm- 1 (Ca-0) and 530 cm- 1 (Al-0). The absorption at 790 cm- 1 derives from the M-
OH (M = Ca, AI) deformation vibration. In conclusion, the IR spectra also confirm that
intercalation has occurred.
Elemental Analysis
Chemical analysis performed on the precipitated intercalates confirms the formation of
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
organa-mineral phases as welL The results are shown in Table 4.
As can be seen, the carbon and hydrogen content increases with increasing side chain
length of the polycarboxylate. For PC with nEO = 17 and 45, the organic part in the
organo mineral phase exceeds 50%.
Although some PC adsorption on the cationic surface of the top and bottom layer of an
Ca-Al-LDH particle can be expected, an organic content of between 30 and 50 % is too
high for only adsorption. Thus, it confirms that intercalation has occurred. Based on the
analytical data, the approximate composition for each Ca-Al-PC-LDH was calculated and
is shown in Table 4.
The layered structure of the PC intercalates also was con finned by TEM. As an example,
the layer stackings for Ca-Al-45PC-LDH is shown in Fig. 6. As expected, it shows a
parallel stacking of layers with a basal spacing of approx. 4 nm corresponding to the
basal spacing of 4.27 nm obtained from XRD analysis.
Steric Arrangement ofPolycarboxylate Intercalated into Layered C1A Hydrate
Surprisingly, intercalation of large PC molecules into the layered C3A hydrate structure
occurred easily and completely. When repeating the intercalation experiment in air, i.e.
without argon protection and in presence of C0 2, the same intercalates were obtained.
This is remarkable because it is well known that C0 32- has an extremely strong tendency
to intercalate. It prevents most other anions from being intercalated [14]. This experiment
confirms the high tendency of PCs to intercalate into C3A hydrate phases. In our
experiments, the only limiting factor we found to prevent intercalation was the length of
the PC side chain: Whereas 45PC with a side chain length of 45 EO units intercalates
well, lllPC shows very little intercalation. It can be concluded that there is an upper
limit for the gallery height between the [Ca2Al(OH) 6t main layers. It is determined by
the steric size of the ethylene oxide side chain.
To investigate on the steric arrangement of intercalated PC, for each intercalate the
distance (gallery height) between two neighboring [Ca 2Al(OH)6t main layers was
determined. The gallery heights are obtained by subtracting the thickness of the cationic
layer which is 0.48 nm (see Fig. I) from the basal spacing d obtained by XRD (see Fig.

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4). The resulting gallery heights are shown in Table 3. Comparison of calculated PC side
chain lengths with the gallery heights in Table 3 reveals that, except for 8.5PC, the side
chains of all other PC molecules are either compressed to a mushroom type or tilted to fit
in between the [Ca2Al(OH) 6 f layers. Fig. 7 indicates potential steric arrangements of PC
r
macromolecules in between the [Ca2Al(OH) 6 main layers. It is safe to assume that the
intercalated PC molecules always will be attached to the cationic layer through their
anionic carboxylate groups in a train type. Varying amounts of intercalated water (see
compositions in Table 4) resulting from the drying process can produce slight variations
of the basal spacing d.
Conclusion
In this work we have demonstrated that although polycarboxylate superplasticizers are

. relatively large molecules, they can intercalate into layered calcium aluminum hydrate
phases obtained from C3A hydration in absence of sulfate. PC macromolecules with side
chain lengths (nEo) up to 45 were successfully intercalated. To overcome the steric
hindrance of long PC side chains, the PEO chains are either tilted or compressed to fit in
between the layers. The interlayer distance of 3.79 nm for Ca-Al-45PC-LDH is among
the highest ever found for Ca-Al-X-LDH composite materials.
Most remarkable is the stability of the organa mineral phases containing PC. Whereas
layered Ca-Al-OH-LDH quickly converts to the more stable cubic phase C3AH6 , the PC
intercalated phases maintain their lamellar structure once they are formed. Based upon
these results, the possibility of PC intercalation into C3A hydrate phases also in the
presence of sulfate which occurs in cement pore solution, should be considered.
According to a model developed by Flatt et al. [15], such intercalation might explain the
differences in concrete flowability observed for some PCs upon early and delayed
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
addition to the concrete.
ACKNOWLEDGEMENT
The authors wish to express their appreciation to following institutions for generous
support of this work: "Jtirgen Manchot-Stiftung", "Deutsche Forschungsgemeinschaft
(DFG)" and "Friedrich Schiedel-Stiftung". Dr. Marianne Hanzlik from TU Munich is
thanked for taking the TEM photos.
References
A. Ohta, T. Sugiyama and T. Uomoto, "Study of Dispersing Effect of

Polycarboxylate-Based Dispersant on Fine Particles", Sixth CANMET/ACI
International Conference on Superplasticizers and Other Chemical Admixtures
in Concrete (Editor V. M. Malhotra) ACI, SP-195, 2000,211-227
2 J. Plank and C. Hirsch, "Superplasticizer Adsorption on Synthetic Ettringite ",
Seventh CANMET/ACI Conference on Superplasticizers and Other Chemical
Admixtures in Concrete (Editor V. M. Malhotra), ACI, SP-217, 2003, 283-298
3 A. Ohta, T. Sugiyama andY. Tanaka, "Fluidizing mechanism and application of

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208 Plank et al.
polycarboxylate-based superplasticizers", Fifth CANMET/ACI Conference on
Superplasticizers in Concrete, SP-173, 1997, 359-378
4 K. Yamada, T. Takahashi, S. Hanehara and M. Matsuhisa, "Effects of the
chemical structure on the properties of polycarboxylate-type superplasticizer",
Cern. Concr. Res., 30, 2000, 197-207
5 K. Yamada, S. Ogawa and S. Hanehara, "Controlling f!,f thP. adsorption and
dispersing force of polycarboxylate-type superplasticizer by sulfate ion
concentration in aqueous phase", Cern. Concr. Res., 31, 2001, 375-383
6 J. Plank, D. Vlad, A. Brandl and P. Chatziagorastou, "Colloidal chemistry
examination of the steric effect of polycarboxylate superplasticizers ", Cement
Intemational3, 2005,3, 100--110
7 V. Femon, A. Vichot, N. Le Goanvic, P. Colombet, F. Corazza and U. Costa,
"Interaction between portland cement hydrates and polynaphthalene
suljonates", Fifth CANMET/ACI Conference on Superplasticizers in Concrete
(Editor V. M. Malhotra) ACI, SP-173, 1997, 225-248
8 H. F. W. Taylor, Cement Chemistry, 2nd ed., Thomas Telford, London. 1997
9 M. Meyn, K. Beneke and G. Lagaly, "Anion-Exchange Reaction of layered
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Double Hydroxides", Inorg. Chern. 29, 1990, 5201-5207
10 F. Leroux, P. Aranda, J.-P. Besse, E. Ruiz-Hitzky, "Intercalation of
Poly(Ethylene Oxide) Derivatives into Layered Double Hydroxides", Eur. J.
Inorg. Chern. 6, 2003, 1242-1251
11 N.T. Whilton, P.J.Vickers, S. J. Mann, "Bioinorganic clays: synthesis and
characterization of amino- and polyamino acid intercalated layered double
hydroxides", J. Mater. Chern. 7,1997,1623-1629
12 C.O. Oriakhi, I.V. Farr, M.M. Lerner, "Incorporation of poly(acrylic acid),
poly(vinylsuljonate) and poly(styrenesuljonate) within layered double
hydroxides"
J. Mater. Chern. 6, 1996, 103-107.
13 P. Faucon, T. Charpentier, D. Bertrandie, A. Nonat, J. Virlet, J. C. Petit,
"Characterization of Calcium Aluminate Hydrates and Related Hydrates of
Cement Pastes by 27Al MQ-MAS NMR", Inorg. Chern. 37, 1998,3726-3733
14 C. Delmas, Y. Borthomieu, "Chimie Douce Reactions: A New Route to Obtain
Well Crystallized Layer Double Hydroxides", J. Solid State Chern. 1993, 104,
345-352.
15 R.J. Flatt, Y.F. Houst, "A simplified view on chemical effects perturbing the
Table 1: Characteristic properties ofsynthesized polycarboxylate copolymers

Polycarboxylate Copolymer Molar Masses [~!1101) Polydispersity Anion. Charge Density
nPC M.._ _M.. 1\!. M,,M._ [eq/Jl.10'i_
4.5PC 14,000 67,460 204,500 4.8 §,542
8.5PC 71,800 153,400 296,000 2.1 6 086
17PC 26,640 135,600 308,200 5.1 3,823
45PC 40,420 152,600 473,000 3.8 1,704

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Table 2: Calculation of main and side chain length for synthesized polycarboxylate
copolymers
Polycarboxylate M ••u M. n=Mn!Mu Length [nm]

copolymer fl!lmol) (l!fmol] Main Chain Side Chain
4.5PC 814 14,000 17.2 30.3 17.2
8.5PC 1,012 71,800 47.7 84.1 47.7
17PC 1,364 26,640 19.5 34.4 19.5
45PC 2,596 40,420 15.6 27.5 15.6
Table 3: Basal spacing d and gallery height ofsynthesized Ca-Al-PC-LDHs
Intercalate Basal spacing d Gallery height Side chain length

lnml l_om~ lnml
Ca-Al-OH-LDH 1.03 0.55 -
Ca-Al-4.5PC-LDH 1.15 0.67 1.2
Ca-Al-8.5PC-LDH 2.95 2.47 2.4
Ca-Al-17PC-LDH 3.54 3.06 4.8
Ca-Al-45PC-LDH 4.27 3.79 12.6
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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...0N
Table 4: Elemental analysis and calculated composition ofCa-Al-OH-LDH and Ca-Al-

PC-LDH intercalates
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Intercalate Ca AI c H Organic Composition

wt.% wt.% wt.% wt.% ~artwt.%
Ca-Al-OH-LDH 19.9 16.5 4.43 CazAl(OH)7.00 •3.48Hz0, 1.46Al(OH)3
Ca-Al-4.5PC-LDH 20.9 6.9 17.09 4.95 30.40 CazAlo.9s(OH)6.to{-PCn~.5-]o.t4'3.36Hz0
Ca-Al-8.5PC-LDH 14.8 4.9 24.75 5.87 44.94 CazAlo.97(0H)s.4t'[-PCn=s.s- ]o.zs·5 .48Hz0
Ca-Al-17PC-LDH 12.0 3.9 28.39 6.87 51.23 CazA1o.96(0H)s.3s·[-PCn~l7-]o.zs·7.14H20
Ca-Al-45PC-LDH 13.3 5.4 29.80 6.44 53.94 CazAI(OH>6.2s·[-PC,=4s-]o.tz·2.45HzO, 0.21Al(OH)3

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Fig. 1: Schematic drawing of lamellar Ca-Al-LDH structure
Fig. 2: Chemical structure of synthesized polycarboxylate copolymers
4.5 PC 6.5 PC
Main chain: 3:1.:3 nm Main chain: 84.1 nm
Side Chain: 1.2 nm Side chain: 2.4 nm
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
17 PC 45 PC
Main chain: 34.4 nm Mam chain· 27.5nm
Side chain: 4.6 nm Side chain: 12.6 nm
Fig. 3: Schematic representation of molecular size and conformation of synthesized

polycarboxylate copolymers

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212 Plank et al.
doo1.03rm
0 10 Ill 30 10 10
2 Theta-scale
Fig. 4: X-ray diffraction pattern of Ca-AI-OH-LDH and Ca-AI-PC-LDH intercalates
4000 35110 3000 :zsoo ZOllO 1500 1000 !100

1
W8WIIIIIIIber I cm"
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. s: IR spectra of Ca-AI-OH-LDH and Ca-AI-PC-LDH intercalates

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Fig. 6: TEM micrograph of Ca-Al-45PC-LDH intercalate with polycarboxylate 45PC

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
a) 8.5 PC
11111111111 II 1111
or
b)4.5 PC, 17 PC or 45 PC
JJIIIIIIIIIIIIIIIIII
or
IIIII I 111111 Ill
or
Fig. 7: Potential steric arrangements of PCs intercalated between

[Ca 2 Al(OH) 6]+ layers

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214 Plank et al.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-15
Influence of Sulfates Content in

Cement on the Performances of
Superplasticizers
by R. Magarotto, F. Moratti, and N. Zeminian
Synopsis: Extreme performances are required in superplasticizers technology

nowadays; the new generation of polymers makes it possible to reach a high water
reduction together with a good workability retention, ensuring excellent properties to
the hardened concrete.
With most of the cements, outstanding performances are achieved with the right
combination between cement and superplasticizer; on the other hand, high
performing superplasticizer are inevitably highly sensitive to the materials used, and
in particular to the cement.
Among the parameters that characterize the chemical composition of cement, the
sulfate amount and type are recognized as key factors for understanding the reasons
of possible problems of incompatibility between cement and superplasticizer;
however, little was done on the concrete scale.
In this article, five samples of cement containing different amounts of sulfates were
selected. The influence of the sulfate content on the performances of PNS- and
polycarboxylate-type superplasticizers was evaluated by means of adsorption tests,
minislump tests and mortar tests. In the case of addition of sulfates to cement,
concrete tests were also made in order to check the results on the concrete scale.
The results of this study highlight the importance of an adequate content and
balance between the different types of sulfates in cement, in order to guarantee the
right interaction with superplasticizers.
Keywords: f3-naphtalensulphonate; incompatibility; polycarboxylate;

sulfates; superplasticizer
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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216 Magarotto et al.
Roberta Magarotto, graduated in Industrial Chemistry, Venice University, Italy, 1993.
She has been working in the field of concrete admixtures, focusing on the development of
new polymeric superplasticizers. Since 1997 responsible of Admixture Department of
R&D at Degussa Construction Chemicals Italia S.p.a.
Francesca Moratti, graduated in Industrial Chemistry at Venice University, Italy, 2001.

Research Chemist at Degussa Construction Chemicals Italia S.p.a., R&D Department.
Nicoletta Zeminian, graduated in Industrial Chemistry, Padua University, Italy,l997.

Senior Research Chemist at Degussa Construction Chemicals ltalia S.p.a., R&D
Department.
INTRODUCTION
In recent years advanced superplasticizers have been developed in order to meet the
increasing performances required by the application. The new technology is essentially
based on polycarboxylate-type admixtures, which allow to reach outstanding
performances, both for fresh and hardened concrete, in terms of high fluidity, high
workability retention, very low water to cement ratio, high strength and high durability.
But if on one hand this new generation of superplasticizers is able to give such properties
to the concrete, on the other hand it shows a very high sensitivity towards cement
composition (mainly C3A and alkali content), cement fineness, amount and type of added
calcium sulfates, SP dosage and addition method, mix design, mixing procedure for
concrete preparation, etc [ l-4].
Among these parameters, many studies have been carried out in the last years about the
influence of sulfates (amount and type) on the performances of superplasticizers,
recognizing them as key factors for understanding the reasons of possible problems of
incompatibility between cement and admixtures [5-15]. Especially soluble sulfates (alkali
sulfates) are believed to play the main role in the interaction with superplasticizers.
According to earlier studies, the behaviors of polynaphtalenesulphonate-type (PNS)
superplasticizers and polycarboxylate-type (PCE) superplasticizers are significantly
different. Regarding PNS, Jiang et al. showed that an optimum soluble alkali content
exists with respect to the fluidity and fluidity loss, which was found to be 0.4-0.5% Na20
equivalent and which is independent of the superplasticizer dosage and C 3A content: a
lack in the soluble sulfates content (in the form alkali sulfates of the clinker) causes
problems of incompatibility between cement and NS-admixture, that can be overcome by
adding the right amount of soluble sulfates. This addition leads to significant increases in
fluidity and fluidity retention[5]. The same conclusions were drawn by Li eta!. [6).
Nakajima and Yamada examined the influence of the kind of calcium sulfates on the
dispersing ability of PNS, concluding that the kind of calcium sulfates influences flow
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
loss of cement paste, which is lower when the cement used contains a higher hemihydrate
to gypsum ratio [7].
The first studies regarding the influence of sulfates on the performances of
polycarboxylate-type superplasticizers were carried out by many researchers in the 1998
- 2003 period [8-14]. Results of these works show that the sulfate ion concentration in
cement paste affects the adsorption behavior of PC on cement particles: the adsorption of

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PC decreases in case of high sulfate concentration as the sulfate ions and PC are adsorbed
on cement particles competitively. Moreover, it seems that the EO side-chains, which
give the dispersion capability to the PCE polymer, are shrunk by the sulfate ions, thus
decreasing the steric repulsion. Magarotto et a!. showed that the addition of sodium
sulfate brings about a reduction in the adsorption capability of cement towards PCE
admixture, leading to reduced performances in terms of water reduction [15]. Moulin and
Broyer studied the effect of the different nature of added calcium sulfates on the
performances of superplasticizers as a function of C3A level in cement: they concluded
that for a high C3A level, cement dispersion is very sensitive to the nature of added
calcium sulfates: the initial fluidity increases as a function of the rate of calcium sulfate
solubilisation; while for a moderate level ofC 3A the cement dispersion is less sensitive to
the nature of added calcium sulfates [ 16).
Most of the earlier work was carried out using cement paste or mortar tests, and very
little was made in concrete.
The aim of the present work is to study the influence of the amount and type of soluble
sulfates (alkali sulfates) on the performances of superlasticizers, both PNS and PCE-type,
in cement paste, mortar and concrete. Results show that PNS-type superplasticizers seem
not to be influenced by the different types and amounts of sulfates, while, with PCE,
there exists a competition between polymer and sulfates for the adsorption on cement
particles: the most soluble sulfates (alkali sulfates) tend to be adsorbed faster then the
polymer on the cement. Therefore, with a high amount of soluble sulfates a lower amount
of admixture will be adsorbed onto the cement particles, leading to a lower water
reduction; a high amount of polymer will remain free in solution, allowing a delayed
adsorption: this should improve the workability retention.
EXPERIMENTAL DETAILS
Materials
Four Italian commercial portland cements type I 52,5 (according to EN 197/l) and one
portland cement type I 42,5 were investigated, which will be named in the following as
cement A, B, C, D and E respectively. Their complete chemical analysis was carried out
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
according to the methods reported in EN 196/2. Total and soluble sulfates (within 2
minutes at w/c of 0.5) were determined by means of ionic chromatography. Three
different superplasticizers were investigated, one based on ~-naphtalensulphonate (PNS)
and two based on ether polycarboxylates (PCE-1 and PCE-2). All the superplasticizers
are water solutions with 38% solid content, pH 7.5 and density 1.195±0.05 g/cm3 for
BNS, 35% solid content, pH 7 and density 1.095±0.05 g/cm 3 for PCE-1 and 30% solid
content, pH 7 and 1.060±0.05 g/cm3 for PCE-2. PCE-1 and PCE-2 are characterized by
the same chemistry but different side chain length (PCE-1 has shorter side chains than
PCE-2) and were chosen to study the possible influence of the side chain length on the
interaction with sufates.
Minislump tests
A cement paste prepared with cement, water and superplasticizer (dosage 0.40% active
bwc for PNS, 0.20% active bwc for PCE-1 and PCE-2) was poured, after mixing, into a
metallic truncated cone mould (internal top diameter: 21 mm, external top diameter: 31

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mm, internal base diameter: 40 rnrn, external base diameter: 50 mm) standing on a flat
plexiglass surface; the cone was then lifted and the diameter of the collapsed paste
measured. The right amount of water necessary to reach 150 mm diameter of the
collapsed paste was determined.
Adsorption Analysis
The degree of adsorption onto cement of the ~-naphtalensulphonate-based and
polycarboxylate-based admixture was determined in cement paste by T.O.C. analysis
performed with a Shimadzu 5000-A. BNS was dosed at 0.40% active bwc, while PCE-1
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
and PCE-2 were dosed at 0.20% active bwc. The w/c was kept constant at 0.5. The
samples were prepared according to the following procedure: powder and water,
containing the admixture, were stirred for the defined time and then filtered by a vacuum
pump. The amount of polymer adsorbed was determined by difference between the
organic carbon originally contained in the polymer solution and the amount left in the
solution filtered from the paste.
Mortars
Standard mortars were prepared according to EN 196/1 with all the five cements studied,
in the presence either of PNS and PCE superplasticizers. PNS was dosed at 0.40% active
bwc, PCE-1 and PCE-2 at 0.20% active bwc. The flow was evaluated for each mortar
according to the EN 413-2 after 15 shocks.
Concrete tests
Concretes were prepared with cements A and B at 20°C, adopting the mixture
composition shown in Table 1.
The dosages of the superplasticizers were 0.40% active by weight cement for PNS,
0.20% active bwc for PCE-1 and PCE-2. A second series of concrete mixes was carried
out, only with cement B, adding the amount of S04=necessary to bring the soluble sulfate
to the level of sample A (0,77% So 4= added as K2S0 4). The concrete composition was
the same as reported in Table I.
Chemical Composition
Table 2 shows the chemical composition of the five cement samples, obtained according
to the methods reported in EN 196/2. The most relevant differences between the five
samples is seen in the soluble sulfates contents: sample A contains the highest amount of
soluble sulfates, while sample B the smallest ones. Sulfate contents of sample C, D and E
are between those of samples A and B. It is interesting to point out that the total sulfate
contents of sample A and B are not so different. As the soluble sulfates are taken after
two minutes of hydration, it is reasonable to suppose that most part of these sulfates are
in the form of alkali sulfates, which are the most soluble.
Table 3 shows the phase composition of the five samples, obtained by means of the
Bogue equation: cement D is characterized by the highest C3A content (~ 11%).

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Minislump tests
The results of the rheological evaluations from minis lump measurements are reported in
Fig. l. Table 4 shows the water reduction capability of every admixture. The percentages
of water reduction cover a very wide range, from a minimum of 16% to a maximum of
63%. The results of Fig. 1 clearly show that the amount of soluble sulfates is not a key
parameter for the water-cement ratio without admixture, as can be observed from sample
A and B.
Cements A, D and E, which contain the highest amount of soluble sulfates, seem not to
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
be so sensitive to the specific chemistry of the admixtures, as the water reduction

capability is nearly the same for PNS and PCE superplasticizer. In these cements PNS
shows a good performance in comparison with polycarboxylates, while with the other
cements (B and C) PNS leads to a water reduction of even 25% less than that of
polycarboxylates.
Looking at the water reductions of the same superplasticizer on the different cements, it
seems clear that polycarboxylates reduce the water depending on the amount of soluble
sulfates: a high amount of soluble sulfates leads to a low water reduction. On the other
hand, a low amount of soluble sulfates leads to a high water reduction.
The water reduction of PNS is almost independent of the soluble sulfates content, as it is
similar for all the five samples studied, around 35%. Cement D shows a poor water
reduction, both with PNS and PCE, which cannot be explained only by the amount of
soluble sulfates; it seems that a relatively high content of C 3A ( 11%) of this cement could
be responsible for its poor performances.
Adsorption tests
The results of the adsorption tests are shown in Fig. 2, 3 and 4.
There is a quite good correlation between the adsorption values and the soluble sulfates
content in the case of PCE: the admixtures are in fact adsorbed in higher amount on
cements that present the lower soluble sulfates content. This seems to confirm the fact
that there is a competition between sulfates and polymer for the adsorption onto cement
particles. In the case of PNS, the adsorption is very high but very similar for all the
cements, meaning that the sulfates content does not seem to be a key parameter in the
interaction between cement and PNS-type admixtures.
The adsorption generally remains constant over time for all the cements and all the
admixtures.
Regarding polycarboxylates, PCE-2 shows the widest range of adsorption, from 30 to
80%, but it is adsorbed on all the cements to a lower extent with respect to PCE-1, which
had shown a better water reduction capability in cement paste. Cement E always shows
the lowest adsorption values, due to its lower specific surface area.
Mortar tests
The results of mortar tests are presented in Fig. 5-8. Table 5 shows the water reduction
capability of every admixture, and Table 6 the corresponding spreading flows. Regarding
the water reduction of polycarboxylates, in this case also, a quite good relation between
water reduction and soluble sulfate content can be found: cements B and C, which
contain the lowest amounts of soluble sulfates show the highest percentage of water
reduction. This behavior is also in accordance with the results of the adsorption tests.

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Cements A, D and E, which contain the highest amount of soluble sulfates, also show a
lower sensitivity to the chemistry of the admixtures, as the water reduction capability is
nearly the same for PCE and PNS admixtures.
Also in mortar tests, the water reduction capability of PNS admixture is almost the same
for all the cement studied, thus meaning that the performance of PNS polymers seems to
be independent of the soluble sulfates content of cement This behavior is well reflected
by the adsorption tests.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Looking at the workability retention, some considerations can be drawn from the analysis
of the results:
regarding PCE-1, the workability retention seems to improve for the cement
with the highest content of soluble sulfates. Mortars made with cement B and E
contain the same amount of water, but the workability retention is very different,
as cement B, which contains the lowest amount of soluble sulfates, shows a
.workability reduction within the first 30 minutes. Cement A, which contains the
highest amount of soluble sulfates, retains workability better than cement D,
although the water content of the mortar is lower;
also in the case of PCE-2 a high content of soluble sulfates seems to improve
the workability retention. Mortar made with cement B looses workability very
quickly with respect to the one made with cement C, which contains the same
amount of water but a higher amount of soluble sulfates;
regarding PNS, no clear correlation was found between the soluble sulfates
content and the workability retention, although mortar made with cement B,
which contains the lowest amount of soluble sulfates and the highest amount of
water, shows a reduction in the workability within the first minutes.
A possible explanation for the better workability retention could be the fact that a higher
amount of superplasticizer remains in the pore solution, thus acting as a dispersant for a
longer time.
Concrete tests
The results of concrete tests are presented in Tables 7, 8 and 9. Figure 9 shows the
compressive strengths of all the trials. A very good correlation was found between the
water reduction and the soluble sulfates content, as the water reduction obtained with
cement B, which contains the lowest amount of soluble sulfates is considerably higher
than the one obtained with cement A.
According to the mortar tests, PCE-1 seems to perform better than PCE-2 with cement A,
while the performances of the two PCE admixtures are the same with cement B. No clear
correlation was found between PNS performances in mortar and in concrete tests, as the
water reduction capability of PNS is higher with cement A than with cement B in mortar
and lower with cement A than with cement B in concrete. Since the water content of the
concrete mixtures made with cement A and B is so different, the workability retention
was not recorded. The compressive strengths of concrete made with cement B, although
the water content of concretes made with PCE-1 and PCE-2 is the same, is higher at all
ages.
Further concrete tests were made with cement B adding the amount of soluble sulfates
(0, 77% of S04 ~ as K 2S0 4} necessary to bring the soluble sulfate to the level of sample A.
Results are shown in Table I 0.

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```,,,,```,-`-`,,`,,`,`,,`---
Looking at these results, it is clearly shown that the addition of soluble sulfates to cement
B leads to a worse water reduction in the case of PCEs, while PNS seems not to be
sensitive to the sulfates variation.
The water reductions obtained in this series of concrete mixes are quite similar to the
ones obtained with cement A, meaning that the soluble sulfates content is a key
parameter for the understanding of the interaction between cement and admixture.
CONCLUDING REMARKS
Among the chemical parameters that characterize the analysis of cement, the amount and
type of sulfates seem to be the most important to understand the interaction between
cement and admixtures. In particular, the soluble sulfates content (alkali sulfates in the
clinker phase) plays a crucial role in determining the performances of superplasticizers.
Polycarboxylate-type superplasticizers are proved to be very sensitive to the presence of
soluble sulfates, which compete with polymers for the adsorption on cement particles. It
was demonstrated that high amounts of soluble sulfates lead to low water reduction
capability and generally to a better workability retention, at least in mortar, as the
superplasticizer that remains in the pore solution can act as a dispersant for a longer time.
No clear trend was detected regarding the influence of the chemical structure (side chain
length) on the interaction with sulfates. PNS-type superplasticizers seem to be much less
sensitive to the soluble sulfates content, as no clear correlation between water reduction,
workability retention and sulfates content was found.
Of course, there are several other chemical parameters, such as C 3A content and type,
that have to be taken into consideration for a deeper understanding of the mechanism of
action of superplasticizers.
REFERENCES
[I] C. Jolicoeur and M.A. Simard, 1998, "Chemical admixture-cement interactions:

phenomenology and psycho-chemical concepts", Cement and Concrete Composites, V.
20, No. 2-3, pp. 87-101.
[2) P-C. Aitcin C. Jolicoeur and J.G. MacGregor, 1994, "Superplasticizers: how they
work and why they occasionally don't", Concrete International, V. 16, No.5, pp. 45-52.
[3) K. Yamada, S. Hanehara and K. Honma, 2001, "Working mechanism of the effects of
initial hydration reactivity of cement on the performances of polycarboxylate-type
superplasticizers", Taiheiyo Semento Kenkyu Hokoko, V. 141, pp. 3-13.
[4) R.J. Flatt and Y.F. Houst, 2001, "A simplified view of effects perturbing the action of
superplasticizers", Cement and Concrete Research, V. 31. No. 8, pp. 1169-1176.
[5] S. Jiang, B-G. Kim and P-C. Aitcin, 1999, "Importance of adequate soluble alkali
content to ensure cement/superplasticizer compatibility", Cement and Concrete Research,
V. 29, No. I, pp. 71-78.
[6) G. Li, A. Tagnit-Hamou and P-C. Aitcin, 2003, "Improving cement-superplasticizer
compatibility by using soluble alkalis as a chemical additive in concrete", Proceedings oj
the 11 1h International Congress on the Chemistry of Cement: Cement's Contribution to
development in the 2 F' Century, Durban (South Africa), May 11-16 2003, Ed. G. Grieve
and G. Owens, V. 2, pp. 655-665.

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[7] Y. Nakajiama and K. Yamada, 2004, "The effect of the kind of calcium sulfate in
cements on the dispersing ability of poly ~-naphtalene sulfonate condensate
superplasticizer", Cement and Concrete Research, V. 34, No. 5, pp. 839-844.
[8] K. Yamada, S. Ogawa and T. Takahashi, 2001, "Improvement of the compatibility
between cement and superplasticizer by optimizing the chemical structure of the
polycarboxylate-type superplasticizer", Proceedings of the Second International
Symposium on Self-Compacting-Concrete, Tokyo (Japan), October 23-25 2001, Ed. K.
Ozawa and M. Ouchi, pp. 159-168.
[9] S. Hanehara and K. Yamada, 2001, "Interaction between cement and chemical
admixture from the point of cement hydration, absorption behavior of admixture and
paste rheology", Cement and Concrete Research, V. 29, No.8, pp. 1159-1165.
[10] K. Yamada and S. Hanehara, 2001, "Interaction mechanism of cement and
superplasticizers - The roles of polymer adsorption and ionic conditions of aqueous
phase", Concrete Science and Engineering, V. 3, No. 11, pp. 135-145.
[11] K. Yamada, S. Ogawa and S. Hanehara, 2001, "Controlling of the adsorption and
dispersing force of polycarboxylate-type superplasticizer by sulfate ion concentration in
aqueous phase", Cement and Concrete Research, V. 31, No.3, pp. 375-383.
[12] E. Sakai, K. Yamada and A. Ohta, 2003, "Molecular structure and dispersion-
adsorption mechanism of comb-type superplasticizers used in Japan", Journal oj
Advanced Concrete Technology, V. 1, No. 1, pp. 16-25.
[13] K. Yamada and S. Hanehara, 2003, "Working mechanism of polycarboxylate
superplasticizer considering the chemical structure and cement characteristics",
Proceedings of the 1th International Congress on the Chemistry of Cement: Cement's
Contribution to development in the 21st Century, Durban (South Africa), May 11-16
2003, Ed. G. Grieve and G. Owens, V. 2, pp.538-549.
[14] L. Coppola, R. Troli, P. Zaffaroni, M. Collepardi, 1998, "Influence of the sulfate
level in the clinker phase on the performances of superplasticized concrete", Proceedings
of the 41h CANMETIACI International Conference on Recent Advances on Concrete
Technology, Tokushima (Japan), June 7-111998, pp. 271-281.
[ 15] R. Magarotto, I. Torresan and N. Zeminian, 2003, "Effect of alkaline sulfates on the
performance of superplasticizers", Proceedings of the I 11h International Congress on the
Chemistry of Cement: Cement's Contribution to development in the 21'' Century, Durban
(South Africa), May 11-16 2003, Ed. G. Grieve and G. Owens, V. 2, pp.569-580.
[16] E. M. Moulin and V. Broyer, 2003, "Effect of superplasticizer type on the fluidity
retention of Portland cement mortars as a function of the C3A level and the nature of
added calcium sulfates", Proceedings of the 1I'h International Congress on the Chemistry
of Cement: Cement's Contribution to development in the 21st Century, Durban (South
Africa), May 11-16 2003, Ed. G. Grieve and G. Owens, V. 2, pp.550-559.

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Table 1 -Mil< desisn for concrete tests
Kglm 3
Cement I 52.5 400
Limestone filler IS
SandO·! 380
Sand 0-2 234.4
Sand 2-4 316.6
Gravel8-12 268
Gravell2-19 632
K,so, 5.58
(only in the second series)
Table 2- Chemical composition of the cement samples(% by weight)

CEMA CEMB CEMC CEMD CEME
I 52.5 I 52.5 I 52.5 I 52.5 142.5
Loss on ignition 1.44 3.28 1.59 1.85 3.61
Si02 19.51 20.66 19.85 19.17 20.20
CaO 64.77 62.01 65.18 63.73 63.76
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MgO 1.55 3.29 1.16 2.25 1.09

Fe,o, 3.35 3.14 2.87 2.75 2.87
AJ,o, 4.59 3.84 4.86 5.89 4.28
Na,o 0.26 0.18 0.15 0.16 0.18
K 20 0.54 0.19 0.14 0.50 0.33
Na,o"" 0.62 0.31 0.24 0.49 0.40
so,~ (total) 3.91 3.S9 4.48 4.13 3.41
SO,~ (soluble)• 0.87 0.10 0.27 0.52 0.52
Free CaO 0.28 0.22 0.13 1.26 0.17
I.R. 2.40 1.98 0.60 0.79 1.16
• at 2 min and w/c - 0.5
Table 3- Phase composition of the cement samples(% by weigl!t)

70.41 56.55 67.03 60.37 65.19
2.90 16.66 6.43 9.50 8.82
6.50 4.87 8.03 10.96 6.49
10.18 9.55 8.72 8.36 8.72
Table 4 - % of water reduction in minislwnp tests

PCE-1 33 63 55 17 40
PCE-2 30 53 52 16 42
PNS 33 38 35 16 38
Table 5 - % of water reduction in mortar tests

PCE-1 27 32 31 17 28
PCE-2 19 31 26 15 22
PNS 17 8 17 23 12

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Table 6 - Spreading flows of mortar tests (mm)
PCE-1 125 130 123 128 120

PCE-2 130 119 123 128 132
PNS 130 120 130 120 120
Table 7 - Concrete tests with CEM A

Admil:ture dosage Water Initial slump
AdmiJ:ture W/C
(active%) (Vm) (mm)
256 0.64 200
PCE-1 0.20 180 0.45 210
PCE-2 020 196 0.49 210
PNS 0.40 232 0.58 200
Table 8 - Concrete tests with CEM B

Admixture dosage Water Initial slump
Admixture W/C
(active%) (Vm) (mm)
252 0.63 210
PCE-1 0.20 160 0.40 220
PCE-2 0.20 160 0.40 210
PNS 0.40 196 0.49 210
Table 9- o/o of water reduction in concrete
CEMA CEMB
PCE-1 29.7 36.5

PCE-2 23.4 36.5
PNS 9.4 22.2
Table 10- Concrete tests with CEMB and addition of 0.77% S04-
Admil:ture dosage Water Initial slump
Admixture W/C
(active%) (Vm) (mm)
244 0.61 200
PCE-1 0.20 192 0.48 210
PCE-2 0.20 192 0.48 200
PNS 0.40 !96 0.49 Selflevelling
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0,9
0,79 0,80
0,8
0,7
0,6
~ 05
3:: '
0,4
0,3
0,2
0,1
0
Figure 1- Water-cement ratios of a given minislump test of 150 mm
100
90
80
CEMB ---:::::::: -
~
70 ~
~
II:
w
::1! 60 ~
~
0
a. 50
~
cw
Ill
II: 40
0
fll
~ 30
20
10 --
0
0 10 20 30 40 50 60
TIME(MIN)
Figure 2- Adsorption tests with PCE-1
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100,---------------------------------------------------------------~
90
~
~
I1J
...~
...0
0
I1J
80
70
60
50
---
CEMB
CEMD
----
Ill .,~EMA
~ 40
0
rJ)
-
Q CEME
c 30
20
10
10 20 30 40 50 60
TIME(MINI
Figure 3 - Adsorption tests with PCE-2
100
90
"'"ceMo
80
CEME
70
~
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~
I1J
IE 60
...>-
fl 50
Q
I1J
Ill
~ 40
0
rJ)
Q
c 30 --------
20
10
0 10 20 30 40 50 60
TIME(MINI
Figure 4- Adsorption tests with PNS

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0,9
0,8
0,7
0,64
0,6
(J
3: 0,5
0,4
0,3
0,2
0,1
0
i•Piain.PCE1 DPCE2DPNS\
Figure 5 - Mortar tests- Water reduction
140r-------------------------------------------------------~
20
10 20 30 40 50 60
TIME(MIN)
Figure 6- Workability retention in mortar with PCE-1
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228 Magarotto et at.
80
~
~
....... 80
40
CEMB
20
0
0 10 20 30 40 50 80
TIMECMIN)
Figure 7- Workability retention in mortar with PCE-2
140
120
100
80
~
~....
... 60
40
20
10 20 30 40 50 60
TIME(MIN)
Figure 8- Workability retention in mortar with PNS
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Figure 9- Concrete tests- Compressive strengths
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SP-239-16
Tailor-Made Superplasticizers for

Modern Concrete
by M. Corradi, R. Khurana, and R. Magarotto
Synopsis: The concrete industry is heading towards more sustainable development

and aims to make concrete an even more cost-effective building material. In this
effort, the cement industry uses increasing amounts of secondary fuels to improve
efficiency. Cement kiln dust from the clinker cooling and grinding processes are
returned to the cement. Also, the use of supplementary cementitious materials,
marginal and recycled aggregate in concrete production is increasing. These practices
introduce materials, not foreseen, in the past, in the concrete composition. They are
not always inert and often negatively affect the performance of the superplasticiser.
In this paper the parameters that cause incompatibility between the cement, other
components of the concrete mixture and the superplasticiser are examined. Tailor
made superplasticisers are required to overcome these incompatibilities. Some case
studies are presented, where the tailor made approach made a positive difference.
Keywords: adsorption; cement; cement kiln dust; chain length;

density; PCE superplasticisers; performance; secondary fuels;
superplasticizers; supplementary cementitious materials
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232 Corradi et al.
Dr. M. Corradi, is a graduate in Industrial Chemistry from Milan University. He is the
Senior Vice President of Technology and Development for Business Unit Admixtures
System Europe of Degussa Construction Chemicals. He has more than 30 years of
experience in R&D and technology management in construction chemicals.
Eng. R. Khurana, obtained his post-graduate diploma in reinforced concrete structures

from Milan Polytechnic, Italy. He has more than 30 years of experience in concrete
technology and admixtures applications world wide. At present he is the Technology
Director for Business Unit Admixtures System Europe of Degussa Construction
Chemicals.
Dr. R. Magarotto, graduated in Industrial Chemistry, Venice University, Italy, 1993. She
has been working in the field of concrete admixtures, focusing on the development of
new polymeric superplasticisers. At present she is Development Head for the Business
Line Admixture Systems at Degussa Construction Chemicals in Treviso (Italy).
INTRODUCTION
Cementitious materials have been in use for construction for about 9000 years. They have
undergone numerous changes in composition, performance and applications. Depletion of
natural resources has led to an increased concern for sustainability in the construction
industry. It has been estimated that some 8% to I 0% of carbon dioxide emitted into the
atmosphere is traceable to the construction industry (cement and steel production,
aggregate processing, mixing, transporting and placing the concrete, etc.). Major steps
have been taken by cement producers to utilise secondary or supplementary materials in
cement production. Some of these steps include:
• Use of secondary fuels such as used tyres, plastic bottles, oil industry residues,
(petroleum coke), paints and solvents, oily rags; just to cite a few.
• Use of supplementary cementitious materials such as fly ash, natural pozzolan, silica
fume and blast furnace slag.
• Limestone blended cements such as type L or LL with limestone content between
6% and 35%; EN 197-1[1].
In order to reduce or eliminate the discharge of the cement kiln dust (CKD) in to the
atmosphere or in landfills, CKD is recycled back into the cement, thus increasing the
presence of unknown or unfamiliar substances in to the concrete mixture. The Portland
Cement Association of the USA sums this up very nicely with the question:
"What has the cement industry done to improve its manufacturing process?"
The answer is "New technology and equipment, coupled with increased use of alternative
fuels and raw materials, have reduced energy consumption by one-third since 1975.
Today, cement and concrete can contain recycled materials that utilize industrial by
products that would otherwise clog landfills. The industry has reduced its own waste by
recycling more than 75 percent of cement kiln dust (nearly eight million tons each year)
directly back into the cement kiln as raw material. By doing so, manufacturers conserve
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energy and reduce use of limestone and other virgin raw materials. The effect of
secondary fuels on cement composition is shown in Table 1.
The situation in Europe is more or less similar. The need and the importance of
sustainable construction has been recognized the building industry, especially regarding
energy consumption and the use of natural resources. A European set of guidelines has
been set up with more than 200 recommendations, subdivided in to 16 categories. These
recommendations not only cover environmentally friendly constructions but, also cover
social and economic aspects. The most important benefit will be of help, in the very near
future, to include sustainable construction practices [2]. Therefore, for environmental
considerations the concrete industry will continue to increase the use of recycled and by-
product materials, originating within the industry and from other sources, in concrete
production. It is foreseen that by 2030, the concrete industry will achieve zero net waste
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in its production process. Fig. 1 shows the trend towards the increase of secondary fuels
in cement production, and Fig. 2 indicates the amount of supplementary cementitious
materials that will have to be used in concrete, perhaps as cement replacement, in order to
reach zero emission of carbon dioxide from cement production.
TOTAL PERFORMANCE CONTROL
The continuous demand for extreme performances of admixtures has led to an excellence
in tailor made solutions which lead to an economy for the state of the art applications in
concrete. This requires a:
• New understanding of chemical-cement interaction of the polymer
• Better knowledge of relationship between chemical structure of the polymer and its
performances in cement base systems
• Synthesis of tailor made polymers
• Extended competence from organic chemistry to inorganic chemistry of cement and
concrete
• Solid connection between the market and R&D
Recent trends in admixtures science indicate that the ready-mixed concrete industry
demands that the admixtures provide the following characteristics:
• Stronger water reduction for improved durability
• Faster hydration rate for rapid strength development and construction
• Longer workability retention time for reliable transportation and placing
• Rheology control of concrete for easy form filling
The challenge for the admixtures science and technology is to propose a valid solution for
the above stated requirements. To meet all these properties simultaneously is an arduous
task. Strong water reduction leads cement particles to be very close to one another and
workability is lost very quickly. Long workability retention requires extra water to be
added to the concrete mixture.

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234 Corradi et al.
NEW TRENDS IN ADMIXTURES TECHNOLOGY
Nanotechnology has brought new light in to the admixture science. It is now possible that
chemicals or polymers can be engineered to bring together functional groups aimed at
targeted performance. Polymers are built for strong or weak adsorption onto the cement
particles for dispersion effectiveness and for hydration control p J
Through investigation of the nano-behaviour, a technology that allows the control of

water demand and workability retention of concrete has now been developed. The
chemical and physical behaviour of polymers can be controlled through:
• Chain length
• Side chains length
• Electrical charges
• Side chain density
• Free functional groups
The Total Performance Control (TPC) concept ensures that the concrete producers,
contractors and the owner get a concrete that is of the same high quality as originally
specified by the design engineer; starting from the production at the central hatching
plant to the delivery and placing into the forms and followed by its hardening. Through
TPC I it is possible to regulate the:
• Rheology of the fresh concrete
• Placing
• Reliable form filling
• Optimal slump retention
and through the water cement ratio reduction it is possible to regulate the:
• Strengths development
• Durability
• Engineering properties
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The positioning of such a superplasticiser (TPC) in comparison with a state of the art
high-range water reducing superplasticiser (HRWR SP) and long slump retention
superplasticiser (LSR SP) are synthesised in Fig. 3.
EFFECTS OF SECONDARY FUELS AND SUPPLEMENTARY MATERIALS
In actual practice it has been observed that polycarboxylate ether (PCE) superplasticisers
show different performances with different cements and materials comprising the
concrete. The differences may be in the water reduction or workability retention. The
incompatibilities that interfere with the performance are traceable to alternative fuels
used in cement production, secondary components in cement and concrete production,
mineralogical and chemical composition of aggregate and the chemical nature of the PCE
superplasticisers.
The consequences of secondary fuels usage in clinker production affecting fluctuation of
performances are the degree of sulphatization which affects the kinetics of ettringite

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formation; the ratio of C3A cubic to C3A orthorhombic which influences the speed of
C3A reaction and the sulphate carrier which affects the speed of sulphate dissolution [4].
Cement is very often blended with secondary components such as slag, pozzolan,
limestone, fly ash, silica fume, etc. In some cases these materials are added to cement
during the grinding and in other cases in to the concrete during the mixing. Very often,
secondary materials are not inert materials. In many cases they interact vigorously with
admixtures. Admixtures are designed to act with cement, but in many instances they
interact with secondary materials too and are also adsorbed on their surface. This
behaviour subtracts active ingredients from being effective in water reduction or
workability retention. Some crushed limestone aggregate, especially sand, slags and
pozzolans show absorption up to 80% of the active polymer of a superplasticiser. The
adsorption of a PCE polymer on eight different limestone and quartz sands, two types of
fly ashes and five types of limestone fillers are shown in Fig. 4 to 6. The chemical
analysis of the fly ashes and the limestone fillers are reported in Tables 2 and 3 and their
porosity parameters are reported in Table 4.
The adsorption of the polymer on to the sands, limestone fillers and the fly ashes may be
summarised as follows:
• Sands show a different adsorption behaviour with a particular polymer
• Fly ashes show very high adsorption values. The reason could be related to their
physical and chemical nature (shape of the pores, high amount of un-bumt carbon).
See figure 6.
• Limestone fillers show a large range of adsorption values. Limestone Ll and L2
used, show very high adsorption. They have low purity and high surface area.
L4 and L5 show very low adsorption. They have high purity and low surface area.
L3 show higher adsorption than L4 and L5. It has a higher surface area and lower pore
size.
There seems to be fairly good correlation between physical and chemical properties such
as purity, size and shape of the pores, total porosity, surface area, and the adsorption.
Preventive characterization of supplementary cementitious materials represents a fast and
easy way to highlight possible problems of incompatibility.
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In our experience if the adsorption value is high (over 30%), these materials could take
the admixture away so that the remaining admixture cannot act as an efficient dispersant
of the cement. It is therefore important to check the adsorption of these concrete
mixtures component.
Under these conditions, only by abnormally increasing the dosage of superplasticiser, the
required performances in concrete can be achieved. However, a too high dosage may lead
to retardation and low early strength.
Considering the impact of parameters such as cement composition, aggregate mineralogy,

filler composition and supplementary cementitious materials (SCM) that are not in the
control of the concrete producer, along with the important role they play on absorption of
polymers it is clear that:

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236 Corradi et al.
One single composition of PCE superplasticiser may not deliver the expected superior
performance in the concrete and "tailor" made adaptation have to be worked out.
"Tailor" made TPC is the adjustment and optimization of performances of PCE
superplasticisers in problematic concrete mixtures, wherever the standard PCE
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superplasticiser does not deliver the desired performances, by

• Engineering suitable polymers
• Blending a few appropriate polymers
• Formulating the PCE polymer with active side materials
• Selecting right composition according to secondary materials.
Most common cases where tailor made solutions may be required are:
• very absorptive cement (low workability retention)
• ground slag showing re-fluidification of concrete (or delayed fluidification)
• very absorptive limestone material such as fillers and sand (no fluidification)
"Tailor" made TPC compositions have to be engineered in the above cases to overcome
inadequate performances. Some cases of this approach are now presented.
LABORATORY INVESTIGATIONS WITH CONCRETE MIXTURES
Four cements corresponding to type CEM II 42.5 AIL, conforming to EN 197, from four
different plants and four PCE polymers (PCE l is a high-rage water reducing
superplasticiser, PCE 2 is a long slump retention superplasticiser, PCE 3 is a high-range
water reducing and long slump retention superplasticiser compatible with most of the
cements and PCE 4 was a "tailor made" superplastiser that performs well also with
problematic cements, listed as cement type C and cement type D. Adsorption tests were
carried out with a total organic carbon (TOC) analyzer in order to compare the amount
of polymer adsorbed on to cement particles. The results are given in Fig. 7. It seems to
be important that at the beginning of the hydration reaction only a reduced amount of
polymer is adsorbed on to the cement particles. The free polymer in water seems to play
an important role for workability retention [4].
Sixteen concrete mixtures were made using aggregates from the same source, the four
cements and the four PCE polymers. The basic mixture composition was:
Sand 0-5 mm = 1018 kg/m 3

Limestone filler 73 kg/m 3
Coarse aggregate 8-12 mm 364 kg/m3
Coarse aggregate 20-25 mm 460 kg/m3

Cement 270 kg/m3
The results of these tests are presented in Table 5 and clearly indicate that PCE 1 has
good water reducing capacity, but does not maintain workability for more than 30
minutes, while PCE 2 has lower water reducing effect but good workability retention
even up to 60 minutes. PCE 3 performs well for water reducing and workability retention

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with all cements except cement type D, while the "tailor made" PCE 4 performs well
with all the cements considered. These results have been confirmed by several field
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applications in various European countries and are illustrated further on.
PRACTICAL APPLICATIONS
One of the most significant example of the "tailor made" solutions was developed for the
construction of the Italian high speed rail network which is a part ofthe European Project
for the reorganisation of the rail transport system to link the countries of the European
Union, by 2010. The section between Milan and Bologna has a length of 182 km and
crosses Lombardia and Emilia regions. In the province of Modena there is a complex
system of bridges that cross the existing motorways, urban roads, the Panaro and Secchia
rivers. The main contractor for the 24,760 m bridges is the Modena Searl Consortium.
The bridge network consist of 755 omega shaped precast beams of 24 to 31.5 m span and
9 cast in situ beams of 136 m span. This complex system required innovative
construction techniques and a special precast factory was set up by the contractor
Pizzarotti. The prefabrication process starts with the assembly of the reinforcement cages
in 8 templates that are able to produce 2 cages per day. The assembly is completed with
the anchor heads and ducts with the
pre-stressing cables. It is then positioned on the casting bed. The particular shape of the
beam and the density of the reinforcement required a concrete with some specific
properties. Durability was another requirement. The concrete for the beams had some
special requirements. The characteristic compressive strength (Rck) was 45 MPa and the
minimum strength at 24 hours was 30 MPa for the application of the initial post
tensioning (35% of the design value). The cement used was type CEM I 52.5. A
limestone filler, two types of sand and three classes of coarse aggregates with a
maximum size of 32 mm were employed. The Consistence class of the fresh concrete was
S5 (slump> 220 mm). The mixture composition, per cubic meter, is indicated in Table 6.
Preliminary tests showed that the required performance of the concrete could not be met
with the usual superplasticisers based on beta naphthalene sulfonates. Therefore, a
superplasticiser had to be specially formulated for this project and is based on the Total
Performance Control concept. The concrete pour for the standard 31.5 m beam requires
276 m3 of concrete and was completely placed in four hours. To ensure trouble-free
casting the owner insisted that the concrete had to retain workability for 4 hours! After
about 24 hours, when the concrete had achieved a compressive strength of 30 MPa, the
internal formwork was extracted and the forms at the two extremities of the beam were
removed. At this stage, the beams were partially prestressed to 35% of the design value
and transported to the stockyard. Two beams are produced daily for a total of ten beams
per week. Figure 8 shows the set-up of the formworks in the casting shed. In spite ofthe
complexity of the works the project was completed ahead of schedule.
Other examples of application of "tailor made" superplasticisers in ready mix concrete in

several European countries are given in Tables 7 and 8 [6].

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238 Corradi et al.
CONCLUSIONS
The concrete industry is heading towards a more sustainable development which aims to
make concrete an even more cost-effective building material. In this effort, the cement
industry uses increasing amounts of secondary fuels to improve efficiency. Also, the use
of supplementary cementitious materials, marginal and recycled aggregate in concrete
production is increasing. These practices introduce materials, not foreseen, in the past, in
to the concrete composition.
They are not always inert and often affect the performance of the superplasticisers
negatively. "Tailor made" TPC superplasticisers are required to overcome these
incompatibilities.
The new engineered polymer superplasticisers developed shows superior performance in
water reduction and workability retention. The innovative aspect of this new polymer
type is that it acts essentially on the kinetics of adsorption on to the cement. The
laboratory tests and field applications validate these aspects. This system can be tailored
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to meet the individual needs of the producer and consumer of concrete in order to obtain
specific benefits.
REFERENCES
I. European Standard EN 197-1. Cement- Composition, Specifications and

conformity criteria for common cements.
2. PRESCO Secretariat. Practical Recommendations for Sustainable
Concrete, Newsletter Issue 7 & 8, February 2005.
3. Corradi M, Khurana R. and Magarotto R., "Total Performance Control: An
Innovative Technology for Improving the Performances of Fresh and Hardened Ready
Mixed Concrete". Proceedings ofERMCO Congress, Helsinki, June 2004.
4. Flatt Robert J., Houst Yves F., "A simplified view of effects perturbing the
action of superplasticisers". Cement and Concrete Research 31 (2001) 1169-1176.
5. Magarotto R., Moratti F., Zeminian N., "Characterization of limestone and
fly ash for a rational use in concrete", Proceedings of "Global Construction:
Ultimate Concrete Opportunities" Congress, Dundee, July 2005, pp. 71-80.
6. Corradi M, Khurana R. and Magarotto R., "New superplasticisers for the
total control of performances of fresh and hardened concrete" Proceedings of "Global
Construction: Ultimate Concrete Opportunities" Congress, Dundee, July 2005.

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Table 1 -- Effect of secondary fuels on cement composition
Parameters Cement without secondary fuels Cement with secondary fuels and
without adjustment
c3s (M %) 60.1 59.7
c2s (M %) 13.6 13.2
C4AF (M %) 5.1 4.9
o-C3A (M %) 6.0 10.0
c-C3A (M%) 5.3 2.2
Sulphatization (%) 60.0 40.0

Di-Hydrate- Anhydryte (%) 50-50 50-50
Setting time (h:m) 3.20 2.05
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 2 -- Chemical analysis of the fly ashes
FLY ASH 1 FLY ASH2

(CiassN) (Class C)
Loss on ignition 7.40 8.30
Si02 51.93 32.27
CaO 7.10 29.86
MgO 1.95 2.36

Fe203 6.61 5.25
AJ203 22.16 14.48
Na20 0.50 0.18
K20 1.00 0.40
S03 0.10 1.52
Free CaO 0.35 0.84
Insoluble residue - -
Table 3 -- CaC03 content and conductivity measurement
CaC03 CONDUCTIVITY
(% by weight) (p.S/cm)
Limestone 1 52 400
Limestone 2 73 2600
Limestone3 99 47
Limestone4 99 40
Limestone 5 99 33

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240 Corradi et al.
Table 4 -- Porosity parameters of the fly ashes and limestone fillers
POROSITY PORE SURFACEAREA

(%) (m2/g)
Fly ash 1 28.1 1.0
Flyash2 35.4 1.1

Limestone I 45.7 1.1
Limestone2 48.1 1.5
Limestone 3 44.5 1.3
Limestone4 43.0 0.2
LimestoneS 40.1 0.1
Table 5- Workability retention of different cements and polymers
Cement Polymer type Dosage(%) W/C Slump(mm) Slump(mm) Slump(mm)

type at 5 min. at30min. at 60min.
A PCE1 1.0 0.52 200 80 0
A PCE2 1.2 0.65 220 190 140
A PCE3 1.2 0.54 210 200 170
A PCE4 1.2 0.52 220 210 210
"Tailor made"
B PCE l 1.0 0.53 200 70 0
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
B PCE2 1.2 0.59 210 210 190

B PCE3 1.2 0.55 220 210 200
B PCE4 1.2 0.52 210 210 200
"Tailor made"
c PCE 1 1.0 0.56 210 100 20
c PCE2 1.2 0.67 210 200 180
c PCE3 1.2 0.58 200 160 90
c PCE4 1.2 0.57 210 210 200
"Tailor made"
D PCB I 1.0 0.58 200 100 30
D PCE2 1.2 0.67 220 210 130
D PCE3 1.2 0.60 220 160 90
D PCE4 1.2 0.60 220 220 !90
"Tailor made"
Table 6 -- The concrete mixture composition
Cement CEM 1 52.5 360kg

Limestone filler 4.5% 85 kg
Sand0-2mm 7.5% 102kg
Sand0-8mm 37% 702kg
GraveiS-12 mm ll% 209kg
Coarse aggregate 15-22 mm 23% 436kg
Coarse aggrelU!te 22-32 mm 17"/o 322kg
Water 1371
PCE Supemlasticizer 5.2 l
W/C 0.39

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Table 7 -- Application of "tailor made" superplasticizers in ready mix concrete in several European countries
COUNTRY DENMARK DENMARK FRANCE FRANCE CH CH SPAIN SPAIN
Cement type CEM CEM CEM CEM CEM CEM CEM CEM
I 52.5 I 52.5 I42.5 I 42.5 I42.5 I 42.5 I 42.5 I 42.5
Cement content 222 + 114 222 + 114 375 375 330 330 300 300
FLY ASH FLY ASH
Admixture type LSRSP TAILOR LSRSP TAILOR HRWR TAILOR HRWR TAILOR
+AEA MADESP MADESP SP MADESP SP MADESP
+AEA
Admixture 1.2 I I I I 1.2 I 0.86
content (%)
W/C 0.56 0.51 0.43 0.39 0.47 0.48 0.49 0.50
Air content (%) 7.1 6.4 1.8 1.6 1.5 0.8 1.6 1.8
Slump (mm) 250 250 200 220 180 210 130 100
illt-5min.
(tiJ t- 30min. 240 250 190 195 130 210 60 80
(< t-60min. 230 250 180 190 7 21 0 8
(G t-90 min. 220 230 170 180 3.5 18 0 7
Temperature of
fresh concrete 23.2 27.1 27.0 29.5 25.8 28.6 30.0 32.0
COCJ
Compressive
strength (MPa)
@!day 7.4 11.5 20.8 27.4 29.1 28.6 25.8 24.9
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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
242 Corradi et al.
Table 8 -- Application of "tailor made" superplasticizers in ready mix concrete in Italy
Cement type CEMII CEMII CEMII CEMll CEMII

AIL42.5 AJL42.5 A/L42.5 AIL42.5 AIL42.5
+FLY ASH +FLY ASH
COUNTRY ITALY ITALY ITALY ITALY ITALY

Cement content 280 280 280 240+60 240+60
Admixture type HRWR LSRPCE TAILOR HRWRPCE TAILOR

PCE MADESP MADESP
Admixture content 1.0 1.2 1.2 1.0 1.0
(%)
Wlbinder 0.53 0.59 0.53 0.52 0.51
Air content (%) 2.3 2.4 2.2 1.5 1.4
Slump (rnm)
@t=5min. 200 210 220 210 220
@t=30min. 70 210 210 170 220
@t=60min. 30 190 200 130 210
@t=90min. n.d. 160 190 90 200
Temperature of 26 26
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
30 30 30
fresh concrete ( 0 C}
Compressive
strength (MPa)
@!.day 25.0 20.5 24.1 20.3 25.0
Compressive
strength (MPa)
@28days 49.9 45.4 52.0 27.5 36.7

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Supetrpiastkizers; <a~llil~ <C!hemka~ Admixtures; i11 Concrete ~43
40
s
e
c 35
0
n
d 30
a
r 25
y
M 20
a
t
e 15
r
i 10
a
I
s 5
(%)
0
1992 1993 1994 1995 1996 1997 1998 1999 2000 2001
Figure 1 --Secondary fuels in cement production
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
lliiY.......,u"IDa
Olhar I!Ur'Dp<l
llluodi.... Food..... ~
• 11'110
..J
l
Nerlll AniiOftm ln.
-·1-
«l&&INS.Amori..., sw
AM""' 24V.
Mioi. . ECIGO
IBiootAila
I
2ft
SOI!Iheii'A.,
o.-• s:n 41
Figure 2 --Supplementary cementitious material use for zero carbon dioxide increase

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244 Corradi et at.
W/C
Low sticldness
Cement
£2l!l!l!lf
Extended
Workability
Potential for High

Differentiating Versatility
Figure 3 -- Positioning of the various types of superplasticizers based

on their performance
Adsorption of PCE
70
~50
BO
~ ----== --+-S1
i
I;
~ -40
11 30
-----=== - _,.
-+-S2
__._S3'
--><--84
--oE-S5
~
i 20
---+---87
-sa
10 r--- --
10 15 20 25 ao
timo(mln)
Figure 4 --Adsorption of PCE polymer onto different sands
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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A 100
D
s 90
0 80
R
B 70
E
D 60
p 50
0 40
L
y 30
M
E 20
R 10
(%) 0
0 5 10 15 20 25 30
TIME (MIN)
Figure 5 --Adsorption pf PCE polymer onto different fly ashes
A 100
D
5 90
0
R so ~
B 70
E -+--Limestone 1
D 60 ~Limestone 2
p 50 -+-Limestone 3
0 40 --- Limestone 4
L
y 30 --Limestone 5
M
E 20
R
10
(%)
0 10 15 20 25 30
TIME(MIN)
Figure 6 --Adsorption of PCE polymer on different limestone fillers
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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246 Corradi et al.
Ad'sorpt1on on CEM 11/A-L .&2 6 Adsorption on CEM IIIA-l 42.5 ~.
Cement A Cement B
F~~~-2? o
~
iJ---..-~-~---~~~~~-~ EJI
~r==i ~-~:~------! 1==:1
~::r····_
--
,D ~:f~=~--~~~-~~-=~~-=u-1
--
01
.
Adsorption on CEM II/A-LL 42.5 AdsOiptionon CEM WA-LL 42.5

Cement C Cemer1 D
Figure 7 -- Adsorption of the PCE polymers on to the cements A- B-C-D
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 8 --Positioning of internal formwork

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Figure 9 --Construction of Modena west inter-crossing

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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248 Corradi et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-17
Effectiveness of Commercial Corrosion

Inhibitors for Reinforced Concrete
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
by F. Bolzoni, S. Goidanich, M. Ormellese,

M.P. Pedeferri, and A. Lolli
Synopsis: This paper presents five years of data on the effectiveness of six
commercial corrosion inhibitors: four admixed and two migrating. Both chloride
and carbonation induced corrosion were considered, and the performance of the
inhibitors was evaluated by long-term rebar corrosion monitoring, chloride profiles
and carbonation depth. ln chloride containing concrete, inhibitors seems to increase
time-to-corrosion: this is mainly related to a reduction of chloride penetration rather
than a significant increase in critical chloride threshold for corrosion initiation. The
inhibitors had negligible effect on carbonation rate; once corrosion occurred, they
were not effective in reducing corrosion rate. Migrating inhibitors delayed initiation
of chloride-induce corrosion if applied before corrosion initiation. No effect was
observed on corrosion rate.
Keywords: carbonation; chloride-induced corrosion; concrete;

corrosion inhibitors; corrosion rate; critical chloride threshold

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250 Bolzoni et al.
F. Bolzoni, graduated in Engineering in 1990, got Electrochemical Engineering PhD in
1995. Since 2002 he is associate professor in the Department of Chemistry, Materials and
Chemical Engineering (CMIC) of Politecnico di Milano. From 1999 he is teacher of
Materials Technology for Civil Engineering.
S. Goidanich graduated in Chemistry at the Universita degli Studi di Milano in 200 I; got
PhD in Materials Engineering at the CMIC Department of Politecnico di Milano in 2005.
M. Ormellese, graduated in Chemical Engineering in 1998, got Electrochemical

Engineering PhD in 2001. From 2001 he is teacher of Cementitious and Ceramic
Materials for Materials Engineering. From 2005 he is researcher at the CMIC Department
of Politecnico di Milano
M.P. Pedeferri, graduated in Chemical Engineering in 1995, got Chemical Engineerin!

PhD in 1998. From 1995 to 1998 she worked at the ETH of Zurich. From 2001 she is
researcher, and since 2006 she is associate professor at the CMIC Department of
Politecnico di Milano.
A. Lolli graduated in Chemical Engineering at the Politecnico di Milano. He is presently

co-operating with MAPEl as expert of applicative tests at the concrete department of
Mapei Research Laboratory in Milan. He is author of several papers on concrete
technology and cement chemistry.
INTRODUCTION
Corrosion inhibitors are chemical compounds that delay initiation and/or propagation
of corrosion of reinforcement in concrete structures. They may be used both as preventive
measures for new concrete structures, through addition to the fresh concrete, as well as a
repair techniques for existing structures. Obviously, the prevention of corrosion is
primarily achieved in the design phase by using high quality concrete, adequate concrete
cover and suitable casting and curing. Additional prevention methods are mandatory
when severe environmental conditions occur or on structures requiring very long service
life (Bertolini eta!. 2004 ) . Among available methods, corrosion inhibitors can offer a simple and
cost effective prevention technique to delay chloride induced corrosion and as a remedial
job for carbonation (Eisener 20011 .
Nowadays, several admixtures are available in the market: inorganic compounds

based on nitrites, as additives (Berke et al. 1990; Berke and Wei! 1992; Berke and Hicks 2004), or sodium
mono-fluoro-phosphate (MFP) as migrating inhibitor (Andrade et aL 19961 ; organic compounds
based on mixtures of alkanolamines, amines or amino-carboxylate ions, or emulsions of
fatty acids, used as admixed and migrating inhibitors (Elsener 2001; Welle et al. 1997; Bjegovic and Miksic
1999; Mader 1999; Page 2000; Nmai and Paci 2003)
Among admixed corrosion inhibitors (ACis), nitrite-based compounds are considered

the most effective products: they have been studied since the SO's, and several
applications confirmed their effectiveness. Nitrite acts as a passivating compound, due to
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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its oxidizing properties, provided that a sufficient nitrite ions/chloride ions molar ratio is
assured and maintained for inhibition effectiveness (E1sener 2001; Berke et a1. 1990; Berke and Wei11992;
2004
Berke and Hicks l. Concerns are with its harmfulness, solubility and possible increase in
corrosion rate in the case of low dosage or in the presence of cracks when leaching
occurs. Controversial results were obtained in severe condition (cracking of concrete,
seawater) (Conepardi eta!. 1990l in which also some commercial organic products showed low
inhibition efficiency (Fratesi eta!. 1994).
Organic corrosion inhibitors act by adsorption on the metal surface, forming a layer,
that may inhibit both anodic and cathodic processes (mixed inhibition mechanism (Elsener
2001
; Welle eta!. 1997 ; Nmai and Paci 2003 l. Laboratory tests, both in solution and in concrete, showed
conflicting results about the efficiency and the minimum effective inhibitor concentration
(Pazini eta!. 1998; Trepanier eta!. 2001; Saricimen et al. 2002\ moreover, their relatively recent introduction
and fewer field applications provide little data on their long-term efficiency.
With regard to migrating corrosion inhibitors (MCis), their effectiveness is related to

their ability to reach the rebar surface: they are claimed to migrate into the hardened
concrete with a penetration rate of 2 mrn/day (E1sener 2001 l. The corrosion behaviour of steel
in the presence of MCis has been widely studied (E1sener 2001; Mader 1999; Morris and Vazquez 2002;
Tritthart 2003; Bavarian and Rainer 2003; Mader 2005), however the published results are SOmetimeS
contradictory. There are doubt on migration ability (Trirthart 2003 l, or inhibitors may penetrate
only in conditions (low concrete cover, high permeability concrete) that favours
penetration of aggressive agents too (Andrade et • 1· 1996l. Probably not surprisingly, only tests
carried out by the manufactures show the good penetration of MCls (Bjegovic and Miksic 1999;
BavarianandRainerZOOJ). Some authors affirmed that MCis do not influence the corrosion rate in
mortar specimens exposed to chlorides. According to the literature, the low inhibiting
properties can be attributed to the fact that one of the inhibitor constituents does not reach
the embedded steel, reacting instead with cement paste (Eisener 2001 >. Contrasting to this
opinion, other authors claim that MCis are very effective in reducing reinforcement
corrosion (Bavarian and Rainer 2003; Mader 2005).
This paper summarises results of 5 years of testing on the effectiveness of admixed

and migrating commercial inhibitors on corrosion of rebars embedded in both chloride-
contaminated and carbonated concrete. Four different admixed inhibitors (three organics
and a calcium nitrite based product) and two organic migrating inhibitors were added to
concrete mixture or applied on its surface following each manufacturer's
recommendations. Corrosion was monitored by rebar potential and corrosion rate
measurements. Results are discussed in terms of ability of the inhibitors to delay
corrosion occurrence or to decrease corrosion rate, once corrosion started.
EXPERIMENTAL
Concrete specimens
Concrete specimens (20 x 25 x 5 em) were cast using 367 kg/m3 of cement CEM II
AIL 42.5R (as specified in EN 197-1), w/c = 0.6 and 1,770 kg/m 3 of limestone aggregate
with 1.2 em maximum diameter. Concrete mixture proportion and curing conditions are
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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252 Bolzoni et al.
described in Cerulli et a!. 2006. Two carbon steel rebars (1 em in diameter and 29 em
length) were placed in each specimen. Concrete cover was 2 em. A thin wire of mixed
metal oxide activated titanium (MMO) and three AISI 304 stainless steel wires (0.2 mm
in diameter) were embedded in the specimens and used for polarisation resistance
measurements (Fig. 1). Admixed inhibitors did not impair concrete properties:
workability and strength (Table 1).
Exposure conditions
Three different corrosion conditions were studied: Series 1: concrete specimens cast
with admixed chlorides in dosages 0.8% and 1.2% by cement weight; specimens were
exposed to the atmospheric condition of Milan. Series 2: concrete subjected to ponding
cycles to accelerate chloride penetration, each cycle being three weeks long: first week of
wetting the concrete surface with I L of 3.5% NaCI solution, and two weeks of drying in
the laboratory (T = 20-25°C; RH = 50-60%). Series 3: concrete exposed to carbonation.
Carbonation was achieved by fluxing in a chamber pure C0 2 one hour per day until
complete carbonation of concrete samples. After carbonation, concrete specimens were
exposed outside in Milan.
Inhibitors dosages
Three organic commercial ACis (org A, B and C) and a nitrite-based product (N)
were added to the fresh concrete following the manufacturers' prescriptions (Table l).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Two commercial MCis were tested: they were amines and alkanolamines based with
phosphorous inorganic compounds in their mixture. Applied dosages were 400 g/m2 of
concrete surface for inhibitor MIG-1, and 250 g/m 2 for inhibitor MIG-2. The number of
applications depended on the test series (Table 2). MCis were applied once on specimens
with 0.8% admixed chlorides; three times on specimens with 1.2% admixed chlorides,
and twice on carbonated concrete. In the case of specimens of series 2, two conditions
were analysed: applications of MCis before corrosion initiation (series 2a) and after
corrosion initiation (series 2b). In this latter case, at the end of experimentation, since no
corrosion rate reduction was observed, 1 L of inhibitor was put on the upper surface of
the concrete samples for more then 8 months to verifY if in this case the inhibitors would
be able to reduce corrosion rate.
Corrosion tests
Corrosion potential was measured with an external saturated calomel reference
electrode (SCE) placed on the concrete, following the procedure in ASTM C 876.
1978
Corrosion rate was evaluated by the linear polarisation technique (Andrade and Gonzales >,
applying a potential scan rate of 10 mY/min in the range of ±10 mV with respect to the
free corrosion potential. Mean corrosion rate was calculated by means of the Stem-Geary
relationship: icorr (rnNm2) = B/Rp, where B is equal to 26 mV and Rp (0 m2) is the
measured polarisation resistance. In the case of carbon steel, 1 rnNm2 corrosion rate
correspond to a penetration rate of 1.1 7 J.Lmlyear. Since corrosion penetration lower than
l-2 J.Hnlyear can be considered negligible (Andrade 1998>, a polarisation resistance value of

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about 10-20 n m2 would be the threshold value below which corrosion can be
considered significant.
Chlorides profile
Concrete cores, extracted from concrete specimens, were sliced. Each slice, after
milling, was then dissolved in nitric acid and the total chloride ions content was
determined by potentiometric titration with 0.1 moi!L AgN0 3, as specified in UNI 9944.
Carbonation penetration
Penetration of carbonation was detected by means of phenolphthalein tests on
100 mm cubic concrete specimens (as specified in UNI 9944), and was also confirmed on
concrete cores extracted from the reinforced concrete specimens.
RESULTS
Series 1: Chlorides containing concrete with admixed inhibitors

Concrete specimens were exposed to the external atmosphere for 5 years. Free
corrosion potentials and polarisation resistance of the rebar were periodically measured.
Free corrosion potential of rebars in concrete without inhibitor decreased as admixed
chloride content increased (Fig. 2), ranging from values close to 0 mV SCE in the
chloride free concrete, to -300 mV SCE in concrete with 1.2% admixed chlorides by
cement weight. Scattering in the potential trend may be attributed to seasonal weather
variations from wet to dry conditions. In the presence of commercial inhibitors, corrosion
potential is between -200 mV and 0 mV SCE in concrete with no admixed chlorides,
while, in specimens with 0.8% and 1.2% admixed chlorides by cement weight the
potential is between --400 mV and -50 mV SCE, and between --450 mV and -100 mV
SCE, respectively. Also corrosion rate was influenced by chloride concentration. In the
chloride-free concrete, the rate is negligible, in specimens with 0.8% chlorides by cement
weight the corrosion rate is low and in the 1.2% chloride specimens, corrosion rate is
medium to high, except for concrete with inhibitors A and N, in which corrosion rate was
negligible for more than l 000 days.
Series 1: Chlorides containing concrete with migrating inhibitors

In specimens with 0.8% admixed chlorides by cement weight, migrating corrosion
inhibitors were applied only once after 800 days of external exposure, when a significant
corrosion was measured on the rebars, i.e. low polarisation resistance. After the
application no significant variations were observed neither on the corrosion potential nor
on the polarisation resistance (Fig. 3). In specimens with 1.2% admixed chlorides, MCis
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
were applied three times, after 8 months, 1 and 2 years of atmospheric exposure. Also in
this case, polarisation resistance, and so corrosion rate, seem to be not affected by the
presence of the two inhibitors (Fig. 3). Comparing Fig. 2 and Fig. 3, no difference in
behaviour of rebars in concrete without inhibitors or applied MCis was observed. The
potential increase may be attributed to seasonal variation.

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,,`,,`,`,,`---
254 Bolzoni et al.
Series 2: Ponding tests with admixed inhibitors
Free corrosion potentials of rebars in specimens subjected to ponding cycles are
shown in Fig. 4. Two specimens were cast for each inhibitor, so that four carbon steel
rebars in the same conditions are considered. 86 ponding cycles were performed. In all
specimens initial rebar free corrosion potential was -100 mV SCE and polarisation
resistance was 100 n m2, i.e. reinforcements were passive. The sudden potential decrease
to values lower than -300 mV SCE indicates corrosion occurrence. At the end of the
tests, all the rebar were under active corrosion conditions. In the absence of inhibitors the
four rebars showed a potential decrease at the lOth, 18th, 21st and 38th cycle, respectively.
A similar behaviour was observed in the presence of inhibitor B. The higher increase in
time-to-corrosion was measured in the presence of inhibitor A: the potential decrease was
observed in the range of the 55th and 85th ponding cycle. All the rebars in concrete with
inhibitor C showed a reduction around the 65th cycle. Rebar potential decrease in concrete
with inhibitor N show a wider range, from the 1th to the sth cycle.
Five chloride profiles were estimated during the five years test, respectively at the
14'h, 30'\ 47th, 65th and 86th ponding cycle, at the end of the test. Results are described in
Bolzoni et al. 2006. After I 4 ponding cycles, chloride content was higher than 0.1% by
concrete weight only for concrete depths lower than 20 mm, so lower than the cover. No
difference was observed among the concrete specimens cast with or without inhibitors.
As expected, chloride contents increased with time: the highest values were always
measured in concrete without inhibitor, while the lowest in concrete with organic
inhibitor A. Concrete with inhibitor N behaved as the reference concrete. At the end of
the tests, at the rebar level (2-3 em), the chloride content in the reference concrete is in
the range of0.6-0.7% by concrete weight; similar values were measured in concrete with
inhibitor N, while in the presence of organic inhibitors chloride concentration is in the
range ofO.Z-0.4%.
Series 2: Ponding tests with migrating inhibitors applied before corrosion occurrence
Fig. 5 reports potential trend for rebars embedded in concrete samples subjected to
accelerated chloride penetration. Before initiation of corrosion, migrating inhibitors MIG-
I and MIG-2 were applied at the 8th and 14th ponding cycle. Up to now 80 ponding cycles
have been performed. In the case of concrete treated with migrating inhibitor MIG-1 a
potential decrease was detected on all the rebars at the !51\ 24t\ 27th and 71 st cycle, while
in the case of migrating inhibitor MIG-2 only three of the four rebars showed a potential
reduction, at the 23'd, 28'h and 57th ponding cycle, respectively. One rebar is still passive
after 80 ponding cycle.
Series 2: Ponding tests with migrating inhibitors applied after corrosion occurrence
Four concrete specimens were cast with w/c = 0.65 in order to accelerate chloride and
inhibitor penetration. After 4 ponding cycles, that is approximately 80 days, both
potential and polarisation resistance lowered, indicating corrosion occurrence. Then
application of migrating inhibitors was carried out after 100 and 210 days. Measured
rebars polarisation resistance are reported in Fig. 6. No variation was detected after each
corrosion inhibitor application. Since ponding cycles continued after MCI application,
chloride concentration at the rebars level increased reaching values close to 2% by

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cement weight after 350 days. After 380 days, ponding cycles were stopped, and 1 L of
migrating inhibitor was applied on the upper surface of each concrete sample in order to
verify if such application would lead to a corrosion rate reduction. As illustrated in Fig. 6,
no significant variation in polarisation resistance was measured. Tests finished after 250
days of continuous inhibitor application.
Series 3: Carbonated concrete with admixed inhibitors

The influence of commercial ACis on carbonation rate was measured by means of
phenolphthalein tests. Two tests were performed (Table 3). The total duration of
carbonation process was about 110-120 days. The inhibitors showed no significant
influence with respect to the carbonation penetration measured for the reference concrete.
After carbonation, specimens were exposed outside to Milan atmosphere (carbonation
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
was verified on a concrete core extracted from the samples). Both corrosion potential and
polarisation resistance decreased to values close to -400 mY SCE and lower than
lO Q m2 (Fig. 7), irrespective of the presence of any inhibitors.
Series 3: Carbonated concrete with migrating inhibitors

Migrating corrosion inhibitors MIG-I and MIG-2 were applied after 8 months and
1 year on carbonated concrete samples. Steel rebars exhibited free corrosion potential of
about -500 mY SCE and low polarisation resistance value, i.e. corrosion rate higher than
5 mA/m 2 (Fig. 8). No significant difference was observed after inhibitor treatment. A
slight potential increase to -300 mY SCE in noticeable, even if this behaviour was
measured still on the reference samples (see Fig. 7). Similar behaviour is observable on
the polarisation resistance values.
DISCUSSION
An effective corrosion inhibitor should influence service life: it could delay time-to-
corrosion (i.e. initiation), by increasing the critical chlorides threshold or reducing
chloride ingress or carbonation penetration rate, or, once corrosion occurred, reduce
corrosion rate (i.e. propagation).
Chloride-induced corrosion
Influence of inhibitor on time-to-corrosion - The presence of admixed inhibitors
increase initiation time in the case of chloride-induced corrosion. Fig. 9 reports the
number of the ponding cycle in which the occurrence of corrosion was measured by the
reduction of both potential (Fig. 4) and polarisation resistance. Admixed organic
inhibitors A and C provided the strongest increment, while no effect was noticed in the
presence of inhibitor B. Nitrite-based inhibitor (N) effect is scattered: time-to-corrosion
ranged from values similar to those measured in the absence of inhibitors to values
slightly lower than those obtained in the presence of inhibitor C.
Fig. 9 also reports time-to-corrosion obtained in the presence of migrating inhibitors

applied on concrete surface. While MIG-I had a minimum effect, inhibitor MIG-2
appeared to increase corrosion initiation: one rebar is still passive after 86 ponding cycle
(5 years test).

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256 Bolzoni et al.
The influence of inhibitors on time-to-corrosion may be related to an increase in the
critical chloride threshold or to a reduction of chloride diffusion coefficient. These two
parameters were estimated by interpolating the experimental chloride profiles (five
determinations (Bolzoni et al. 2006 )) with the analytical solution of the second Fick's law, which
describes the non-stationary diffusion phenomena: Cx = C, . xj(2~ D,i! . t )J where Cs is
{1-
the surface chlorides content, Deff is the effective diffusion coefficient (Table 4), Cx is the
chloride content at the depth x and t is time (Bertolini et al. 2004l.
Influence of inhibitor on critical chloride content - Critical chloride content was

determined taking timet equal to time-to-corrosion (Fig. 9), depth x = 20 mm (concrete
cover) and considering the extrapolated values of Cs and Deff· Also a graphical approach
was performed for each inhibitor using for the five measured profiles. Obtained values
are reported in Table 4: it must be underlined that they are related to the described
experimental conditions, so they should not be considered as absolute values, but used
only for comparison purposes.
In the absence of inhibitor, critical chloride content is in the range 0.4-1.3% with
respect to cement weight: those values are in accordance with the literature, at least the
minimum ones (Bertolini et al. 2004 J. Organic inhibitors A and C provided significant increase
in critical chloride content (both minimum and maximum are doubled with respect to
reference condition), while inhibitor B did not show any significant influence. The effect
of inhibitor A was also confirmed by results of specimens of series I: in the presence of
1.2% admixed chlorides no corrosion has been measured even after 5 years. In the case of
nitrite-based inhibitor (N), considering inhibitor dosage and the obtained critical chloride
content, the estimated molar ratio [N0 2-]/[Cr] is in the range 0.21-0.44, that is lower
than 0.5, considered the threshold value above which the inhibitor is effective (Berke et al.
1990; Berke and Wei! 1992; Berke and Hicks 2004)
It is worth noticing that in any case values are scattered (Table 4): so the effect of
inhibitors is not so clear, above all in experimental conditions different from those used
in this research. Nevertheless, five years of testing show that organic inhibitor A and C
provide an increase in the critical chloride threshold.
Influence on chlorides diffusion coefficient - Extrapolated effective chloride

diffusion coefficients are reported in Table 4. Diffusion coefficient decreased with time
as a result of continued cement hydration and interaction of inhibitor with cement paste.
The presence of organic inhibitors reduce diffusion rate: the maximum reduction
occurred in specimens containing organic inhibitor C. The sudden increment measured at
the 86'h ponding cycle in the case of concrete without inhibitors and specimens with
inhibitors N can be attributed to cracking of concrete due to rebar corrosion.
Influence on corrosion rate - Table 5 summarises the performances of the four

admixed commercial inhibitors in terms of influence on corrosion rate ().Jm/year). Mean,
maximum and minimum measured values during the 5-years test are reported. Corrosion
is considered negligible if the rate is lower than l-2 ).1m/year (Bertolini et al. 2004 ). In specimens
with 0.8% admixed chlorides by cement weight there was no significant difference in
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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corrosion rate with or without the commercial inhibitors; the highest values were
measured in concrete with inhibitors B and C, but they are quite low. In specimens with
1.2% admixed chloride, only rebars in specimens with organic inhibitor A and with
nitrite had lower corrosion rate. The other commercial inhibitors did not show a
significant reduction.
No significant reduction in corrosion rate was measured after migrating inhibitors

application, neither in the case of admixed chlorides (Fig. 3), nor in the case of
penetrating chlorides (Fig. 6): corrosion rate is higher than 2 llmiY (i.e. polarisation
resistance lower than 10 0 m2). Even the continuous application for 250 days of 1 L of
MICs on the concrete surface after the end of chloride ponding did not reduce the
corrosion rate (Fig. 6). Experimental data show that the influence of inhibitors on
corrosion rate may be considered low, or negligible. Nevertheless, it must be underlined
that, due to the high penetration rate, typical of the localised corrosion, the effect on
propagation period is not so significant; in fact, in the case of chloride-induced corrosion
the world-wide approach is to consider only the corrosion initiation period (Bertolini et al. 2004 >.
Carbonation induced corrosion

Influence on carbonation penetration - Carbonation of concrete was monitored by
means of phenolphthalein tests on cubic specimens: results are reported in Table 3. As
carbonation penetration follows a parabolic law (Bertolini et aL 2004l, carbonation coefficients
K were estimated interpolating the experimental data (Table 3). The results show that the
commercial corrosion inhibitors did not reduce carbonation penetration; only in concrete
with organic inhibitor A the carbonation coefficient was lower by about 7.5% with
respect to the one determined in the reference concrete. This reduction is not considered
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
significant.
Influence on corrosion rate - Mean, maximum, minimum values of rebar corrosion

rate in carbonated concrete specimens are reported in Table 5. Admixed corrosion
inhibitors did not influence corrosion rate: values were generally higher than 2 llmly, so
corrosion is not negligible. Inhibitor efficiency has been evaluated (Table 5), as the
percentage reduction of corrosion rate with respect the value in reference concrete (mean
values of corrosion rate were considered). It is worth noticing that only inhibitors B and
C provide an efficiency of about 20-25%. This is a poor effect, since an inhibitor should
reduce the corrosion rate by more than 90%. Besides, in the presence of inhibitor B (the
one with the best mean efficiency) high corrosion rate values, higher that 10 llrnly, were
measured.
The nitrite dosage suggested by manufacturer, in this case 1% by cement weight, was
not adequate to reduce corrosion rate in carbonated concrete. This is in agreement with
literature data that report a dosage close to 2-3% in order to reduce corrosion rate in
carbonated COncrete (Alonso and Andrade 1995).
The application of MCis slightly reduced corrosion rate: in the presence of MIG-2,
polarisation resistance increases from 2-5 n m2 to 20 n m2 (Fig. 8), so the corrosion rate
decreased from 10-20 1-lm/y to values close to 2 1-lm/y.

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258 Bolzoni et al.
Mechanism of inhibition
Aim of this experimental research was to evaluate and compare the effectiveness of
commercial corrosion inhibitors (both inorganic and organic), and to understand the
mechanism by which the organic compounds inhibitor rebar corrosion. In fact, while
there is full agreement on the mechanism and the dosages by which the nitrite-based
compounds inhibit rebar corrosion, there is lack of knowledge as regard organic mixtures.
As reported in literature, nitrite compounds act as anodic passivating inhibitors, provided
that a nitrite ions/chloride ions molar ratio lower than 0.5 is assured and maintained for
inhibition effectiveness (Eisener2001; Berke et al. 1990; Berke and Wei!l992; Berke and Hicks 2004). On the other
hand, organic-based corrosion inhibitors act by adsorption on the metal surface, forming
a layer, that may inhibit both anodic and cathodic processes; from an electrochemical
point Of View, the mechanism iS that Of mixed inhibition (Eisener ZOO I; Welle et al. 1997 ; Nmai and Paci
2003
1. But no indication both about the effect on critical chloride threshold and on the
minimum inhibitor dosage in order to guarantee the presence of an organic layer on the
rebar surface able to delay corrosion occurrence is reported in literature.
Taking into account results obtained in five-years research, the tested organic
inhibitors are able to delay the onset of chloride-induced corrosion, while, on the other
hand, no significant effect was detected on both the penetration rate of C0 2 and the
reduction of corrosion rate, once corrosion occurred. The delay of chloride-induced
corrosion is mainly related to a reduction of the penetration rate of chlorides (as
suggested by the lower estimated chlorides diffusion coefficient) rather than an increase
in the critical chlorides threshold for the occurrence of localised corrosion. It is possible
to state that the commercial organic inhibitors act reducing the ingress of chlorides by
filling concrete pores and blocking the porosity of concrete with the formation of
complex compounds. This effect is also reported in literature (Nmai and Paci 2003 l. The slight
increase in the critical chlorides threshold is not so important, and it seems not always
reproducible and also influenced by experimental test condition. Summarising, the
inhibitors interact mainly with the cement paste, whereas no significant actions has been
measured at the interface with the reinforcement.
Nevertheless, it must be underlined that the effect on chloride diffusion is not a pure
electrodic inhibitive action, but it is only related to interaction of organic compounds with
cement paste. A similar or stronger reduction of chlorides diffusion may be obtained
simply with lower w/c, or by using blended cement, such as pozzolanic, fly ash or ground
granulated blast furnace slag addition (Bertolini et al. 2004).
Nitrite-based inhibitor must be considered separately. Considering inhibitor dosage

(1% by cement weight) and composition (30 % nitrite solution), and the obtained critical
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
chlorides content (Table 4), a molar ratio in the range 0.21-0.44 has been estimated, thus
confirming the fact that the inhibitor is effective only if the molar ratio [N02-]/[Cr] is
higher than 0.5. In the case of carbonation-induced corrosion the considered dosage is too
low to guarantee corrosion prevention.

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CONCLUSIONS
Commercial corrosion inhibitors studied in this work provided a limited effectiveness

in chloride-contaminated concrete and they were substantially ineffective in carbonated
concrete. Their performance was evaluated by long-term rebar corrosion monitoring,
chloride profiles and carbonation depth.
Experimental results show that:

in concrete containing chloride, admixed inhibitors increase time-to-corrosion: this is
mainly related to a reduction of chloride penetration even if increase in critical
chloride threshold has been determined;
in carbonated concrete, admixed inhibitors do not influence carbonation of concrete;
once corrosion occurred, they are not effective in reducing corrosion rate;
applied migrating inhibitors are effective in increasing time-to-corrosion in chloride-
induced corrosion only if they are applied before corrosion initiation. No effect was
observed on corrosion rate;
results obtained in the presence of nitrite base inhibitor are in agreement with the
literature.
REFERENCES
Alonso C. and Andrade C., 1995, "Effect of nitrite as corrosion inhibitor in contaminated
and chloride-free carbonated mortars", ACI Material Journal, 3-4, p. 130.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Andrade C. and Gonzales J.A., 1978, "Quantitative Measurements of Corrosion Rate of

Reinforcing Steels Embedded in Concrete Using Polarization Resistance Measurements",
Werkstoffe und Korrosion, Vol. 29, pp. 515-519.
Andrade C., 1998, "An initial effort to use the corrosion rate measurements for estimating
rebar durability", Symposium on corrosion rate of reinforcement in concrete, ASTM,
Baltimore, USA.
Andrade C., Alonso C., Acha M. and Malric B., 1996, "Na2P04F as Inhibitor of
Corroding Reinforcement in Carbonated Concrete", Cement and Concrete Research, 26,
pp. 405-415.
ASTM C876-91, 1991, Standard Test Method for Half-cell Potential of Reinforcing Steel
in Concrete, American Society for Testing and Materials.
Bavarian B. and Rainer L., 2003, "Improving durability of reinforced concrete structures
using migrating corrosion inhibitors", Int. Conference EUROCORR, Budapest, Paper 19.
Berke N.S. and Hicks M.C., 2004, "Predicting long-term durability of steel reinforced
concrete with calcium nitrite corrosion inhibitor", Cement and Concrete Composites,
Vol. 26, pp. 191-198.

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260 Bolzoni et al.
Berke N.S., El-Jazairi B. and Grace W.R., 1990, "The use of C.N. as a
corrosion inhibiting admixture to steel reinforcement in concrete", Conf on
Corrosion of Reinforcement in Concrete, Birmingham, pp. 571.
Berke N.S. and Wei! T.G., 1992, "World-Wide Review of Corrosion Inhibitors in
Concrete", Advances in Concrete Technology, Ed. V.M. Malhotra, Athens, Greece,
pp. 899-924.
Bertolini L. Elsener B., Pedeferri P. and Polder R., 2004, Corrosion of steel in concrete,
1'1 edn, Wiley-VCH, 392 pp.
Bjegovic D. and Miksic B.A., 1999, "Migrating corrosion inhibitor protection of

concrete", Material Pe;formance, n. 11, pp. 52-56.
Bolzoni F., Lazzari L., Ormellese M. and Goidanich S., 2006, "Prevention of corrosion in
concrete, the use of admixed inhibitors", International Corrosion Conference NACE, San
Diego, California, Paper 344.
Cerulli T., Coppola L., Maltese C., Lazzari L. and Ormellese M., 2003, "Laboratory tests
111
for evaluation of corrosion inhibitor efficiency", 6 CANMET Int. Conference on
Durability of Concrete, Ed. V.M. Malhotra, ACI International SP 212, Paper 68,
pp. 1109-1125.
Collepardi M., Fratesi R., Moriconi G., Corradetti C. and Coppola L., 1990, "Use of
nitrite salt as corrosion inhibitor admixtures in reinforced concrete structures immersed in
sea-water", Proceeding of the International RJLEM Symposium on Admixtures for
Concrete - Improvement of Properties, Barcelona, Ed. Vazquez, Chapman and Hall,
London, UK, pp. 279-288.
Elsener B., 2001, Corrosion Inhibitors for Steel in Concrete - an EFC State of the Art
Report, EFC, Number 35, IOM Communications, Cambridge, 68 pp.
EN 197-1 :2000, "Cement -Part 1: Composition, Specifications and Conformity Criteria

for Common Cements", European Committee for Standardisation.
Fratesi R., Moriconi G. and Simoncini S., 1994, "Corrosione delle armature di acciaio nel
calcestruzzo fessurato immerso in acqua di mare", Giornate Nazionali sulla Corrosione e
Protezione, AIM, Milano, 1994, pp. 139-148 (in italian).
Mader U., 1999, "A new class of corrosion inhibitors for reinforced concrete", Concrete,
p. 215-232.
Mader U., 2005, "Surface applied corrosion inhibitors for concrete repair strategies", Int.
Conf. 16'" ICC, Bejing, China.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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`,,`,`,,`---
Morris W. and Vazquez M., 2002, "On the performance of a migrating corrosion
inhibitor applied on reinforced concrete", Cement and Concrete Research, 32, pp. 259-
267.
Nmai, C.K. and Paci P.E., 2003, "A critical review of corrosion inhibitors and their use in
improving concrete durability in the middle east", th Int. Conf. on Concrete in Hot and
Aggressive Environment, Bahrain, Paper 14.
Page C.L., 2000, "Aspects of the performance of corrosion inhibitors applied to

reinforced concrete", 9'h Conf SEIC, Ann. Univ. Ferrara, N.S., Sez. V, Suppl. N. 11,
Ferrara, Italy, pp. 261-276.
Pazini E., Leao S. and Estefani G., 1998, "Corrosion inhibitors. Behaviour ofNaN02 and
Amine-based Products in the Prevention and Control of Corrosion in Reinforced
Concrete"; NACE Latin-American Congress, Cancun, pp. 134-143.
Saricimen H., Mohammad M., Quddus A., Shameem M. and Barry M.S., 2002,
"Effectiveness of Concrete Inhibitors in Retarding Rebar Corrosion", Cement and
Concrete Composites, 24, pp. 89-100.
Trepanier S.M., Hope B.B. and Hansson C.M., 2001, "Corrosion inhibitors in concrete-
part III: effect on time to chloride-induced corrosion initiation and subsequent corrosion
rates of steel in mortar", Cement and Concrete Research, 31, pp. 713-718.
Tritthart J., 2003, "Transport of a surface-applied corrosion inhibitor in cement paste and
concrete", Cement and Concrete Research, 33, pp. 829-834.
UNI 9944, 1992, Corrosione e protezione dell'armatura del calcestruzzo.

Determinazione della profondita di carbonatazione e del profllo di penetrazione dei
cloruri (in italian).
Welle A., Liao J.D., Kaiser K., Grunze M., Mader U. and Blank N., 1997, "Interactions
of N,N-dimethylaminoethanol with rebar surfaces in alkaline and chlorine solutions",
Applied Surface Science, n. 119, pp. 185-190.
Table 1 - Concrete properties and admixed inhibitors' dosages.
Dosage+ Slump Rc2..,*

Inhibitor (kg/ml) (mm) (MPa)
No inhibitor 190 39.8

A Liquid- amino-alcohols 10 190 42.4
Organic B Liquid- alkanolamines 1.6 160 41.6
c Liquid- amine-esters 5 160 39.6
Nitrite based N 30% Ca(N0:!)2 solution 10 160 43.1
+Dosages of commercial corrosion inhibitors suggested by the producers
+Mean value measured on three concrete cubic specimens (100 mm side)

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262 Bolzoni et al.
Table 2 - Application of migrating inhibitors.
Series Exposure condition Number of MCis applications

Chlorides in the 0.8% vs cern I - after 2 years
nrixnrre ------------------~~-------------------
proportion 1.2% vs cern 3 - after 8 months, 1 and 2 years
2a Chlorides penetration 2 - after the 8th and the 14th ponding cycle
2b Chlorides penetration 2- after the 5th and the 8th ponding cycle
3 Carbonation 2 - after 8 months and 1 year
Table 3 -Carbonation depth evaluated by means of phenolphthalein tests on cubic

concrete specimens (I 0 em side) in accelerated tests.
1" pbenophtalein test 2•• pbenophtalein test

Carbonation
Days in Days in
Inhibitor Carbonation Carbonation coefficient K
carbonation carbonation
depth (mm) depth (rom) (mm/year'/2)
chamber cbamber
Noinhib 10 8 23 117 23
A 10 7 21 117 21
B 14 7 22 121 22
c 47 17 22 103 22
N 10 7 22 110 22
Table 4 - Critical chloride content and effective chlorides diffusion coefficient.
Critical chloride content " Diffusion coefficient (108 cm2/s)

Inhibitor
vs concrete vscement 14th 30th 4~ 65"' 86'h
No inhib O.Q7- 0.20 0.47-1.34 7.2 4.0 4.8 8.4 10.2
A 0.17-0.27 1.13-1.80 6.8 3.5 3.0 3.4 3.6
Org B 0.11-0.19 0.73-1.27 4.7 2.9 2.3 1.9 3.1
c 0.19- 0.39 1.27-2.60 3.2 2.8 2.0 2.4 1.8
NIT 0.15-0.35 1.00-2.33 6.1 4.2 2.5 2.7 8.2
• Values as weight percentage
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Table 5 - Mean, maximum and minimum values of corrosion rate (f11111y) measured in
five years test for chloride and carbonation induced corrosion.
Chloride-induced corrosion
Carbonated concrete
Inhibitor C/ = 0.8% vs cern C/ = 1.2% vs cern
mean max min mean max min mean max min Tf*
No inhib 1.8 3.9 0.2 9.0 20.0 2.5 6.8 15.5 2.0 ---
A I.l 3.5 0.3 2.5 11.8 0.5 6.7 14.6 2.5 1%
Org B 3.1 5.4 1.4 9.1 20.0 4.0 5.1 11.2 1.5 25%
c 2.6 6.8 0.5 6.7 12.1 2.4 5.2 9.3 2.1 23%
NIT 0.9 4.6 0.2 2.7 9.8 0.5 5.7 12.5 1.9 15%
• '7 =efficiency, calculated using mean value of corrosion rate
Carbon steel Stainless steel

Ti electrode rebar
.------+-------4,-----\---,-----~---~-
0
20: :
·-·-~- :
--~ ! 50
20:
1------i-----..:;<1>:....__ _-+-----f-----~--~·
I
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
o I o
.~----~~---~- ----- ~~----- -~----- ?~--- --~-----~~----~-

-f----------------- ------------------------------- -~-
200
Figure t-Reinforced concrete specimen (dimension in mm)

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264 Bolzoni et al.
- - no inhib ~ org A ---<r- org B -a- org C -- N
100 !00
<;;
!,
-100 ~ -100
t! -200 t! -200
!"' -300 !"' -300
-400 -400
chlorides "" 00~ chlorides ""'0.8%
-500 -500
500 1000 1500 2000 500 1000 1500 2000
Time(days) Time(days)
100
~ -100
~ -200
! -300
-400
chloride$ = 1.2%
-500
0 500 1000 !500 2000
Tlme(days)
Figure 2-Rebar-free corrosion potential in specimens with added chlorides in the

presence of admixed inhibitors (series 1)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Concrete specimens with 0.8'Yoadmixed chlorides vs cern
-e--MlG-1 ----MIG-I
100 A-MIG-2 1000
-O-MIG-2
--MC!application --MCI application
~ -100 "'E 100
~ -200 g
...
! -300 0:
-400
-500 +-----,---'-~--~-~
0 500 1000 1500 2000 500 1000 1500 2000
Concrete specimens with 1.2% admixed chlorides vs cern
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
------MIG-I ------MIG-I
100 --6-----MIG-2 1000
------6--MIG-2
--MClapplication
--MCiapp!ication
~ -100 100
"8
~ -200 g
...
~ -300
0:
10
-400
-500 +--'-.1....,-....L.~--~-~
0 500 1000 1500 2000 500 1000 1500 2000
Time(days) Time (days)
Figure 3-Rebar-free corrosion potential and polarization resistance in specimens

with added chlorides in the presence of migrating inhibitors (series 1)
111
30111 cycle
111
15 cycle 45 cycle 601hcycle 75"'cycle -.-no inhib
100 -IJ.~orgA
-o-orgB
0
-o--org C
~ -100 . , ---N
t:l
"'~
~
-200
-300
vf1 I l
-400
-500
~
0 500 1000 1500 2000
Time(days)
Figure 4-Rebar-free corrosion potential in specimens subjected to ponding cycles in

the presence of admixed inhibitors (series 2)

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266 Bolzoni et al.
MCI MCI
100 application l 00 l\p~lieatioo
! inhibitor MIG-I I J inhibitorMIG-2!
i -100 ,... J' i I'" __......, ~ -loo idll!fi!llll~w,i~~"JaM~~

!:l
~ -2oo ~I L -200
~ -300 ~ ., !"' -300
-400 -400
-500 +---L-1-,----,------,.---, -500 +--__._'-r----.----,--.,

500 1000 1500 2000 500 1000 \500 2000
Time (days) Time (days)
Figure s-Rebar-free corrosion potential for specimens subjected to chloride

penetration and application of migrating inhibitors before corrosion occurrence
(series 2a)
MCI MC!
1000 appllcatkm 1000 application
! illbibiturMIG·I \
100 100
M-e
'<g&' 10 ,j--'ll!aiH- ---,- -
' - - g lO .,.--,-go,.--,.- ---,- - - -
: ~
200 400 600 800 200 400 600 800

Time(day!) Time (days)
Figure 6-Polarization resistance of rebars embedded in specimens subjected

to chloride penetration and application of migrating inhibitors after corrosion
occurrence (series 2b)
--no inhib ~ org A -<>- org B -o- org C --N

End of End of
0 ~Citlrbunation 100 cuburwtion
Q
0
•
-;
g \0
:
-600
-700 +--L----.---....----,--.,
500 1000 1500 2000 500 1000 1500 2000
Figure 7-Rebar-free corrosion potential and polarisation resistance in carbonated

concrete specimens with admixed inhibitors (series 3)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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0 1000
• WhibiiOrMICH
-100 b. inlnbitorMIG-2
;;
.!
fol
-200 100
1.)
"S
"'!l -300 g
i
a-400
: 10
£.
-500
-600
0 500 1000 1500 2000 500 1000 1500 2000
Time(days) Tlme(days)
Figure 8-Rebar-free corrosion potential and polarisation resistance in carbonated

concrete specimens and application of migrating inhibitors (series 3)
100
admixed inhibitor migrating inhibitor
80 ~
.!I
.;;"
t' 60
l.= 40
20
0
nolnhlb orgA orgB orgC N MIG-I MIG-2
Figure 9-Ponding cycle in which a potential reduction was measured for rebar
embedded in concrete with admixed inhibitors
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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268 Bolzoni et al.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-18
Cement-Superplasticizers Interaction:
The Influence of Superplasticizers on
the Formation ofSyngenite
by H. Kucerova and C. Ro"Bler
Synopsis: Interaction of Portland cement and superplasticizer is significantly

influenced by the alkali sulphate content of the cement. It is widely recognized that
the alkali sulphates are a fast source of sulphate ions that slow down the amount
of superplasticizers molecules that are adsorbed on cement particles. Potassium
sulphate occurs widely as an alkali sulphate in European cements and its higher
content leads to the crystallisation of syngenite immediately after mixing of the
cement paste. However the formation of syngenite influences the rheological
behaviour of cement pastes and this factor has been generally overlooked in
subsequent studies of incompatibility between cement and superplasticizers.
The aim of this study was to reveal the influence of potassium and sodium sulphates
on the dispersing effect of superplasticizers. Two types of superplasticizers have
been used for investigations: polycarboxylate (PC) based and a naphthalene
sulphonate formaldehyde condensate (PNS). By using the combination of rheological
testing, quantitative X-ray diffraction analysis, environmental scanning electron
microscopy and measuring the superplasticizer adsorption, It was possible to
investigate the different influence of K2 50 and Na 2 50 4 on the fluidity of cement
4
pastes. Thereby it can be proven that syngenite formation is an important factor
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
that changes the rheological behaviour of cement pastes and that it is specifically
influenced by superplasticizers.
Keywords: alkali sulphate; cement; fluidity; superplasticizer; syngenite

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270 Kucerova and Ro"Bler
Hana Kucerova, Ph.D. is a Head of Building Materials Laboratory of Chryso Czech
Republic. She also works as a researcher at the Institute of Technology and Building
Materials and Components, Bmo University of Technology, Czech Republic. Part of the
presented data were obtained during her research activities at the F.A. Finger Institute for
Building Materials Science, Bauhaus-University Weimar, Germany
Christiane RoBier, Dipl. earth sc., Ph.D. student F.A. Finger Institute for Building
Materials Science, Bauhaus-University Weimar, Germany.
INTRODUCTION
Rheological behaviour of a cement paste is determined by phenomena occurring in

the early phase of the cement paste hydration (0 - 2 h). The hydration of CA, set
regulator and dissolution of free lime and alkali sulphates, all affect the rheological
properties of the paste. Knowledge of the chemical reactions during the early phase of
cement hydration is essential for studying the effects of superplasticizers on the hydration
of Portland cements. The change of the rheological properties of cement paste in the
presence of superplasticizers is caused, not only by electrosteric stabilisation of the in
cement paste, but also due to changes in the formation of hydration products (ettringite,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
monosulphate, secondary gypsum and syngenite). 1• 2
Soluble alkalis affect both the mechanism of hydration in the cement and the
adsorption of a superplasticizer on cement particles. 3• 4• 5• 6 Alkalis in the cement are
either bound in the structure of clinker minerals (Na 20, K2 0) or they are present in a
form of alkali sulphates. Often calculated as alkali oxide in composition of cements K20
(0.1...1.5 wt.%) outweighs Na20 in European cements (0.1. .. 0.8 wt.%; in US cements:
LO wt.%). 7 After water addition to the cement powder alkali sulphates dissolve
immediately. Thereby the level of sulphate-, potassium- and sodium ions in the pore
solution of the cement paste increases. The amount of soluble alkali sulphates present in
the cement is known to be very important for the rheological behaviour and setting of
cement.
The first hydration product during Portland cement hydration is ettringite. Calcium,
sulphate and aluminate ions are consumed by ettringite crystallisation. At a certain level
of calcium-, potassium- and sulphate ions in the pore solution the supersaturation for
syngenite is reached, leading to crystallisation of syngenite. The syngenite forming
reactions can be represented as (J.Bensted) 8 :
KzS04 + CaS04·2HzO => KzS04·CaS0 4·H20 + H20

KzS04 + KzS04·2CaS04 + 2H 20 =>2(K2S04·CaS04·H20)
Crystals of syngenite are long prismatic and thereby they are able "to bridge" cement
particles and cause a false setting. Similar effect can be observed if secondary gypsum
precipitates. No sodium analogue of syngenite is known. 8 Kurdowski and Grzeszczyk
showed that yield stress and plastic viscosity of cement pastes increase when potassium
sulphate concentrations exceed a certain value (2 %). 9

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The influence of superplasticizers based on polycarboxylate (PC) and naphthalene
sulphonate formaldehyde condensate (PNS) on the hydration of Portland cement with
varying potassium sulphate or sodium sulphate content was investigated. The aim of the
present investigations was to determine whether the crystallisation of syngenite affects
the rheology of the paste, and if the morphology or quantity of syngenite formed is
influenced by molecular properties of PC-type superplasticizer.
Materials
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
A commercial cement of type CEM I 52.5 R according to European Standard EN

197-1 was used for investigation. The chemical composition of studied cement is given in
Table l. XRD Rietveld analysis has been used to quantify the mineral phase composition
(Table 2).
The low alkali content was the main reason for selecting this cement type. Mixtures
of cement and solutions of potassium sulphate, or sodium sulphate, at different
concentrations were prepared in order to simulate cements with higher alkali content.
This method assured invariable cement properties, except for the content of alkali
sulphates.
Assuming that all the water soluble potassium is bound to sulphate the starting
cement contains 0.74 % K 2 S04 • The potassium sulphate content of the cement was
increased in three steps as shown in Table 3. Added quantity of 1.94 % (1.05 % K20,01 )
simulates high alkali cement. In practice higher alkali quantities are not found. For the
present investigation, one higher alkali level was chosen to enhance effects and to
compare with findings for regular alkali contents. For comparison the content of sodium
sulphate was also increased to the same molarities (0.12; 0.18; 0.29 M) in parallel batches
of cement pastes (Table 3).
The water to cement ratio of 0.39 was constant for all samples. The mixing of
cement with water or potassium/sodium sulphate solution was carried out with a standard
mixer according to a defined protocol (Table 4). For investigation of hydration by
Environmental scanning electron microscope (ESEM) and TOC-analysis, samples were
mixed by hand.
Two polycarboxylate based (PC) superplasticizers and one commercial

superplasticizer based on naphthalene sulfonate formaldehyde condensate (PNS) were
used in this study. The basic information concerning the superplasticizers can be found in
Table 5. The differences between the two PCs are the length of side chains and the
amount of free carboxyl groups.
The added amount of SPs was determined by preliminary rheological testing (see
below). The superplasticizer was first mixed with water or with the solution of alkali

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272 Kucerova and RoBler
sulphate and then added to the cement. The mixtures were prepared under laboratory
conditions, i.e. at room temperature of 20°C and a relative humidity of about 65%.
Methods
Fluidity of cement pastes - The rheology of the cement pastes was investigated using a
true speed controlled viscometer Viskomat NT, manufactured by Schleibinger Gerate
GmbH, Germany. One of the possible applications of this device is to monitor changes in
the fluidity of cement pastes due to hydration reactions. The torque (T) with time (2
hours) was measured under the constant rotation speed (60 rpm) and temperature (19.5 ±
0.5 °C). An increase in torque is equivalent with a decrease in fluidity of cement paste.
Viscometer measurements at constant rotation speed are affected by both factors that
define fluidity: (apparent) viscosity and (apparent) yield strength.
Adsorption amount of supemlasticizer - The superplasticizer adsorption on the cement

surface was determined by measuring the amount of superplasticizer in the pore solution
of the cement paste by thermal combustion and quantification of C0 2 evolved. Thereby
the total amount of organic carbon (TOC) in the cement pore solution was determined
(Liqui TOC, Foss Heraeus, Germany, TOC analysis in the following). After 10 minutes
of cement hydration, the pore solution of the cement paste was separated by centrifuging
(11 000 rpm, 5 min). The solution obtained was then filtered through a 0.45 J.tm syringe
filter. Adsorption was calculated by subtracting SP concentration in the filtrate from
initial SP concentration.
X-ray diffraction - Syngenite content in the cement pastes was quantified by Rietveld
Analysis of XRD data. Therefore cement hydration was ,stopped" after 10 minutes by
adding 2-propanol to the paste. The samples were dried at 35 oc on a metal plate and then
homogenised. Due to the fact, that syngenite is a minority phase in the hydrating cement,
it was necessary (to increase precision of the results) to extract the cement phases in the
solution of salicylic acid and methanol. By applying this procedure calcium silicate
phases were removed from the cement paste. The remaining powder was analysed by
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
XRD (05000, Siemens, Germany). The CuKa (A-= 1.5418 A) radiation was generated at
40 rnA and 40 kV. Data have been collected over a Bragg angle range of 8-60° (28),
using an angular step size of0.05° and 5 s counting time.
Calculation of the syngenite content was done by Rietveld analysis with software
Autoquan (BGMN, Germany). Because only short hydration periods were investigated it
has been assumed that the samples contain a small amount of amorphous phases,
therefore no standard was added.
ESEM-FEG Analyses- The morphological analyses of cement pastes with various alkali
sulphate levels and containing the different superplasticizers were performed by using an
Environmental Scanning Electron Microscope (ESEM, XL30, FEI Netherlands) equipped
with a Field Emission Gun (FEG). The operational parameters for the "Environmental"
mode were the following: water vapour in the chamber was set to 8.32- 9.36 mbar and
sample temperature to 12 °C (humidity between 75 % and 90 %). For ESEM

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observations of the early hydration it is crucial to avoid drying artefacts. A special
preparation procedure developed by a research team ofF.A. Finger Institute for Building
Materials Science, Bauhaus-University Weimar, Germany was carried out on samples to
solve this problem. Pastes were washed several times in ethanol and blotted with filter
paper in order to remove the solution of the cement paste and then inserted into the
microscope chamber where a few millimetres of the sample surface were removed by
scratching with a micromanipulator.
RESULTS AND DISCUSSIONS
Preliminary rheological test
The superplasticizer saturation point - according to Aitcin 18 - was determined by
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
increasing progressively the added amount of superplasticizer during the measurement of
the fluidity (i.e. torque at constant rotation speed in the Viskomat NT). Results are shown
in Fig. I. A gain in fluidity (minimum in torque) curves was reached in the samples
without addition of SP after 20-30 minutes. According to the flocculation model 10 , the
floc structure is destroyed by mixing and rebuilt at rest of the paste. The minimal torque
is achieved as soon as the flocculation - deflocculation equilibrium of cement particles
occurs. The torque value which was reached after 30 minutes of measurement was
determined (Fig. 1). Subsequently SP dosage was increased at defined steps until a
maximum fluidity was gained. On this way saturation point can be measured.
It is obvious (Fig. I) that the saturation point of both PC-type superplasticizers lays
around 0.8 %. The addition of 1.8 % PNS superplasticizer to the studied cement is
necessary for reaching the saturation point.
Due to the comparatively high efficiency of PC-based superplasticizers, the dosage

to obtain a similar torque value (approx. 40 Nmm) is lower for PC! and PC2 (i.e. 0,4 %)
than for PNS (i.e. 1.5 %). For the following investigations the superplasticizer dosage
required to obtain 40 Nmm torque was applied to the mixtures.
Effect of Alkali Sulphate on the Fluidity of Cement Pastes without Superplasticizers
Figure 2a shows the influence of increasing potassium sulphate content on the

measured torque values of cement pastes without addition of superplasticizer. Within the
first 5 minutes of measurement due to increase of the potassium sulphate content, a
significant increase of the torque maximum is detected. Cement paste with 0.29 M K2 S04
solution as mixing water developed a fluidity that was over the detection limits of the
viscometer (i.e. > 300 Nmm).
The sodium sulphate content in the m1xmg water was increased to the same
molarities as potassium sulphate. Compared to potassium sulphate, increasing amounts of
sodium sulphate cause higher fluidities (lower measured torque) of the pastes. The torque
maximum immediately after starting of measurement is significantly lower if sodium
sulphate instead of potassium sulphate was added (compare Figs. 2a and 2b). By

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increasing the amount of alkali sulphate the ionic strength of the pore solution is
increased. According to Flatt 19 this might be a cause for a stronger flocculation, i.e. lower
fluidity of the paste. If the low fluidity of the paste in the presence of potassium sulphate
originated purely from an increase in the flocculation state due to the increased ionic
strength of the pore solution, one should expected the same loss in fluidity of the paste
when sodium sulphate is added. The present results show that this is not the case and an
additional factor must have an important impact on the cement paste fluidity (fluidity
loss).
Investigations of the cement paste microstructure by ESEM-FEG clearly show that

long prismatic crystals appear after increasing the amount of potassium sulphate in
cement paste. The dimensions of these crystals are in the micrometer range, i.e. approx.
2-10 !Jill long and 0.25- 0.5 ~m wide (Fig.9b). This typical morphology and results of
XRD-Rietveld analysis indicated that those crystals are syngenite. No crystals of
syngenite were observed in cement pastes with increasing sodium sulphate content
(Fig.9c).
Results of the determination of syngenite content by XRD-Rietveld analysis are

listed in Figure 7 .The data clearly show that the increase of the potassium sulphate
concentration causes a higher content of syngenite in all cement pastes. Comparing the
rheological measurement and XRD-Rietveld-analysis indicates that the fluidity of the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
cement paste is significantly influenced if the syngenite content exceeds approx. I %.

The added amount of 0.12 M and 0.18 M K2 S04 is similar to the potassium sulphate
content found in ordinary cements (Tab. 3).
Effect of Alkali Sulphate on the Fluidity of Cement Pastes with Superplasticizers
The content of syngenite that was formed after 10 minutes of hydration in the
presence of superplasticizers was determined by XRD-Rietveld analysis. It can be seen
that the type of superplasticizer influences the syngenite content in cement pastes
specifically (Fig. 7). Especially PCI (superplasticizer for ready-mix application)
decreases the syngenite content significantly. At the same time, compared to PC2 and
reference pastes, PCl achieves relatively high fluidification at all levels of potassium
sulphate addition (Figs. 2a-5a). These data show that in the presence of syngenite the
fluidity of PC-containing cement pastes is decreased.
It is known that due to the increasing concentration of sulphate ions in the cement
pore solution, the adsorption ofsuperplasticizers is decreased6• 12 • According to Yamada6
the fluidity of cement paste with PC-type superplasticizers is diminished by addition of
sodium sulphate. Nawa 12 has reported that sodium sulphate increases the fluidity ofPNS
containing cement pastes due to inhibited adsorption (competitive adsorption). Kim et al.5
determined an optimum content of soluble alkalis in cement that results in a minimal
fluidity loss. These results are confirmed by the data presented in Figs. 6, 2b-5b and
extended by results in Figs. 2a-5a: there it is obvious that the decrease in fluidity due to
increased sodium sulphate addition is much less than for potassium sulphate addition.

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It was demonstrated for the potassium sulphate containing reference samples that the
reduced fluidity is caused by syngenite formation. Thus it is concluded that in the
presence of superplasticizers and potassium sulphate there are two factors affecting the
fluidity of cement pastes: the competitive adsorption and the formation of long prismatic
syngenite crystals.
Since no syngenite or equivalent (sulphate consuming) mineral is formed if sodium

sulphate content of cement pastes is increased, the influence of the higher sulphate
concentration only, and following diminished SP adsorption (competitive adsorption), on
fluidity is evaluated (Figs. 3b-5b). The effect of both syngenite formation and
competitive adsorption can be seen in Figs. 3a-5a, where the content of potassium
sulphate was increased. It is obvious, that the addition of 0.18 M Na2 S04 solution and
lower molarities have a negligible impact on the fluidity of cement pastes with all studied
PC-type superplasticizers. Whereas addition of potassium sulphate decreases the fluidity
of PC containing cement pastes significantly.
Due to the low alkali content, the investigated cement is incompatible with the PNS-
type superplasticizer; this results in a high fluidity loss of the paste (Fig. 3b: OM Na2S0 4).
After the addition of 0.12 M Na2 S04 and 0.18 M Na2 S0 4, the fluidity of cement paste
with PNS was increased. The results shown in Fig. 3b are in accordance with previous
studies (5, 6 , 12). In the presence of syngenite the gain in fluidity of PNS-containing
paste is generally lower (Fig. 3a). During the first 60 minutes of hydration, at highest
molarity of mixing water (Fig. 3a: 0.29 M K2 S0 4), the fluidity of the paste is even
decreased as compared to the reference sample without superplasticizer. This loss in
fluidity can definitely be attributed to high rates of syngenite formation.
As shown in Fig. 6, the investigated PC-type superplasticizers are less adsorbed

on the cement surface than the superplasticizer based on PNS (at the same dosage of 1.5
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
%). Addition of potassium sulphate causes a decrease of superplasticizer adsorption in all
investigated samples. Comparison of PC! and PC2 adsorption shows that at higher
sulphate content, adsorption ofPCl is more influenced by potassium sulphate than PC2.
Change of the superplasticizer adsorption on cement particles was not investigated in

connection with the increase in sodium sulphate content. But according to previous
studies (6, 12) similar trends as for potassium sulphate addition can be expected.
The experimental results presented by Yamada6 and others 2• 13 • 14• 15 demonstrated a

correlation between quantity of adsorbed superplasticizer and fluidity of cement paste
(the higher the adsorption- the higher the fluidity). Results of the present investigation
show that despite similar adsorption behaviour of PC 1 and PC2 the fluidity of cement
pastes containing PC! is higher. Thus it is deduced that for the investigated PCs the
fluidity is significantly influenced by the length of side chains, i.e. the steric effect.
XRD-Rietveld analysis was furthermore carried out to determine, whether the C3A
consumption is affected by alkali sulphate addition. Therefore after 10 minutes of
hydration the C3A content in cement pastes was determined (Fig. 8). The graph in Fig. 8

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276 Kucerova and RoSter
shows, that the addition of potassium sulphate did not cause a significant change in C3A
consumption in cement pastes. This indicates that in the present study the most important
factor affecting the rheological behaviour of cement pastes with potassium sulphate is the
quantity of syngenite.
In our microstructural investigations of the early hydration by ESEM - FEG,

significant changes in the morphology of syngenite or ettringite due to the presence of
polymers were not observed. The microstructure of cement pastes containing
superplasticizers was similar to the microstructure presented in Fig. 9. But, in comparison
to cement pastes without superplasticizers the surface of cement particles was less
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
covered by hydration products if superplasticizers were present (Fig. 9d). Anyway,

differences in the syngenite quantity were documented by XRD-Rietveld analysis.
Fig. 10 illustrates the model for the rheological behaviour of cement pastes in the
presence of long prismatic hydrate phases (like syngenite or secondary gypsum). It is
known 16• 17 that the long prismatic crystals rotate into the shear direction in simple shear
conditions. Depending on the crystal asymmetry the particles reorient to the shear
direction in preference (high crystal length/diameter ratio) or rotate infinitely
(axisymmetric particles) during continuous stirring. The alignment of long prismatic
crystals into the shear flow is accompanied by gain in fluidity. Considering the model in
Fig. 10 it is possible to explain why the high decrease in fluidity of cement pastes with
high potassium content, which occurs immediately after addition of mixing water, can be
overcome by intensive stirring.
CONCLUSIONS
The results show that for a complete understanding of the action of superplasticizers
the amount and type of alkali sulphate, and the respective hydration products and their
morphology, have to be considered. It was shown, that syngenite formation is a factor
that has a marked influence on fluidity of cement pastes with higher content of potassium
sulphate. The amount of syngenite formed is specifically influenced by the presence of
superplasticizers. The increase in syngenite content results in a decrease of the cement
paste fluidity in the first minutes of hydration. The gain in fluidity during continuous
stirring is related to the subsequent alignment of elongated crystals into the shear
direction.
ACKNOWLEDGMENTS
The experiment was fmanced by GA CR # I 03/04/0668: "Correlation of

microstructure and prediction of long-term changes in stability of high-value composite
materials with defined properties" and funds of F.A. Finger-Institute for Building
Material Science at the Bauhaus-University Weimar (Germany).

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REFERENCES
1. Flatt, R. J., 2004, "Towards a prediction of superplasticized concrete rheology,"

J Mat. Struct,. V. 37, No. 269, pp. 289-300.
2. Jolicoeur, C.; Simard, M.-A., 1998, "Chemical Admixture-Cement Interactions:

Phenomenology and Physico-chemical Concepts," Cern. Caner. Camp., V. 20,
pp. 87-101.
3. Gartner, E.M.; Young, J.P., Damidot; D.A., Jawed I., 2000, "Hydration of
Portland Cement" in Bensted, J.; Barnes, P., Structure and Performance oj
Cements. 2nd Edition, E+FN Spon, pp.57-139. ISBN 0-419-23330-X.
4. Chandra, S., 2000, "Properties of concrete with admixtures," in Bensted, J.,

Barnes, P., Structure and Performance of Cements, 2nd Edition, E+FN Spon,
pp. 150-156. ISBN 0-419-23330-X.
5. Jiang, S.; Kim, B.-G.; Aitcin, P.-C., 1999, "Importance of adequate soluble
alkali content to ensure cement/superplasticizer compatibility", Cern. Caner.
Res, V. 29, pp. 71-78.
6. Yamada, K.; Ogawa, S.; Hanehara S., 200 I, "Controling of the adsorption and
dispersing force of polycarboxylate-type superplasticizer by sulphate ion
concentration in aqueous phase", Cern. Caner. Res, V. 31, pp. 375-383.
7. Stark, J.; Wicht, B., 2000, Zement und Kalk. Der Bausta.ff als Werkstoff, I st
Edition, Basel; Boston; Berlin: Birkhauser, ISBN 3-7643-6216-2.
8. Bensted, J., 2000, "Gypsum in cements", in Bensted, J.; Barnes, P. Structure

and Performance of Cements, 2nd Edition, E+FN Spon, pp. 150-156. ISBN 0-
419-23330-X.
9. Kurdowski, W; Grzeszczyk, S, 1997, "The influence of K2S04 on action of

superplasticizers and properties of cement paste and mortar", In A. Nonat (Ed.)
Hydration and Setting - Why does cement set? An interdisciplinary approach,
Proceedings of the second international RILEM workshop, Dijon, RILEM
Publications S.A.R.L. Cachan Cedex, pp. 403-417
10. Tattersall, G. H, 1955, "The rheology of Portland cement pastes", Brit. J Appl.
Phys., V. 6, pp. 165-167.
11. Yang, M.; Neubauer, C.M.; Jennings, H.M., 1997, "Interparticle potential and
sedimentation behaviour of cement suspension - Review and results from
paste", Advn Cern Bas Mat, V. 5, pp 1-7.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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12. Nawa, T.; Eguchi, H.; Hukara, Y., 1992, "Effect of cement characteristics on the
fluidity of cement paste containing an organic admixture", in 9'h International
Congress on Cement Chemistry, New Delphi, pp.579-603.
13. Uchikawa, H.; Hanehara, S.; Shirasaka, T.; Sawaki, D., 1992, "Effect of
admixture on hydration of cement, adsorptive behavior of admixture and fluidity
and setting offresh cement paste", Cem Caner Res, V. 22, pp. 1115-1129.
14. Collepardi, M. et a!., "Influence of polymerization of sulfonated naphthalene

condensate and its interaction with cement" In Developments in the use of
superplasticizers. ACI SP-68. Ed V.M. Malhotra, pp. 485-498.
15. Flatt, R. J.; Houst, Y.F., 2001, "A simplified view on chemical effects
pertrubing the action of superplasticizers", Cem Caner Res, V. 31, pp. 1169-
1176.
16. Jeffery, G.B, 1922, "The motion of ellipsoidal particles immersed in a viscous
fluid". Proe. R. Soc. London Ser. A, V.l02, pp. 161-179.
17. Goldsmith, H.L., Mason, S.G., 1967, "Chapter 4. The Microrheology of

Dispersions," in F.R. Eirich, ed., Rheology: Theory and Applications, VA,
Academic Press, NY.
18. Ailcin, P.-C., 1998, High Performance Concrete.!" Edition, E&FN SPON,
London.
19. Flatt R. J., 2004, "Dispersion forces in cement suspensions", Cem. Caner. Res,
v. 34, pp. 399-408.
Table 1 • Chemical composition of cement CEM I 52.5 R ·given in wt. o/<>l
CaO Si02 AhOJ FC!03 K20 Na20
66.0 22.9 4.0 1.3 0.66 0.23
K20•ol Na20•ol S03 CaO&ee MgO Blaine
0.4 0.06 3.1 0.0 0.6 5170cm2/g
Table 2 - Mineral phase composition of cement determined by XRD-Rietveld (given in

wt.%).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Table 3 - Content of K 2S04 resp. Na2S04 (in brackets: respective amount of water
soluble Kz0/Na20) in laboratory cement pastes (addition of potassium I sodium sulphate
to the mixing water).
Concentration of added
solution ofK2S04 or Na2S04 OM 0.12M 0.18M 0.29M
l(mol!ll
KzSO. (K20,.1) content in 2.74
0.74 (0.40) 1.57 (0.85) 1. 94 (1.05)
cement in wt.-% (1.48)
Na2SO• (Na20,.1) content in 1.15
0.09 (0.06) 0.53 (0.35) 0.76 (0.50)
cement in wt.-% (0.76)
T able 4 - Mixing protocol of cement pastes (preparation for viscometer measurement)

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
s~ _]lrocedure duration
1. cement added to water or potassium/sodium sulphate solution <10 s
containing superplasticizer
2. mixing in laboratory mixer according EN 196-1 by 140 rpm 60s
3. stop for cleaning 30 s
4. mixing by 140 rpm 120 s
TblSCharac
a e . . of superpJasllctzers
tenzatton 1·· -
Description PC1 PC2 PNS
Naphthalene
Type Polycarboxylate Polycarboxylate sulphonate
Formaldehyde
Backbone chain Polymetbacrylic acid --
Side chain Metboxypolyetbylenglycol --
Connection between
Ether --
backbone and side chain
COO'/etber 3.5 8.0 --
Molecular weight of side
chains
Low High --
Solid content (wt.- %) 30
Application Ready-mix Precast Ready-mix
~o.--,---,--f-:~P~C~1_f0~M~~~S~0~4--~-~~-~PC~1_no1,1RBMMK~;S~0~4
~··~••,!---+----i ........ pc2_o M ~so4 · ... PC2_0,1BM ~S04
200
e
E
1so ··.. ·· ..
~ •• ---NSF OM~S04 . .,. NSF_0,1BM~S04
~ 160 ~~·• .....,~ ••
gE 140
120
\\.'·
.
~.
~ 100 H .'··;:-r-- - .._.~s;_ ! ---
'·f~
"'
~ :BO
20
c___ \ \ . ·....
\-.._ ·..
\..._-.......;~:i ...
•
··.:-:-.._
.. ..~ ....
........... ........
0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8
superplasticizer dosage %
Fig. 1- Effect of superplasticizer dosage on the torque after 30 minutes hydration;

without (oM) and with (0.18 M) addition of K2 SO 4 .

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280 Kucerova and RoSier
300
270
.,.I ••o \--0.18 M

1 2f0
K2so.
180
150
•""-
~
-0.12M
K~SO,
-~MK,S~
tlme(mln
20 40 00 80 100 120
Fig. 2a- Increasing K,SO 4 content, without addition of SPs. The torque in the cement
paste with 0.29 M K,S0 4 solution is out of measurement range (>)oo Nmm).
300
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
270
1240 -0.12M
i 210
-0.29 N
Nazsf. - OM
N~
Na,SO,
180 ~ Na,s\o,
~
160 Ume(ml~)
20 40 60 100 120
Fig. 2b -Increasing Na,S04 content, without addition ofSPs.
150
120
My
--- ---
-0.2811
i 00
K2 S0 4
1
i """""""'
00
I i~:o~
•• -o.u_M"
K2so ..
0 lme (ml~)
• •• •• •• •• 100
•••
Fig. 3a- Increasing K2504 content and addition of PNS.
Fig. 3b- Increasing Na,SO content and addition of PNS.

4
Figs. 2-5- Viscometric measurements of cement pastes fluidity (expressed as
torque): influence of the alkali sulphates addition on the fluidity during.the first
2 hours of cement hydration at constant rotation speed of the vessel (6o rpm).

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150
:'-o::N.
120
-o.2eM
K,$0~
30 - K.SO
20 40
-0.12_1#"
K~o.
80
-o~A Kti04
80
time(mln)
100 120
Fig. 4a- Increasing K2 S0 content and addition of PC1.

4
150
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
120
Ii!:. eo
j eo
-o.29M
! Na~o.
-o.12M
/Na2so. N~;8o~
-
30
-N~% tlme(mi':l)
20 40 60 80 100 120
Fig. 4b- Increasing Na 2 S0 content and addition of PC1.

4
120-H.----------------j
}•o~~~~--~~~~~~~~~
"'" -OM K,SO
}eo ~::::===::::::;5~~
0~-~-~--~-~-~~~
0 20 40 60 80 100 120
Fig. sa- Increasing K2 SO 4 content and addition of PC2.
180,---------------------.
I •o
i 60~:::::::;~~~
tlme(mln)
0~--~--~----~--~--~~~
0 20 40 60 80 100 120
Fig. sb - Increasing Na 2 SO content and addition of PC2.

4
Figs. 2-5- Visco metric measurements of cement pastes fluidity (expressed as
torque): influence of the alkali sulphates addition on the fluidity during the first
2 hours of cement hydration at constant rotation speed of the vessel (6o rpm).

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282 Kucerova and RoSter
100
90
80
70
0~
I: 60
0
i.
... 50 --·- f-·· --
~ 40 '-·· -- 1-
~ 30
20
Pc-'11 0.4%
Pczl.j
1-
I- - 1- -- 1- :--
10
0.4~ PC 1 1.5% 1[ PC 2 1.5% l[ NSF 1.5%
0
0 0.18 0 0.18 0 0.12 0.18 0.29 0 0.12 0.18 0.29 0 0.12 0.18 0.29
K2S04 concentration of mixing water (M=molesflitre]
Fig. 6- Superp!asticizer adsorption on cement surface after to minutes of hydration

in dependence of K2 SO 4 concentration. Dosages of PCt and PC2 were 0-4% (tess than
the saturation point) and 1.5% (more than the saturation point).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~ 2,0
~
E
fii
1.5
~ 1,0 .J-----------·--
:0
0
~ 0.5
0,0
0 0.12 0.16
K2S04 concentration of mixing water [molesll~re]
Fig. 7- XRD-Rietvetd analysis: Syngenite content in cement pastes with K SO after

2 4
10 minutes hydration.

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`,,`,`,,`---
•without SP tllPC1-1.5% OPC2-1.5% 0 PNS-1.5% '
0 0~2 Q18
K2S04 concentration of mixing water [moles/litre]
Fig. 8- C3A content in cement pastes after 10 minutes hydration. C A content in the
3
unhydrated cement was 7-5 %.
Fig. 9a- Reference cement paste without addition of alkali sulphate: short prismatic
ettringite (approx. 500 x 200 nm) covers cement particles.
Fig. 9b- Addition of 0.18 M K,S0 : long prismatic syngenite and short prismatic
4
ettringite on cement particle.
Figs. 9a-d- ESEM micrographs of cement pastes, 10 minutes hydrated

(25 kV, approx. 8o% humidity)

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Fig. 9c- Addition of 0.29 M Na 2 50 4 : short prismatic ettringite, microstructure similar

to reference (Fig. 9a).
Fig. 9d- Cement paste with PNS and without addition of alkali sulphates: short
prismatic ettringite, microstructure similar to reference (Fig. 9a).
Fig. 10- Rotation of long prismatic crystals like syngenite into the shear direction
(indicated by arrows).
Figs. 9a-d- ESEM micrographs of cement pastes, 10 minutes hydrated

(25 kV, approx. 8o% humidity)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-19
Adsorption of Lignosulphonates
on Cement and the Hydration
Products of Cements
by B.O. Myrvold
Synopsis: The adsorption of sodium lignosulphonate onto cement was investigated.

The cement has either been pre-hydrated or hydrated with the lignosulphonate
present. The pre-hydrated cement particles grow with time, thus a larger surface is
created and the plateaus in the adsorption isotherms increase. With lignosulphonate
present there is hardly any growth of new surface. lt is found that, a lignosulphonate
that adsorbs strongly to the surface causes, less retardation than weakly adsorbed
lignosulphonates. This can be explained by different interactions with the different
minerals present.
Keywords: adsorption; cement; clinker; hydration products;

lignosulphonates
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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286 Myrvold
Bernt 0. Myrvold received his Ph.D in physical chemistry from the University of Oslo
(Norway). He is a senior researcher at Borregaard Industries. His research interest
includes the structure of lignosulphonates, and their structure property relationships. He
has previously worked on the structure property relationships of organic compounds for
electro-optical flat panel displays.
BACKGROUND
Lignosulphonates are widely used plasticizers, or dispersing agents, in the

concrete industry. Their mode of function is not well known. Lignosulphonates also
retard the setting of concrete to a smaller or larger degree. This is not only due to the
sugar components, also highly purified lignosulphonates retard to some extent. This
retarding effect can be beneficial e.g. in oil well cementing, or when concrete has to be
transported longer distances in a warm climate, but particularly in colder environments it
restrict the use of lignosulphonates as plasticizers, or superplasticizers.
There have been several investigations of the interactions between

lignosulphonates and cement or cement minerals [1-20]. Only a few of the studies uses
sodium lignosulphonates [9-12, I 8]. Steric interactions [2 I] and electrostatic repulsion
[20] has been suggested as the mechanism responsible for the stabilisation of the
dispersion. Irrespective of the mechanism the first step will be for the lignosulphonate
molecule to adhere to the particle surface. This adhesion can be probed directly with
adsorption isotherms. There has only been few studies of this kind [1-5,8, 22]. Most of
these studies use calcium lignosulphonates.
EXPERIMENTAL
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Substrates
The cement used was CEM I 52.5N ordinary Portland cement
Cement hydration products were obtained by shaking a mixture of water and

cement w/c ratio 0.5 for the given time. The reaction was stopped by adding methanol.
The methanol water solvent was filtered of through a 3 J..lm millipore filter. The product
was washed with several aliquots of methanol to remove all the water. The products were
dried at 65 °C for 30 minutes. These hydration products were made fresh for each study.
Adsorption isotherms
1 gram of substrate was shaken with 20 ml of lignosulphonate solution of known

concentration, for the required time. Normally a time of20-25 minutes was used, but
some were shaken for as long as I 6 hours. The solution was filtered off a 0.22 micron
millipore filter. The solution was diluted with NaOH solution (pH >12). The UV spectra
were recorded. The remaining lignosulphonate concentration was determined by
comparing the adsorbance at 284 nm with known standards. Fresh standards were made
each day.

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The consumed amount (r) was calculated as the difference between the initial
concentration (C.,) and the final concentration (C,). The consumed amount was
normalised by the amount of substrate used (m,ub).
r = (C,,-C,)*V/m,ub" (I)
Vis the volume of the solution.
(2)
With m,ub in grams, C,, and C, in ppm and a fixed volume of 20 ml the factor 50
gives r in mg lignosulphonate pr. gram substrate.
r was plotted as a function of C,. In a reactive system like cement C, is not a true
equilibrium value.
There were a few slight variations to the procedure above. With the hydrated
clinker phases, I 0 ml of a lignosulphonate solution of twice the final strength was used to
keep the total volume at 20 ml.
Lignin modification
Most of the studies presented here were performed with the same batch of high
molecular weight softwood sodium lignosulphonate. (Mw = 47.8 kDa, M, = 5.8 kDa,
reducing sugar 0.4%, Ca2+ 0.01%)
The high molecular weight lignosulphonate was partially desulphonated by

heating to 170 °C at pH 10.7 for I hour. These products were esterified and the phenolic
hydroxyl groups partially blocked by reaction with dimethylsulphate.
Lignosulphonate (350 gr/1) was adjusted to pH 11. Dimethylsulphate was added.

The amount of dimethylsulphate was chosen to give different degrees of blocking of the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
phenolic groups. The amount of phenolic hydroxy Is left was determined by standard UV
spectroscopic methods [23], while the carboxylic acids were determined by conductivity
titration [24].
Isotherms
In all the isotherms presented here we use the term "consumed" about the
reduction of lignosulphonate amount in the solution. There might be several mechanisms
operating. There might be true adsorption where the lignosulphonate interacts strongly
with the surface. There are several possible isotherms, but the most common types will
all have a plateau value where the surface is covered by one monolayer of the solute.

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288 Myrvold
There might also be precipitation where the lignosulphonate interacts with
cations in the solvent to form insoluble complexes that precipitates. In this case there are
no direct interactions between the substrate and the lignosulphonate, but the substrate
provides the ions that cause precipitation. For these cases there will be no upper limit on
the amount of lignosulphonate consumed and the amount consumed will be a linear
function of the amount added.
There is also the intermediate situation of the cation assisted adsorption [25].
Here the substrate provides ions that, partially or fully cancels the charges in the
lignosulphonate molecule. These new ion pairs adsorb to the surface. There will be no
adsorption in the absence of the ions. This is different from the precipitation, and the
lignin will not be consumed without a substrate to adsorb to. There will be a plateau
value where the surface is fully covered by the lignosulphonate.
For cement we also have the possibility that the sulphonate groups of the
lignosulphonate takes part in reactions (probably replacing sulphate). This will bury the
lignosulphonate inside the newly formed reaction products.
In most of the isotherms we plot the consumed amount in mg lignosulphonate pr

gram of substrate vs. the concentration of lignosulphonates remining in the solution. In a
reactive system that clearly changes over time, this can not really be called an
equilibrium concentration, though. As the surface areas for the different substrates are
unknown we can not compare the plateau values directly. In some cases we have also
shown the isotherms as fractional coverage which is the consumed amount divided by the
consumed amount at the plateau value. This gives a better indication of the strength of the
interactions in cases where we compare different surfaces.
The Langmuir isotherms assumes a reversible process where both adsorption to

the surface and desorption from the surface occurs at the same time [26). The energy of
interaction is independent of the surface coverage. The rate of desorption (R,) is given by:
(3)
where 0 is the fractional coverage and k, is a rate constant. Thus the rate of desorption is
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
proportional to the amount adsorbed. The rate of adsorption (R,) is given by:
R, = k, (l-0)c, (4)
where c is the concentration in solution and k, is a rate constant. At equilibrium the two
rates are the same.
R, = Rd or k, (l-0)c = kd 0, (5)
rearranging we obtain
be= 0/(1-0) or 0 =be/( I +be), (6)

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where b = k/kd and can be treated as an adjustable parameter. The larger the value ofb,
the steeper the isotherms will rise, and the stronger the interactions between the surface
and the adsorbate will be. We find the Langmuir isotherms describe the shape of the
experimental adsorption isotherms well (Figs. I b, 2 and 4). This is unexpected since no
desorption process is observed, one of the underlying assumptions thus seems to be
violated. A good fit to the Langmuir isotherm has also been found previously for calcium
lignosulphonates adsorbed onto cement and several cement minerals [8]. The good fit to
the Langmuir isotherms also seems strange as the surface coverage found corresponds to
much more than a mono layer coverage [6, 8, 13]. However, the use of the constant b is
still useful to parametrize the data.
To obtain isotherms, solutions with varying concentrations oflignosulphonates

are in contact with the cement, or other substrates. The lignosulphonates retards the
reactions of cement. This retardation is dependent on the lignosulphonate dosage (see e.g.
[14]). The same effect is seen for the C4AF [17], the C,A-gypsum and C4 AF-gypsum
systems [19]. Thus the reactions might be different in the various samples. This effect has
been seen for C,S where there is some adsorption at low calcium lignosulphonate
concentrations, none at a higher concentration where the hydration is suppressed, and
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
some again at the highest concentrations where the system is well dispersed [2, 15]. The
reaction will proceed faster in the samples with low concentrations of lignosulphonate
than in samples with much lignosulphonate. This could lead to abnormally shaped
isotherms. The effect will depend on the relative affinity of the starting material and
reaction products towards the lignosulphonates.
Cement isotherms
Two sets of isotherms are shown in Figure I and 2. In the first (Ia) the cement
has been hydrated for the given time before the lignosulphonate solution is added. The
solution and prehydrated cement has been in contact for 25 minutes. We could not
prehydrate cement for more than 8 hours due to the hardening. We clearly see how the
adsorption rises strongly with time, except for the product hydrated for 1 hour, where
there is a small decrease. It has been shown that hydrated C,A and C4AF [1] consumes
less lignosulphonates than the unhydrated material. C,A and C4AF also are reported to
adsorb less calcium lignosulphonates with longer contact times [27], but then contact
times of 12-24 hours were used. On the other hand the hydration of C3S/C 2S proceeds so
slowly that it has hardly started at 1 hour [27]. It takes about 4 hours before these
minerals reacts to any significant degree [9). This can explain the small decrease when
the aluminate phases are converted to their hydration products, while strong rise is due to
the new surfaces created by the hydration of the silicate phases. A new and larger surface
is formed and thus the plateau value increases, strongly. In Figure I b the data is plotted as
fractional coverage. The initial slope of the adsorption isotherms are the same in all cases
with prehydrated cement. Thus it seems reasonable to assume that a lot of new surface is
created, but the nature of the surface is the same. The material formed is the C-S-H phase
A value of 4.0 10-2 ppm- 1 was found for the constant bin eq. 6.

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290 Myrvold
In the second set of data (Figure 2) the lignosulphonate solution has been in
contact with cement for the time shown. A very small increase in the amount of material
adsorbed was observed. The lignosulphonate clearly interferes with the creation of the
new C-S-H surface. We also noted that there was no problem in obtaining good isotherms
for 16 hours contact time, much longer than the time taken for hardening without
lignosulphonates present.
The differences between the two sets of isotherms clearly show that the surface
grows in contact with water, but that this growth is stopped very efficiently with
lignosulphonates present. The reactions between water and the cement minerals release
ions into the solution. These ions might modify the properties of the lignosulphonates.
However, for the pre-hydrated cement (Figure 1) these ions will be washed away when
the water is sucked off, and the hydrated cement isolated. There will thus be less ions in
this system. The larger adsorption can thus not be due to more precipitation due to the
ions. In the system where the cement is in contact with both the water and the
lignosulphonate at the same time, all the ions leached out will also be available to interact
with the lignosulphonate in solution. Still, this does not give a higher consumption.
In Figure 3 the r values for the adsorption plateaus as a function of time are
compared. The growth of new surface is much smaller when lignosulphonate is in contact
with the cement.
Modified lignosulphonates
Figure 4 shows the adsorption oflignosulphonates where the carboxylic groups

are partially esterified and part of the phenolic groups are etherified (see Table 1 for data
on the compounds). We have plotted the curves as percentage of full coverage. The
substrate is non-hydrated cement. The two lignosulphonates with least phenolic groups
also show the strongest adsorption, e.g. the steepest curve.
When we compare the slope of the curve with the setting times in Table 1 it can be seen
that, the lignosulphonates that adsorbs strongest gives the shortest setting times, e.g. the
least retardation. When all the lignosulphonate is adsorbed to the aluminate phases it will
be Jess left to interfere with the hydration of the silicate phases, and thus a lower
retardation.
Table 1 summarises the properties of the different modifications.
In Table 1 we have indicated the number of the different negatively charged

groups (at the pH of cement pore water}, and their total charge. The surface charge is the
total charge of the lignosulphonate in milliequivalents pr gram multiplied by the plateau
value in mg/g. The total charge on the lignosulphonate does not determine the adsorption.
The adsorption mechanism is more complex than just the negatively charged
lignosulphonate neutralizing charges on the surface.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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DISCUSSION
Cement consists of several minerals and the system is thus highly inhomogenous
When suspended in water the cement minerals will partially dissolve and the surfaces
gain a charge (as measured through their zeta-potential). The charge is different for the
different clinker minerals. The C,A!C,AF phases are positively charged, while the
C,SIC,S are negatively charged [20].
The lignosulphonates adsorb to the positively charged areas of the surface. This
cancels the positive charges on the C,AIC,AF parts of the surface or even reverses them
to negative charge. This explains why the dosages of lignosulphonate used in concrete are
much smaller than that needed for full surface coverage. Only the positively charged
areas need to be covered. It also explains why cement that has a zero or negative zeta-
potential will gain a more negative surface potential when lignosulphonates are adsorbed
[16, 21]. The measured zeta-potential for cement is an average over the positive and
negative areas. When lignosulphonates are adsorbed the negative areas stay unchanged
while the positive areas also becomes negatively charged, the average will thus become
lower. It is agreed in the literature that lignosulphonates interact strongly with the pure
aluminate phases [3, 4, 10,11].
Not all of the lignosulphonate adsorbs to the C,AIC,AF part of the surface. Some
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
remain in solution. The lignosulphonate left in solution will interact with the ions
dissolved into the pore water. These ions will partially cancel the negative charges in the
lignosulphonate molecule due to ion pairing. The lignosulphonate with cancelled charges
can adsorb or precipitate onto the C,SIC,S parts of the cement surface. This will interfere
with the normal hydration of the surface and causes the retardation of the setting.
We see that blocking the phenolic hydroxyls give a stronger adsorption to

cement. When the adsorption isotherms becomes steeper there is less material left in
solution to interfere with the hydration of the silicate phases, which takes place at a later
stage. Consequently the retardation etTect is reduced.
CONCLUSIONS
During hydration the surface area of the cement grains grow through the formation of the
C-S-H phase. The growing surface areas are seen by an increased plateau value for the
adsorption isotherms. However, the slopes of the adsorption isotherms remain constant,
suggesting that the surfaces formed have the same characteristics. When lignosulphonates
are added, ions that are released by the rapid hydration of the C,AIC,AF phases interact
with and modify the lignosulphonate. The modified lignosulphonate covers the silicate
phases and there is a very slow growth of new surface area when the lignosulphonate is in
contact with the cement.
For the best dispersing effect we should have a lignosulphonate that adsorbs strongly to
the aluminate phases. As much lignosulphonate as possible should be consumed by the
aluminate phases, as the excess lignosulphonate will interact with the ions released and
then interfere with the hydration of the silicate phases.

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292 Myrvold
REFERENCES
1. D. R. Rossington and E. J. Runk, Adsorption of Admixtures on Portland cement

hydration products, J. Am. Ceramic Soc. 51(1) (1968), pp. 46-50
2. V. S. Ramachandran, Interaction of calcium lignosulfonate with tricalcium silicate,

hydrated tricalcium silicate, and calcium hydroxide, Cement Concrete Res. 2 (1972)
pp. 179-194
3. V. S. Ramachandran, Elucidation of the role of calcium lignosulfonate in the hydration

ofC,A, 71h International Congress on the Chemistry of Cement, Paris (1980) pp. 535-540
4. V. S. Ramachandran, and R. F. Feldman, Effect of calcium lignosulfonate on

tricalcium aluminate and its hydration products, Materiaux et Constructions 5(26) (1972),
pp. 67-76
5. S. Monosi, G. Moriconi, M. Pauri and M. Collepardi, Effect of retarding admixtures on

the Portland cement hydration,, 8th International Congress on the Chemistry of Cement,
Rio de Janeiro (1986) pg. 130-135
6. F. M. Ernsberger and W. G. France, Portland cement dispersion by adsorption of

calcium lignosulphonate, Ind. Eng. Chern. 37(6) (1945) pp. 598-600
7. N. Kawada and M. Nishiyama, Action of calcium lignosulfate upon Portland cement

clinker compounds, Rev. 14th General Meeting Japan Cement Engineering Association,
Tokyo (1960) pg 25-26
8. B. Blank, D. R. Rossington, and L. A. Weinland, Adsorption of admixtures on

Portland cement, J. Am. Ceramic Soc. 46(8) (1963) pp. 395-399
9. M. Y. A. Mollah, Wenhong Yu, R. Schennach and D. L. Cocke, A Fourier transform

infrared spectroscopic investigation of the early hydration of Portland cement and the
influence of sodium lignosulphonate, Cement Concrete Res. 30 (2000) pp. 267-273
10. F. Massazza and U. Costa, Effects ofsuperplasticizers on the C,A hydration, ih

International Congress on the Chemistry of Cement, Paris (1980) pp. 529-534
11. F. Massazza, U. Costa and A. Barrila, Adsorption of superplasticizers on calcium

aluminate monosulfate hydrate, ACI SP-68, Editor V .M. Malhotra 1981, pp. 449-514
12. B. 0 Myrvold, J. Gustafsson and K. Reknes, Adsorption studies on cement and

cement model compounds. II th International Congress on the Chemistry of Cement,
Durban (2003) pp. 217-226
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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13. V. Lorprayoon and D. R. Rossington, Early hydration of cement constituents with
organic admixtures, Cement Concrete Res. 11 (1981) pp. 267-277
14. V. S. Ramachandran, Einfluss von suckerfreien ligninsulfonaten auf die zement-

hydratation, Zement Kalk Gips 4 (1978) pp. 206-210
15. V. S. Ramachandran, Differential thermal investigation of the system tricalcium

silicate- calcium lignosulfnate- water in the presence oftricalcium aluminate and its
hydrates, Thermal Analysis 2 (1971) pp. 255-261
16. D. M. Roy and M. Daimon, Effects of admixtures upon electrokinetic pehnomena

during hydration of C,S, C,A and cement, 7th International Congress on the Chemistry of
Cement, Paris (1980) Septima pg. 242-246
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
17. M. Georgescu and I. Carazeanu, Influence de quelques additiefs fluidifiants sur le
processus d'hydratation et durcissement de 4Ca0Al,O,·Fe,0 3, Rev. Roumanine Chemie
40(10) (1995) pp. 983-992
18. S. Chatterji, Electron-optical and X-ray diffraction investigation of the effects of

lignosulphonates on the hydration ofC,A, Indian Concrete J. (1967) pp. 151-160
19. M. Michaux and E. B. Nelson, Flash-set behaviour of oil well cement slurries
containing lignosulphonates. 9th International Congress on the Chemistry of Cement,
New Dehli (1992) pg. 584-590
20. T. Sebok and 0. Straenel, Relationships between the properties of lignosulphonates

and parameters of modified samples with cement binders. Part II. Study of relationships
between molar parameters of lignosulphonates and characteristics of the samples tested,
Cement Concrete Res. 29 (1999) pp. 591-594
21. H. Uchikawa, S. Hanehara and D. Sawaki, Effect of electrostatic and steric repulsive
force of organic admixture on the dispersion of cement particles in fresh cement paste,
Proceedings 101h ICCC, Gothenburg (1997) paper 3iii001
22. F. M. Ernsberger and W. G France, Some physical and chemical properties ofweight-
fractioned lignosulfonic acid, including the dissociation of lignosulfonates, J. Phys.
Colloid Chern 52 (1948) pp. 267-276
23. Y.-Z. Lai, Determination of phenolic hydroxyl groups, pp 423-434 inS. Y. Lin and C
W. Dence (eds.) Methods in Lignin Chemistry, Springer Verlag (1992)
24. C. W. Dence, Determination of carboxyl groups, pp 458-464 in S. Y. Lin and C. W.

Dence (eds.) Methods in Lignin Chemistry, Springer Verlag (1992)

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294 Myrvold
25. C. Geffroy, J. Persello, A. Foissy, B. Cabane, and F. Toumilhac, The frontier between
adsorption and precipitation ofpolyacrylic acid on calcium carbonate, Rev. L'Institute
Franc. Petrole 52(2) (1997) pp. 183-190.
26. D. J. Shaw, Introduction to Colloid and Surface Chemistry, Fourth Edition,

Butterworth Heinemann, Oxford (1994) pp 128-130
27. I Odler and Th. Becker, Effects of some liquefying agents on the properties and
hydration of Portland cement and tricalcium silicate pastes, Cement Concrete Res. 10
(1980) pp. 321-331
Table I. A summary of tbe roperties o mo d'ified so d'tum il!nosutp

I b ooates
sample so3• COOH <I>-OH total Plateau Surface b Set
# # # charge value charge /ppm-' time/
# mg/g h
Mod-1 1.650.0 0.71 2.36 7.7 18.2 6.010' 8.3
Mod-2 1.650.0 0.61 2.26 8.0 18.1 3.5 10' 6.6
Mod-3 1.651.4 0.35 3.40 7.4 25.2 4.1'10' 5.6
Mod-4 1.651.1 0.16 2.91 7.0 20.4 3.810' 5.9
0 0
# m1lheqmvalents pr gram.
~
tJ)
20
.. .. lo1hour
E 15 .. 6 • "2 hours
"CC • • 4 hours
..''
CD c
E 10 D
•
:I
Ill
"• 0
• 0 0 16 6 hours
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
c 5- .. 8 hours
0
u I • None
0
0 200 400 600 BOO 1000
Concentration I ppm
Figure 1a --Adsorption of a high molecular weight softwood sodium lignosulphonate

to cement that has been prehydrated for the times given. There is a large growth in
maximum consumption.

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1.2.--------------------,
• 1 6 0 rJie o o •
$' 0.8 ~ rf'O
!; 11.•
~ 0.6 ..
c "
~ 0.4 "'
£o.d
200 400 600 800 1000
Concentration I ppm
'---------------- -- -
Figure tb --The adsorption of a high molecular weight softwood sodium

lignosulphonate to pre hydrated cement plotted as fractional coverage.
The strength of the interaction is the same in all cases.
12 1o 8 hours
~ 10 • ~ • . :~
""
"..
E •4 hours
'0
8-. ~ 1c 2 hours
a> '"D.
E 6
I
1.o.1 hour
:J
Ill 4
le.30 min
'
c
0
u 2 • 16 hours
0
0 100 200 300 400 500 600 700
Concentration I ppm
Figure 2-- The consumption of a high molecular weight softwood sodium

lignosulphonate that has been in contact with cement for the times given.
There is a very small increase in maximum consumption.
~
: 15
-g 10
i!0
.a 5- --with LS
-a- Without LS
<C
0 4 8 12 16
Time/hours
Figure 3-- The plateau values forthe different isotherms, as a function oftime.
Filled symbols are with lignosulphonate added initially. Open symbols are for
lignosulphonates added after the given delay. --`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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296 Myrvold
1.2 . - - - - - - - - - - - - - - - - - - - - .
6 • 0 •.to
a • ¢
.
§ 0.8
¢
..
8 0.6 ..
"ii ~ o Mod-1
6 0.4 0 ..
.. Mod-2
'iS oMod-3
I! 0.2
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
u.. • Mod-4
0
0 500 1000 1500
Concentration I ppm
Figure 4--The adsorption of modified lignosulphonates on cement. The less phenolic

hydroxy Is present, the stronger the adsorption will be.

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SP-239-20
A New High Performance Drying

Shrinkage-Reducing Admixture
by M. Masanaga, T. Yamamoto, T. Hirata, and T. Nawa
Synopsis: Cracking caused by autogeneous and/or drying shrinkage is one of the

most important factors that affects to the early deterioration of concrete structures.
In this study, the new high performance drying shrinkage-reducing admixture, NSR-1,
is introduced. The NSR-1 shows higher drying shrinkage-reducing ability with very
low dosage level compared with conventional drying shrinkage-reducing admixtures
(DSRA) without effecting other concrete properties.
Drying shrinkage-reducing mechanism of conventional DSRA is generally
due to reducing the surface tension of water in capillary pores. On the other hand,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
NSR-1, having hydrophobic groups, adsorbs on cement particles and is able to give
hydrophobicity on pore surfaces. As a result, NSR-1 reduces the interfacial tension
between pore surfaces and water in these pores, and can reduce drying shrinkage
effectively.
Drying shrinkage behavior was measured by mortar with W/C of 44%. At 28
days, the shrinkage strain of NSR-1 was 390 x 10·6 at dosage of 0.3% by mass of
cement, and those of conventional DSRA were 380 x 10·6 to 405 x 10·6 at dosage of
2.0% by mass of cement. The NSR-1 showed the same drying shrinkage-reducing
effect at a dosage of about one-seventh of the add it ion amount for the conventional
DSRA.
Keywords: adsorbtion; drying shrinkage; shrinkage-reducing

admixture; surface tension

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298 Masanaga et al.
Mari Masanaga is an Assistant Research Leader of Fine & Specialty Chemicals Research
Center, Nippon Shokubai Co. Ltd., Japan
Takashi Yamamoto is an Assistant Research Leader of Fine & Specialty Chemicals

Research Center, Nippon Shokubai Co. Ltd., Japan
Tsuyoshi Hirata is Nippon Shokubai Fellow and General Manager of Research Project,
Nippon Shokubai Co. Ltd., Japan
Dr. Toyoharu Nawa is a Professor at the Division of Solid Waste, Resources and
Geoenvironmental Engineering Laboratory of Eco-Materials and Resources, Hokkaido
University, Japan
INTRODUCTION
Recently, providing better durability to concrete structures is becoming a matter of

concern. Cracking caused by drying shrinkage is one of the most important factors for
concrete durability, so more effective drying shrinkage-reducing admixtures and methods
of reducing shrinkage are urgently required. Several drying shrinkage mechanisms for
concrete structures such as capillary tension, surface energy, disjoining pressure,
movement of interlayer water and others have been proposed. But it seems that these
mechanisms actually would combine each other to cause drying shrinkage [1]. Many
types ofDSRA have been developed according to the capillary tension theory [2-4]. Most
of the available DSRAs on the market are basically polyoxyalkyleneglycols or their alkyl
ethers. But DSRAs have the following problems that should be resolved.
·Dosage levels of more than I or 2% by mass of cement, are needed to provide
enough reduction in drying shrinkage, thus increasing costs.
·In some cases, the use of DSRA reduces compressive strength and resistance to
freezing and thawing.
In this paper, a new high performance drying shrinkage-reducing admixture, NSR-1,
which was developed according to different mechanisms from conventional DSRA is
introduced. The NSR-1, with hydrophobic and carboxy groups, shows higher drying
shrinkage-reducing effect which is derived from the adsorption ofNSR-1 molecules onto
cement particles.
EXPERIMENTAL
I) DSRA and other admixtures

DSRA and other admixtures used to evaluations are shown in Table I.
SRA-1, SRA-2 and SRA-3, the commercial drying shrinkage-reducing admixtures
(DSRA), have a polyoxyalkyleneglycohol chain in their basic structures. On the other
hand, NSR-1 that developed newly, is a hydrophilic polymer having hydrophobic groups
and carboxy groups which can adsorb onto cement particles.
The flowability and the air content of mortar, concrete, or both, were controlled
when necessary, by using water-reducing admixture (LIG-1 ), superplasticizer (PC-1) and
the air control admixtures (AE-1 and DEF -I).
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2)Measurements of the surface tension of DSRA in the cement filtrate
a) Measurement of the surface tension ofDSRA in the cement filtrate (A)
After stirring 400g of cement and 800g of water for 30 minutes, and filtrating with
5C filter paper, the cement filtrate (A) was obtained.
The surface tension was measured at 0.01, 0.05, 0.5, l.O and 5.0 mass% ofDSRA in
the cement filtrate (A) at 20 ± 3 °C by the duNouy method using a platinum ring.
b) Measurement of the surface tension ofDSRA in the cement filtrate (B)
1OOg of cement was added to 200g of the aqueous solution containing 0.2 mass% of
DSRA and stirred. Taking portions of the filtrate after 1 minute and 60 minutes stirring,
and filtrating them, the cement filtrate (B) was obtained. The surface tension of the
cement filtrate (B) was measured by the duNouy method mentioned above.
3) Measurement of the adsorption ratio ofDSRA on cement particles

The adsorption ratio of DSRA on cement particles was measured by total organic
carbon (TOC) measurement system. Samples for TOC measurement were obtained as
follow.
Ordinary portland cement (OPC: manufactured by Taiheiyo cement corp.) 100g and
200g of the aqueous solution containing 0.2 mass% of DSRA were stirred at 700 rpm.
About 20g of mixture was extracted at 5, 20 and 60 minutes stirring after adding OPC,
and placed for 5 minutes, then the supernatant solution of mixture was filtrated with 5C
filter paper and chromat filter (Chromatdisk 25A).
The adsorption ratio of DSRA on cement particles was calculated as follows.
Adsorption ratio(%)= {TCbl- (TCsam- TCcem)} X 100 I TCbl
TCb1 :amount oftotal organic carbon of solution containing 0.2 mass% ofDSRA
TCcem: amount of total organic carbon of cement filtrate
TCsam : amount of total organic carbon of DSRA sample for TOC measurement
4) Mix proportion and mixing method for mortar

Mix proportion of mortar is shown in Table 2.
OPC (manufactured by Taiheiyo Cement Corp.) and ISO standard sand
(manufactured by Japan Cement Association) were used. The air content of mortar was
adjusted to 7 ± 1 volume%, when necessary, by using the air control admixtures.
Mixing of mortar was carried out according to JIS R520 1 "Physical Testing Method
for Cement" by using a Hobart type mortar mixer.
Water, containing DSRA and other admixtures, and OPC were mixed for 30 seconds
at slow speed (rotation: 140 ± 5 rpm, revolution:62 ± 5 rpm), then ISO standard sand was
added over 30 seconds while mixing at slow speed. After that, the mixing speed was
changed to medium speed (rotation:285 ± 10 rpm, revolution:125 ± 10 rpm) and the
mortar was mixed for 30 seconds. Then, mixing was stopped 90 seconds. During the first
15 seconds of this interval, any mortar that may have been collected on the side of the
bowl was quickly scraped down into the batch. After mixing for an additional 60 seconds
at medium speed, the mortar was obtained for evaluation.
5) Measurement oflength change of mortar specimen

Measurement oflength change of mortar specimen (40 x 40 x 160 mm) was carried
out according to JIS All29-3-2001 "Methods of test for length change of mortar and

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300 Masanaga et at.
concrete- Part 3:Method with dial gauge".
Immediately after mixing, the mortar was poured into the mold, that had gauge
plugs attached on each of the opposite ends. Then, the mold was stored in a container,
sealed tightly therein and cured at 20 ± 3 oc for 2 days. After sealed curing, the cured
mortar was extracted from the retaining mold, and subsequently the mortar was cured
under water at 20 ± 3 oc for 5 days. Measurement of the length change of mortar
specimen was started after water curing.
6) Concrete formulation and mixing method

Table 3 shows the mix proportion of concrete. The concrete was mixed by 50 L dual
axles revolving-paddle mixer. Total mixing volume of concrete was 40 La batch.
Cement and aggregate were dry-mixed for 10 seconds. Then water, containing
DSRA and other admixtures, was added followed by 120 seconds of mixing.
Slump, air content, and setting time by penetration resistance of concrete were
evaluated. The spacing factor of the air voids was measured by Air Void Analyzer (AVA:
Germann Instruments NS), using 20 rnL mortar obtained by screening coarse aggregates
over 5 mm from the fresh concrete.
I) The surface tension of DSRA in the cement filtrate (A) (Method was shown in
experimental 2)-a))
The relationship between the concentration of DSRA in the cement filtrate (A) and
the surface tension is shown in Figure l. The surface tension of the cement filtrate (A),
containing SRA-3 could not be measured because SRA-3 did not dissolve in the cement
filtrate (A). The surface tensions of SRA-1 and SRA-2 in the cement filtrate (A)
decreased with increasing SRA concentration, and achieved constant values of about 40
mN/m at dosages of more than 1.0 mass%. On the other hand, that of NSR-1 achieved
constant value at 55 mN/m at dosages of more than 0.5 mass%. Comparing the surface
tensions of SRA-1 and SRA-2 with that ofNSR-1 at 1.0 mass%, the former were 37.0
mN/m (SRA-1) and 43.2 mN/m (SRA-2), and the later (NSR-1) was 55.7 mN/m. Hence,
the surface tension ofNSR-1 was higher than the others.
2) Adsorption behavior ofDSRA on cement particles

Relationships between elapse time and adsorption ratio of DSRA on cement
particles are shown in Figure 2. The surface tensions of cement filtrate (B) at I and 60
minutes after adding cement into DSRA aqueous solution are shown in Table 4.
As shown in Figure 2, SRA-1 and SRA-2 do not show any adsorption onto cement
particles even after 60 minutes. On the other hand, NSR-1 adsorbed onto cement particles
up to 90% during the initial 5 minutes.
Further, as shown in Table 4 there was hardly any change in the surface tension of
the cement filtrate (B) containing SRA-1 and SRA-2. Their surface tension determined at
1 and 60 minutes after adding cement into DSRA aqueous solution were almost the same;
for SRA-1, 45.5 mN/m and 43.8mN/m respectively; for SRA-2, 50.1 mN/m and 52.3
mN/m respectively. On the contrary, the surface tension of the cement filtrate (B)
containing NSR-1 changed from 54.0 mN/m after 1 minute to 72.8 mN/m after 60

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minutes, which equals to the surface tension of cement filtrate without DSRA. This
suggested that there was not NSR-1 in the solution in the capillary pores because almost
all ofNSR-1 adsorbed on the cement particles.
3) Drying shrinkage-reducing of mortar containing DSRA

Drying shrinkage is strongly affected by the amount of coarse aggregates in concrete
so the drying shrinkage of concrete becomes less than that of mortar. Thus, the
measurement of length change was carried out by mortar to avoid the affect of coarse
aggregates.
Relations between drying shrinkage results of mortar containing DSRA and drying
periods are shown in Figure 3. Also the relationships between drying shrinkages and
dosages of DSRA at 28 days are shown in Figure 4. Figures 3 and 4 suggest that drying
shrinkage-reducing effect ofNSR-1 at the dosage of0.3% by mass of cement, was nearly
equal to those ofSRA-1, SRA-2 and SRA-3 at dosages of2.0% by mass of cement.
Higher drying shrinkage-reducing effect is expected when the NSR-l.adds more.
However, a dosage of NSR-1 more than 0.3% by mass of cement promoted the
segregation. Hence, the evaluation drying shrinkage-reducing effect was carried out at the
dosage ofNSR-1 less than 0.3% by mass of cement.
In this test, the water-cement ratio was kept fixed of 0.44. Accordingly, the initial
concentration of SRA-1 and SRA-2 in water was about 4.5 mass% for their dosage of
2.0% by mass of cement. The surface tensions are then estimated to be 36.0 mN/m for
SRA-1 and 40.0 mN/m for SRA-2 from the results shown in Figure 1. For NSR-1, the
initial concentration in water is about 0. 7 mass% at a dosage of 0.3%, by mass of cement,
corresponding to a surface tension of solution containing NSR-1 of about 55.0 mN/m
from Figure 1.
As shown in Table 4, the surface tension ofNSR-1 increased up to 72.8 mN/m after
60 minutes, while those ofSRA-1 and SRA-2 maintain the initial values over 60 minutes.
This can be explained by the fact that SRA-1 and SRA-2 do not adsorb on cement
particles, but NSR-1 rapidly and strongly adsorbs onto cement particles as shown in
Figure 2.
By these results, it is presumed that as the drying shrinkage-reducing mechanism of
SRA-1 and SRA-2, the surface tension is dominant among the factors influencing drying
shrinkage. However, the surface tension for NSR-1 is not less than that of water.
Therefore, it might be concluded that the drying shrinkage-reducing mechanism of
NSR-1 is different from that of both SRA-1 and SRA-2. At present, it is impossible to
clarify the drying shrinkage-reducing mechanism of NSR-1 because we consider several
influencing parameters. However, one can point out that one of the reasons for these
differences in drying shrinkage-reducing mechanism is that NSR-1 is a
polycarboxylate-type polymer having a larger amount of hydrophobic groups and can
strongly adsorb onto cement particles. Hence, NSR-1 could make surfaces of pores
hydrophobic by adsorbing on pore wall composed of hydrated cement particles, thus
resulting in a reduction of the interfacial tension between surfaces of pores and water in
pores. However, it should be noted also that the concentration of DSRA in water in pores
should vary with time because of the consumption of water for the cement hydration and
the adsorption on the cement particles. Accordingly, the effect of cement hydration
should also be considered. Thus, in future, time dependency the DSRA concentrations in
water in pores and their surface tension should be investigated to clarify the differences

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302 Masanaga et al.
of mechanism on drying shrinkage-reducing NSR-1 and SRA-1, SRA-2.
4) Concrete properties
Table 5 shows properties of fresh concrete containing DSRA. Figure 5 shows air
contents and spacing factors at 5 and 30 minutes after adding water.
Concrete containing NSR-l(C-NSl) achieved the target of slump of 20 em with a
dosage of 0.7%, by mass of cement, and thus C-NS 1 was evaluated without the addition
of a water reducing agent. On the other hand, concretes with 2.0% by mass of cement, of
SRA-1, SRA-2 and SRA-3 (referred as to C-SRl, C-SR2 and C-SR3 respectively) did not
achieve the target of slump of 20 em, and therefore a polycarboxylate-type
superplasticizer (PC-1) had to be used. Further, the air content was controlled by using
air-entraining admixtures or defoamers, if necessary. However, it was difficult to control
the air content in C-SR3, containing SRA-3. Thus C-SR3 was evaluated as non-AE
concrete.
The NSR-1 delayed initial setting by 40 minutes and also final setting by 60 minutes
compared to plain concrete. On the other hand, all the mortars containing SRA-1, SRA-2
and SRA-3 showed no retardation of setting.
The spacing factor of the concrete containing NSR-1 was 230 ~-tm. This value was
much smaller than the values of 300 to 1,200 ~-tm for SRA-1, SRA-2 and SRA-3. This
result means that the air void structure for NSR-1 whould be the most excellent.
Furthermore, Figure 5 shows that the air content and the spacing factor of NSR-1 were
maintained at the superior values of 3.3% and 220 ~-tm between 5 and 30 minutes after
adding water. It is well known that when the spacing factor of hardened concrete is below
200 to 250 ~-tm, hardened concrete shows higher resistance to freezing and thawing [5].
From the results of the spacing factor measurement on fresh concrete, NSR-1 has the
potential for better resistance to freezing and thawing in hardened concrete. In the next
investigations, we would like to evaluate durability of hardened concrete, using NSR-1.
CONCLUSION
The new high performance drying shrinkage-reducing admixture (NSR-1),

introduced in this study, is shown to achieve the same drying shrinkage-reducing effect in
mortar as conventional DSRA at about one-seventh of the addition amount. The NSR-1
adsorbs strongly onto cement particles, without decreasing the surface tension of water in
the capillary pores. Further, fresh concrete containing NSR-1 exhibited the better spacing
factor compared to the conventional DSRA.
REFERENCES
1. Tada S., "Water Transport and Drying Shrinkage Mechanism", Concrete Journal,
Vol.43, No.5, 2005, pp. 43-50
2. Tanimura M. and Tomita R., "Physics and Chemicals of Mass Change Control"
Concrete admixture Handbook, 2004, pp. 78-90
3. Tanimura M., "Countermeasures to Reduce Cracks", Concrete Techno, Vol.23, No.1,
2004, pp. 38-47
4. Fujita Y., "The Mechanism and the Effect of a Drying Shrinkage Reducing Agent",
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Concrete Journal, Vol.43, No.5, 2005, pp. 97-101
5. Sato K., "AE admixture", New Technology and Application of Chemical Admixture
for Concrete, CMC books Co. Ltd., 1995, pp. 29-43
Table 1 -- Drying shrinkage admixture and other chemical admixtures

Sample Name Content
I. Drying shrinkage-reducing admixture (DSRA)
SRA-1 polyoxyalkylenegrycol
SRA-2 low-molecular-weight alcohols-alkylene oxide adduct
SRA-3 polyoxyalkylenegrycol alkyl ether
NSR-1 Newly developed DSRA
2. Water reducing agent
LIG-1 lignine-sulfonate polyol complex
PC-1 Polycarboxylate-type superplasticizer
3. Air control admixtures
AE-1 AE admixture
DEF-1 defoamer
Table 2 - Mixture proportions of mortars

Weight(g) Water reducing agent DSRA
W/C
Name S/A Dosage Dosage
(%) w c s Types (wt"/o/C) Types (wt%/C)
SRAI(0.3) - - 0.30
SRA1(1.0) - - SRA-1 1.00
SRA1(2.0) - - 2.00
SRA2(0.3) - - 0.30
SRA2(1.0) - - SRA-2 1.00
44 2.78 214 486 1350
SRA2(2.0) - - 2.00
SRA3(0.3) - - SRA-3
0.30
SRA3(2.0) - - 2.00
NSR1(0.3) - - NSR-1 0.30
Control LIG-1 0.25 - -
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;J>
if ~
s"'s·
0
-
~
§.
"
....
...., ....
v. "'
;;g
u,
t
.
Oc
;." Table 3 - Mixture proportions of concrete
g
Water reducing agent Air control admixture
Unit content(kg/m3) DSRA
W/C
- "'> "'"~ ...a,f.

Name s/a dosage dosage dosage
v. v. ;;g (%) w c s G Type Types Types
N p (wt"/o/C) (wt"/a/C) (wt"/a/C)
w ,!.,
"'
Plain 60.9 50 195 320 899 929 - - - - -
~ C-SR1 PC-I O.ll5 DEF-1 0.012 SRA-1 2.00
....,
...
v. z §j" C-SR2
50.0 48 160 320 869 973
PC-I 0.140 AE-1 0.005 SRA-2 2.00
N
Oo b "'~ 3 C-SR3 PC-I 0.150 - - SRA-3 2.00
z
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~
C-NS1 - DEF-1 0.014 NSR-1 0.70
"'"'3
....,
N ~
Oo ::tl
Cf
~
"'
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Table 5 - Properties of fresh concrete, using DSRA
Plain C-SRl C-SR2 C-SR3 C-NS1
Formulation
Water reducing agent PC-I PC-I PC-I
dosage (wt"/o/C) 0.115 0.140 0.150
DSRA SRA-1 SRA-2 SRA-3 NSR-1
dosage (wt"/o/C)
· · · - ·io- -~--+--z-.o--1--o-.7--1
Air control admixture DEF-1 AE-1 DEF-1

dosage (wt"/o/C) o.o 12 f-o-=-.-=-oo=-=5c--lf----l--=o-=.oc-:-I4-,----t
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Concrete mixture properties

Slump (em) 20.0 19.0 20.0 19.0 20.5
····-···-··-·······-·-- ····-············-··-···-···1---::-::c-:--J----+---:-:--f
Slump flow (mm) 330 300 320 300 335
Air content (vol%) 0.6 3.0 3.1 0.8 3.3
Setting time
Initial setting (hr:min) 4:45 4:35 4:45 4:40 5:25
7'o-n-:fr:-'=o-m-p7lam-:.=--::-(m-:in-:)-'-l······························ ···---~io······ --o--+---_5=---+--:40:.---f
I::Dev:---ci:-ati
Final setting 6:40 6:15 6:25 6:15 7:40
(hr:min)
Deviation from plain (min)
······· ····-~;zs·····-·r--_-=-,5=---t--_2=-=5,---+---=6.,..o--t
Parameters of the Air-void system in fresh concrete (measured by AVA)
Spacing factor (1-1m) 330 520 1220 230
80
'§' 70
i§ 50
60
'§ 40
.S:!
0) 30
~ 10
0
0.0 2.0 4.0 6.0
Concentration (wt%)
Figure 1 --Relations between surface tension and concentration of DSRA in

cement filtrate (A).

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306 Masanaga et at.
100
,.-_ 90
:::R
~ 80
0 70
·~ 60
.s:= 50
:e£ 40
30
~ 20
10
0
30 40 50
Time (min)
L______
Figure 2- Adsorption of DSRA on cement particles.
700 ·X····control
~~ 600 -~ -SRA1(0.3)
3 -•·-SRAl(l.Oli
~ 500 • · SRA1(2.0) i
= -D SRA2(0.3) j
·~ 400 - SRA2(1.0)\
· • SRA2(2.0) ·
i
-'<)
300 · ll SRA3(0J) i
=
] 200
-6- ·SRA3(2.0)f
···0· '
"' 100
0
0 10 20 30
Figure 3 -·Drying shrinkage behavior of DSRA determined by mortar bars.
0.0 0.5 1.0 1.5 2.0 2.5

Do~eofDSRA(~%)
Figure 4 -- Relation between dosage of DSRA and shrinkage strain at 28 days.

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C-SRI C-SR2 C-SR3 C-NSI

(SRA-1) (SRA-2) (SRA-3) (NSR-1)
Figure 5-- Comparison of air content and spacing factor determined of 5 and 30 min
after adding water.

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308 Masanaga et al.
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SP-239-21
An Amphoteric Copolymer as a
Concrete Admixture
by K.C. Hsu, J.W. Chen, F.T. Jiang, and D.S. Hwung
Synopsis: Superplasticizer is one key component to greatly increase the workability

of concrete. In this study, an amphoteric copolymer (PDA) was prepared and
evaluated as concrete admixture. PDA was prepared froma-N, N-dimethyi-N-(3-(13-
carboxylate) acrylamino) propylammonium ethanate and acrylamide through free
radical polymerization. The test results on cement pastes indicate that this polymer
could uniformly disperse cement particles and enhance the fluidity of the system.
Compared to a commercial sulfonated naphthalene formaldehyde condensates (NSF)
superplasticizer, PDA requires less dosage to achieve good fluidity and provides
better fluidity retention. Limited test data also show that PDA has better performance
than NSF in terms of slump flow and flow retention of the resulting concrete.
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Keywords: amphoteric copolymer; cement; concrete; fluidity;

workability

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310 Hsu et al.
K. C. Hsu is a Professor, Department of Chemistry, National Taiwan Normal
University, Taipei, Taiwan, ROC.
J. W. Chen and F. T. Jiang are Graduate Students, Department of Chemistry,

National Taiwan Normal University, Taipei, Taiwan, ROC.
D. S. Hwung is an Associate Professor, Department of Chemical and Materials

Engineering, Northern Taiwan Institute of Science and Technology, Taipei, Taiwan,
ROC.
INTRODUCTION
Superplasticizer, or high-range water reducer, is an important chemical admixture

commonly used in concrete. Only small amount of the chemical could greatly improve
workability of concrete. Sulfonated naphthalene formaldehyde condensates (NSF) and
sulfonated melamine formaldehyde condensates (MSF) are two typical examples. These
admixtures, after being adsorbed onto cement particles, create electrostatic repulsions and
overcome attractive forces and cause the dissociation of the cement agglomerates into
primary particles. As a result, they provide good dispersing effect on cement and are able
to reduce water demand of concrete of about 25%, while maintaining the flow
characteristics.[l,2] Currently, a new generation of superplasticizers based on
carboxylated acrylic ester copolymer (CAE) has been developed. As these chemicals
contain long, comb-type side chains, they are more effective for the water reducing
capability and for preventing slump loss, because they can disperse cement particles not
only by electrostatic repulsions aforementioned, but also by steric hindrance effects.[2-7]
Up to now, most superplasticizers such as NSF, MSF, or CAE, belong to anionic

polymers. Others, such as amphoteric or cationic admixtures are seldom reported.
Recently, the authors have prepared an amphoteric copolymer (PDA) which shows good
dispersion properties for barium titanate powder in aqueous solutions.[8] In this study,
PDA was evaluated as concrete admixture. PDA was prepared from a-N, N-dimethyi-N-
(3-(13-carboxylate) acrylamino) propylammonium ethanate (DAE) and acrylamide
(AAM) in basic condition through free radical polymerization. PDA samples with
different reactant ratios or molecular weights were prepared, and added into cement
pastes and concrete. The effects of this polymer on the fluidity of cement pastes and the
workability of concrete were examined. Besides, a commercial NSF superplasticizer was
also tested and compared.
EXPERIMENTAL WORK
Materials
The materials used include Type I Portland cement, fine and coarse aggregate, fly
ash and blast-furnace slag, and two chemical admixtures. Cement is from the Taiwan
Cement and complies with ASTM Cl50. Fine aggregate is from the bank of Pearl River,
China. The specific gravity of the sand is 2.59 and its fineness modulus is 2.8. Coarse
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aggregate is from the bank of Da-An River. It has a specific gravity of 2.62 and
maximum-size aggregate of 12.5 mm. Both fine and coarse aggregates meet the standard
of ASTM C33, and were washed and dried before use. Fly ash comes from the Hsin-Da
Thermo-Power Plant, which is a subsidiary of Taiwan Electric Power, and has an LOI
value of 4%. Slag is obtained from China Steel and has a Blaine surface area of 400
m2/kg. Both the fly ash and slag comply with ASTM C3ll. Table I lists the properties of
cement, slag, and fly ash. One chemical admixture used is PDA, which was prepared
from a-N, N-dimethyl-N-(3-(J3-carboxylate )acrylamino) propylammonium ethanate
(DAE) and acrylamide (AAM) in basic condition through free radical polymerization.
Details of the preparation procedure were described elsewhere.[5] Figure 1 shows the
chemical structure of PDA. In this study, polymers with different reactant ratios and
weight-average molecular weights were prepared and tested. As shown in Table 2, the
AAM/DAE ratio ranged from 1/1 to 10/l, and molecular weight was ranging from
1.8x104 to l.lx10 5. P11, P12, and P13 have the same reactant ratio, but different
molecular weight; Pl2, P22, and P32 have close molecular weight, but different
DAE/AAM ratio. Another chemical admixture is a NSF superplasticizer; it was used for
comparison.
Preparation and Fluidity Test of Cementitious Materials
PDA was first dissolved in water to form an aqueous solution with 20% by
weight in solid content. Cement pastes were made by mixing water and cement, with or
without addition of polymer solution. The water/cement ratio (W/C) was fixed at 0.3; the
polymer/cement ratio (SP/C) ranged from 0 to 1 % by mass of cement, expressed in
terms of dry material. The fluidity of cement pastes was indicated by the measured mini-
slump value, which was determined from a mini-slump test.[9] The apparatus for this test
consists primarily of a hollow mold in the form of a frustrum of a mini cone with the base
40 mm in diameter, the top 20 mm in diameter, and the height 60 mm. The minicone was
sat on a plexiglass plate and filled with cement pastes. Ten strokes were given on the top
of the mini cone before it was raised rapidly. The mini-slump value is indicated by the
measured spread diameter of pastes on the plate. Higher spread diameter value represents
greater fluidity of materials.
Concrete was made by mixing water, binder (cement+ fly ash+ slag), sand, and
coarse aggregate, with or without the presence of polymer solution. The water/binder
ratio (W/B) was 0.37; the polymer/binder ratio (SP/B) ranged from 0.54 to 0.8% by
weight. Table 3 lists the mixture proportions of concrete made with various PDA and
NSF. The workability of concrete was indicated by the slump and slump flow values
determined shortly after the end of mixing (0 min) and 60 min after using the slump test
according to ASTM C143.
Adsorption Measurements
Cement pastes (W/C = 0.6) with polymer (SP/C = 0.5 wt %) were prepared. After
the samples were mixed and centrifuged, the clear solutions on the top of the paste
samples were taken. The residual dispersant concentration in the clear solutions was

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312 Hsu et al.
determined by an RI dector.[5] The amount of polymer adsorbed onto cement particles
was calculated from the difference in the admixture concentration before and after
adsorption.
Fluidity of Cement Paste
The major function of superplasticizer is to disperse cement particles and improve

workability of concrete. Examining the fluidity of cement pastes could be used as a
screening test for determining the effectiveness of the chemicals on enhancing
workability of concrete. In this study, the fluidity of cement paste made with different
admixtures was evaluated using flow spread diameter in a minicone test. For most tested
cement pastes containing PDA, the saturation point [9] occurs at a polymer dosage of
about 0.6% and 1.0%. It is well known that both the reactant ratio and molecular weight
of superplasticizer influence the performance of the admixture.[IO,ll] In order to
compare the dispersing effectiveness of PDA samples with different reactant ratios and
molecular weights, the mini-slump of cement paste containing fixed dosage of 0.8%
polymer was measured at 0 and 60 min, as shown in Figure 2. The cement paste
(W/C=0.3) made without any chemical admixture will not flow under such a low W/C.
When PDA was added, the fluidity of the resulting pastes increased. For PDA with
different molecular weights, the fluidity-enhancing effect was in the following order: P12
> Pll > P13. Namely, the optimal molecular weight of this polymer was about 5.7 X 104,
which exhibits the best dispersion effect on cement particles and the resulting cement
pastes have highest spread diameter. Besides, the 60-min slump value is not less than the
initial slump value, indicating no slump loss in the period of 0-60 minutes. When the
molecular weight of PDA is deviated from the optimal value, the performance becomes
worse. Figure 2 also shows the effect of reactant ratio of PDA; the fluidity-enhancing
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effect is in the order: P22 > P12 > P32. The optimal AAM/DAE ratio appears to be about
5/1, which results in mixtures with the highest fluidity on cement pastes. Besides, the 60-
min slump value is higher than the initial slump value by 13.5%.
Figure 3 shows the initial mini-slump of cement pastes incorporating different

admixtures at various dosage rates. When superplasticizer was added, the fluidity of the
resulting pastes is expected to increase. In general, the diameter value is shown to
increase quickly with polymer dosage initially, and then approach a plateau gradually.
The transition point or the saturation point for the three tested admixtures appears to be
close to each other; it occurs at a polymer dosage of about 0.8%. However, the achieved
mini-slump at the plateau is slightly different for each admixture. Apparently, P22 shows
the best fluidity-enhancing effect, followed by NSF and P12. Besides, cement pastes
with PDA were found to show lower slump increasing rate than those with the
commercial NSF one. This is because PDA has molecular weight higher than NSF.
Furthermore, the former molecules contain DAE moiety which has side chains linked
with carboxylate group. The side chains of PDA molecules would cause some steric
effects and hinder the polymer from being adsorbed onto cement particles. Accordingly,
PDA was found in Figure 4 to show lower adsorption rate onto cement particles and

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lower adsorption amount at the plateau than the commercial one; therefore pastes with
PDA showed lower slump with increasing dosage rate than those made with NSF.
Figure 5 shows the 60-min spread diameter of cement pastes made with different
admixtures used at various dosages. It is clear that the two PDA samples are more
effective in maintaining the fluidity than NSF, as the saturation points occur at lower
polymer dosage and the achieved slump values at the plateau are higher for the former.
Again, the difference in slump-retention property between PDA and NSF could also be
attributed to different adsorption behaviors onto cement particles. Furthermore, the
spread diameter of cement pastes with either Pl2 or P22 at 60 min was observed to be
even greater than that initially, indicating that the polymer with proper reactant ratio and
molecular weight would behave like CAE, has slump-releasing property along with
elapsed time.
Although CAE has slump-releasing property, the addition of CAE into concrete
incorporating NSF could not improve the slump retention of the cementitious material
due to the incompatibility of these two admixtures.[12] As PDA shows the slump-
releasing effect, it will be interesting to know if blending this polymer with NSF could
improve the slump-retention property of the commercial admixture. Figure 6 shows the
0- and 60-min spread diameter of cement pastes incorporating NSF/P22 at different
blended ratios. The admixture dosage is 0.8%. Along with increasing P22/NSF ratio, the
0-min slump increases initially, reaches a maximum value at about a ratio of 4/6, and
then decreases afterwards. In contrast, the 60-min slump increases monotonically with
P22/NSF ratio. Apparently, P22 is compatible with NSF. More importantly, blended
admixture replaced by PDA show improved fluidity retention over those containing pure
NSF.
Workability of Concrete
Concretes proportioned with different admixtures were produced and their slump
and slump flow values were measured, as shown in Table 3 and Table 4, respectively. In
this study, concrete did not flow if it did not incorporate any chemical admixture. As the
polymer was added, both the slump and slump flow values of the concrete increased due
to the dispersing effect of the admixture. For concrete made with P22 polymer ( CP 1) at
0.54% by mass of binder, the slump and slump flow value were about 230 mm and 370 x
370 mm 2 at 0 min, and 275 mm and 640 x 630 mm2 at 60 minutes, respectively. It is
noted that the latter slump flow value is higher than the former one. This agrees with the
test results of cement pastes and confirms that PDA indeed could provide slump-
releasing effect. Besides, concrete made with higher admixture dosage showed greater
initial workability. When the polymer dosage was increased to 0.6%, both the initial and
60-min slump values of the concrete (CP2) were about 265 mm, and the initial and 60-
min slump flow values of the concrete (CP2) were about 650x650 mm 2• In contrast,
concrete made with NSF required higher superplasticizer dosage to achieve similar
slump and slump flow. Both CNI and CN2 had worse workability-retention properties
than the CPl and CP2, because concrete containing NSF shows some slump loss along
with elapsed time.
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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
314 Hsu et al.
Table 4 also shows that slump and slump flow values of concrete (CM1)
containing a blended admixture (P22/NSF = 2/8), which presented improved slump flow
and flow retention characteristics over those made only with NSF. This is consistent with
the test results of cement pastes, suggesting that PDA could blend with NSF without
losing its performance. More importantly, the synergetic effect could occur for the
blended admixtures with proper PDA/NSF ratio.
CONCLUSIONS
A new amphoteric copolymer (PDA) has been prepared and examined as a

superplasticizer for concrete. The results indicate that this polymer is as effective as NSF
in dispersing cement particles and enhancing fluidity of cement paste. The use of PDA
yields better fluidity-retention properties than similar system made with NSF. Limited
test data indicate that this new admixture can exhibit good performance in terms of
workability and workability retention of the resulting concrete.
ACKNOWLEDGMENT
The authors are grateful for the support of this work by the National Science
Council of The Republic of China (Contract# NSC-94-2211-E-003-001).
REFERENCES
1. Rixom, M. R., Mailvaganam, N. P., Chemical Admixtures for Concrete, 2"d Edition,
E & F. N. Spon, London, 1986, pp. 12-19.
2. Collepardi, M., "Superplasticizers and Air Entraining Agents: State of the Art and
Future Needs", Concrete Technology Past, Present, and Future: Proceedings ofV.
Mohan Malhotra Symposium, San Francisco, 1994 (SP-144 ), ed. P. K. Mehta,
American Concrete Institute, pp. 399-416.
3. Ramachandran, V. S., Malhotra, V. M., Jolicoeur, C., Spirattos, N., Superplasticizers:

Properties and Applications in Concrete, CANMET, Ottawa, Ontario, 1998, pp. 199-
202.
4. Peng, J. H., Qu, J. D., Zhang, J. X., Chen, M. F., Wan, T. Z., "Adsorption Character-
istics of Water-Reducing Agents on Gypsum Surface and its Effect on the Rheology
of Gypsum Plaster", Cement and Concrete Research, 35 (3), 2005, pp. 527-531.
5. Li, C.Z., Feng, N. Q., Li, Y. D., Chen, R. J., "Effects ofPolyethlene Oxide Chains on
the Perfonrmance of Polycarboxylate-Type Water-Reducers", Cement and Concrete
Research, 35 (5), 2005, pp. 867-873.
6. Jeknavorian, A. A., Roberts, L. R., Jardine, L., Koyata, H., Darwin, D. C., "Condensed
Polyacrylic Acid-Aminated Polyether Polymers as Superplasticizers for Concrete",
Superplasticizers and Other Chemical Admixtures in Concrete: Proceedings of the
Fifth CANMET/ACI International Conference, Rome, Italy,1997 (SP-173), ed. V.M.

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Malholtra, American Concrete Institute, pp. 399-416.
7. Hanehara, S., Yamada, K.,"Interaction between Cement and Chemical Admixture from
the Point of Cement Hydration, Adsorption Behavior of Admixture and Paste
Rheology", Cement and Concrete Research, 29 (8), 1999, PP. 1159-1165.
8. Chen, L. P., Hsu, K. C., "Amphoteric Water-Soluble Copolymer for Barium Titanate
Slurries. I. Synthesis and Dispersing Ability", Journal of Applied Polymer Science, 96
(4),2005,pp.l443-1450.
9. Aitcin, P. -C., High-Performance Concrete, E & FN SPON, New York, 1998, pp. 170-
190.
10. Ferrari, G., Cerulli, T., Clemente, P., Dragoni, M., Gamba M., Surico, F., "Influence
of Carboxylic Acid-Carboxylic Ester Ratio of Carboxylic Acid Ester Superplasticizer
on Characterics of Cement Mixtures", Superplasticizers and Other Chemical
Admixtures in Concrete: Proceedings of the Sixth CANMET/ACI International
Conference, Nice, France,2000 (SP-195), ed. V.M. Malholtra, American Concrete
Institute, pp. 505-520.
11. Ye, Y. S., Huang, H. L., Hsu, K. C., "A Water-Soluble Acrylate/Sulfonate Copoly-
mer. I. Its Synthesis and Dispersing ability on Cement", Journal of Applied Polymer
Science, 100 (3), 2006, pp. 2490-2496.
12. Coppola, L., Erali, E., Troli, R., Collepardi, M., "Blending of Acrylic
Superplasticizer with Napthalene, Melamine or Lignosulfonate- Based Polymers",
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Superplasticizers and Other Chemical Admixtures in Concrete: Proceedings of the

Fifth CANMET/ACI International Conference, Rome, Italy,l997 (SP-173), ed. V.M.
Malholtra, American Concrete Institute, pp. 203-224.

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316 Hsu et al.
Table 1. Properties of cement, slag, and fly ash
Properties Cement (TYPe I) Slag Fly ash
SiOlS) 22.01 34.86 52.66

Ah03 5.57 13.52 29.19
Ft::20JFf 3.44 0.52 3.98
CaO 62.80 41.77 4.14
MgO 2.59 7.18 2.05
so3 2.08 1.74 0.61
FreeCaO 1.05 - -
Chemical
composition Na20 0.40 - -
(%) K 20 0.78 - -
Loss on ilmition 0.51 0.31 4
Insoluble residue 0.08 - -
c3s 40.1 - -
c2s 32.8 - -
C3A 8.9 - -
C.0f" 10.5 - -
Physical Blain surface area
346 435 311
properties (mz/kg)
Soecific gravitv 3.15 2.87 2.21
Table 2. Properties of PDA samples
Polymer AAMIDAE Molecular weight

PI! 111 1.1 X 105
Pl2 111 5.7x to•
Pl3 1/1 1.8 X 104
P22 5/l 5.3 X 104
P32 1011 s.ox
104
Table 3. Mixture proportions of concrete
Concrete SP Materials (kglrn3)

W/B
symbol symbol Coarse Fly
Sand Slag Cement Water SP*
l3.1!greltate ash
CPI P22 0.37 890 943 115 49 246 148 2.21
CP2 P22 0.37 890 943 115 49 246 148 2.46
CNI NSF 0.37 890 943 115 49 246 147 2.95
CN2 NSF 0.37 890 943 115 49 246 147 3.28

P22/NSF
CMl 0.37 890 943 115 49 246 146 3.28
=2/8
•based on the dry mass of polymer or superplasticizer
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Table 4. Properties of concrete
Concrete Unit Air Workability Comp. strength (kg/em')

symbol SP!B weight (%)
(%) (kg!m') Omin 60min 3d 7d 28d
CPl 0.54 2309 6.0 230° 275 242 353 465
CP2 0.6 2336 5.3

(370x370* 0 )
270
(670x640)
(640x630)
265
(670x620)
-
... - -
CN1 0.72 2363 2.1 265 260 - - -

(590x560) (570x550)
CN2 0.8 2366 2.4 265 265 215 317 441
(610x600) (580x570)
CM1 0.8 2366 4.3 270 270 - - -
(640x640) (650x640)
• s1wnp value in mm2•
** slwnp flow value in rnm 2•
••• not measured.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 1. Chemical structure of PDA.
c=:J 0 min
200
-60min
'E
.5. 160
I
.!2 120
0
lQ. so
en
40
P11 P12 P13 P22 P32
Figure 2. Mini-slump of cement paste made with various PDA samples

(SP I C=o.8%).

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318 Hsu et al.
200
'E
~ 160
Ii5 120
~ --o-- P22
I!!
~ P12
c% 80
-w- NSF
SP/C(%)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 3· Mini-slump of cement paste (o min).
0---L~--L-~-L~~~_L~~
0 20 40 60 80 100
Time(min)
Figure 4· Adsorption of admixture onto cement particles.
200
'E
.s 160 ,..-
~E
a 120 /
-c
"'
I!! / --o-- P22
c% 80 ~ P12
/ _ . NSF
0.4 0.6 0.8 1.0

SP/C(%)
Figures. Mini-slump of cement paste (6o min).

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c=:::J 0 min
200
-60min .---
e .--
.---
f 160
*E
~ 120
lQ.
!/) 80
40 -
NSF/P22 10/0 8/2 6/4 4/6 218 0/1 0
Figure 6. Mini·slump of cement paste made with blended admixtures

(SP/C=o.8%).
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320 Hsu et al.
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SP-239-22
Influence of Surfactant Chemical

Admixtures on the Stability and
Rheological Properties of Calcium
Carbonate and Cement Pastes
by N. Mikanovic, C. Jolicoeur, and M. Page
Synopsis: The influence of various types of surfactants on the rheological properties

and on the rates of bleeding and sedimentation of limestone and cement pastes has
been examined as function of surfactant concentration. The surfactants selected
include both low foaming and foaming compounds to enable a distinction of the
effects inherent to the surfactants, from those due to air entrained in the pastes. Over
the range of concentration examined, the rheological characterization performed
shortly after mixing showed little change in the paste rheology due to the presence
of the surfactants, in the absence of entrained air. As expected, with entrained
air, the rheological parameters are all moderately altered. On the other hand, the
stability ofthe CaC0 3 pastes, evaluated through their bleeding and sedimentation
kinetics, is markedly affected by the surfactants. At short times (<1 hr), the stability
is only marginally changed; at longer times, the paste stability is substantially
decreased through cooperative bleeding and sedimentation behavior. Similar effects
were observed in lime-saturated CaC0 3 pastes, though less pronounced due to the
higher stability of these pastes. In relatively stable cement pastes, the bleeding
and sedimentation were initially similar to the limestone pastes, but no cooperative
destabilization was observed, with or without surfactants.
The influence of the surfactants on bleeding and sedimentation kinetics
was attributed to the formation of channels in the pastes, a process facilitated by
the surfactants. The variations observed with surfactant molecular and solution
properties and concentration are discussed; a plausible mechanism is suggested to
explain surfactant-induced effects.
Keywords: admixtures; bleeding; calcium carbonate; cement;

coagulation; consolidation; flocculation; paste; rheology;
sedimentation
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321
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322 Mikanovic et al.
Nikola MIKANOVIC, M.Sc. is a Ph.D. student in the department of chemistry at the
Universite de Sherbrooke, Quebec, Canada. His research addresses cement chemistry and
cement-admixture interactions and the consequence of these interactions on the rheology
and microstructure of cementitious materials.
Carmel JOLICOEUR, Ph. D., is professor in the department of chemistry, Universite de

Sherbrooke, Quebec, Canada. His research interests include the solution and colloid
chemistry of cementitious systems and chemical admixtures for cement-based materials.
Monique PAGE, Ph.D. is Executive Vice-President of Handy Chemicals Ltd., Candiac,

Quebec, Canada. Dr Page specializes in colloidal chemistry and she heads the
development of various types of concrete chemicals admixtures.
INTRODUCTION
The elucidation of mechanistic aspects of chemical admixtures in cementitious systems is

often hindered by the simultaneous occurrence of hydration reactions. Such reactions
alter the different chemical equilibria involving the admixture and the cement particles,
which, in tum, change the physical properties and behavior of the system. For example,
superplasticizers disperse cement particles through physical effects (e.g., electrostatic,
steric ). In addition, they alter the rate of the hydration reactions through specific
interactions at the cement-water interface; the latter also lead to changes in the
morphology of cement hydration products. Under these circumstances, it is obviously
difficult to unravel the various physical and chemical effects, which contribute to the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
overall influence of superplasticizers on fresh cementitious systems.
The search for alternate approaches to investigate the mode of action of concrete
chemical admixtures has occasionally led to studies on inert mineral systems (l· 6l.
Aqueous slurries of various minerals, typically quartz, titanium dioxide, magnesium
hydroxide and calcium carbonate have been used as reference (or model) systems for
cement pastes. If the reference system adequately represents 'non-hydrating' cement
particles, various physical processes involving the admixture, such as binding to the
mineral surface, calcium ion complexation, solution and paste rheology, etc, can be
characterized and better understood. Through a comparison of observations on the
reference system and on cement pastes, a more accurate description of the mode of action
of concrete admixture should then emerge.
In recent work (7, 8l, the authors have established that calcium carbonate exhibits colloidal
properties very similar to those of Portland cement. Indeed, CaC0 3 and cement slurries,
examined over a wide range of the water/solid ratio, showed remarkably similar
flocculation, stability and rheological behavior shortly after mixing. At longer times (> I
hour), the properties (stability, rheology) of the cementitious slurry depart from those of
the limestone slurry, reflecting the consequences of hydration reactions. The work
described below was undertaken to further explore the potential of limestone pastes as a
model system to elucidate the mode of action of chemical admixtures. In its initial phase,
the investigation focused on the influence of surface active admixtures and their role on

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the stability and rheology of limestone and cement slurries. Similar work is currently
being extended to superplasticizers and viscosity-enhancing admixtures.
Materials
A common GU (ASTM Type I) Portland cement was used, the composition of which is
reported in the Table 1. The specific surface area and mean particle diameter (weight
average) of the calcium carbonate and cement used are presented in the Table 2. The
surfaces of both solid materials are comparable, although the particles of the limestone
mineral are somewhat finer.
The nature and origin of the different surfactants used in this study are presented in Table
3, together with some of their key physicochemical properties, namely, critical micelle
concentration (CMC), hydrophilic-lipophilic balance (HLB) and their foaming ability.
The surfactants selected cover different groups of surface-active molecules having widely
different properties. The choice of surfactants was also guided by their availability as
pure substances, or as commercial products of known composition.
Methods
Paste stability measurements.--The bleeding, sedimentation and consolidation

phenomena in pastes of the reference mineral and cement were monitored through a
method based on electrical conductivity measurements, developed earlier by the authors
(?-llJ. In all of the systems investigated, the aqueous phase is electrically conducting, from
naturally occurring electrolytes (cement pastes) or added salts (NaCl, NaOH, Ca(OH) 2, or
mixtures of these electrolytes at constant ionic strength in calcium carbonate pastes).
Since the solid phases are non-conducting, variations in the electrical conductivity of a
paste measured as a function oftime and depth in the sample will directly reflect the local
changes in the mixture composition, which result from the combined effects of water
migration and solids sedimentation-segregation.
Typical conductivity vs. time curves obtained in calcium carbonate pastes, at different
depths in the sample (different electrode pairs), are illustrated in Figure 1 (a); the curves
obtained for cement pastes (9- 10) are somewhat more complex, since the electrolytes which
dissolve upon cement hydration change the conductivity of the solution phase with time.
Nevertheless, the variance in the conductivity values at different depths at a given time is
a direct measure of the heterogeneity of the sample at that instant; such data have been
used to define various indices describing the stability of a cementitious system.
The conductivity curves were analyzed through a protocol described elsewhere (?, 11 ) to
extract density profiles, from which two fronts can be identified:
the bleeding front, which represents an interface between accumulated bleeding
water and the rest of the sedimenting column, and
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the sedimenting front, which represents an interface between the sedimenting
column and compacted sediment.
The evolution of these fronts with time defines the bleeding and sedimentation curves
shown in Figure 1(b). These curves provide quantitative information on the rate of
surface bleeding and the rate of formation of a layer of maximum compaction at the
bottom of the conductivity cell. The bleeding curve derived from conductivity
measurements was shown consistent with results of a standard protocol (ASTM C232) as
illustrated in Figure l(b); the ASTM method involves collecting the surface bleed water
as function of time. Details on the instrumentation, optimization of the experimental
parameters and data analysis procedures may be found elsewhere (Ill.
Rheology. -- All rheological measurements reported in this study were performed with a
Viscotech rheometer (ATS RheoSystems) using cup and bob geometry at constant
temperature (25 'C). The yield stress values of the pastes were determined via a stress-
growth experiment using a vane tool to avoid "wall slippage" (llJ. In these experiments
the pastes were sheared at a low and constant shear rate(- 0.01 rad/s), and the resulting
shear stress was measured as a function of time; the yield stress value was determined as
the maximum stress in the stress-time curve.
In order to obtain pastes with reproducible viscoelastic behavior, all samples were pre-
sheared 30 s at 200 Pa and then allowed to rest for 5 minutes before the beginning of the
dynamic viscosity measurements. In this way, each paste was reduced to a reproducible
reference state prior to rheological characterization. In oscillation stress sweep
experiments, the shear sweeps, usually between 0.1 and 10 Pa were run at a constant
frequency of I Hz; the elastic and loss modulus and the phase angle were determined in
the linear viscoelastic region. Frequency sweeps were also performed at frequencies
ranging from 0.01-IO Hz; the applied stress during the frequency sweeps was well below
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
the critical stress of the particular sample. From these experiments, other rheological
parameters were determined, namely the relaxation time (inverse value of the frequency
at which the phase angle reaches 45') and the zero-shear viscosity (low frequency
extrapolation of the measured complex viscosity).
Adsorption. -- The adsorption of admixtures onto mineral particles in the pastes was
determined by measuring the residual concentration of the admixtures in the liquid phase
of the concentrated suspensions of limestone or cement particles. The pastes for
adsorption measurements were prepared in the same way as pastes for stability and
rheological measurements (see below). A one hour period was considered to be sufficient
for adsorption equilibrium at ambient temperature. After centrifugation of the paste
sample, the supernatant was diluted and the residual concentration of the admixture was
determined by the suitable analytical technique. The admixtures which adsorb in UV and
visible region of the spectrum (PNS and Triton X-100 surfactant) were quantified
spectrophotometrically using a Hewlett Packard 8452A Diode Array spectrophotometer.
The residual concentration of the other organic admixtures in the solution was obtained
by chemical oxygen demand (COD), which determines the total organic carbon in the
solution (IJJ.

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Surface tension measurements
The surface tension of surfactant solutions was measured as a function of surfactant
concentration between 1o-4% and l% in saturated CaC0 3 solution using a Fisher
Surface tensiomat (Model 21). The occurrence of a surfactant aggregation process
(micelle formation) is signaled by a change of slope in the surface tension vs.
concentration curve; in such cases, critical micelle concentration values (CMC) could be
obtained.
Mixing protocols and measurement sequence. The samples used for stability and
rheological measurements were prepared with a Hobart mixer according to ASTM
procedure C305. The required amount of water or electrolyte solution (10 g/1 NaCl in
calcium carbonate pastes) and admixtures were introduced into a mixing bowl before
mixing, except as otherwise indicated. The solids were then slowly introduced in the
mixer and the time recorded as time zero for bleeding and sedimentation measurements;
the total mixing time was 4 minutes. The sample was then transferred into the
conductivity cell and conductivity readings started within 5-6 minutes of initial
solid/liquid contact.
The remainder of the sample was used for rheological characterization as described
above, and for evaluation of air entrainment in the pastes when necessary. The latter
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measurements were made 6 minutes after mixing through the following paste protocol. A
portion of the sample was transferred to overfill a Plexiglas cylinder (9 .5 em height and
5.2 em interior diameter), and the excess paste was skimmed-off with a straight edge. The
air content of the sample was determined by measuring the mass of the sample in the
cylinder, and by comparing this mass with the mass calculated for an air-free paste. Paste
fluidity measurements were also performed 8 minutes after mixing on another portion of
the sample, using the Cantro mini-slump method (l 4l; the paste spread diameters reported
are obtained as an average of 4 readings.
The rheological measurements (ViscoTech rheometer) were executed in the following

order: yield stress measurement (stress-growth technique, 10 min after mixing); at
approximately 15 and 20 minutes after mixing, oscillatory stress sweep and frequency
sweep measurements were performed, respectively. The sample was gently stirred
manually before each of these rheological measurements; as indicated above, a strong
pre-shearing at 200 Pa for 30s was performed before each of the oscillatory
measurements.
The various data illustrating the behavior of the reference limestone and cement pastes, as
well as the influence of admixtures on the properties of these pastes, are collected in
Tables 4 and 5 (4: bleeding and sedimentation, 5: rheology). For discussion purposes, the
following quantities have been extracted from bleeding and sedimentation curves similar
to those in Figure 1 (b):

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Bleeding volume: total volume of bleeding water accumulated at the top of the
cell, at the end of sedimentation experiment, and expressed as volume of water I
unit surface area (ml)
Q0 : initial constant bleeding rate, taken as the initial slope of the bleeding curve
Qch: channel bleeding rate - an accelerated rate of bleeding after a initial period of
constant bleeding rate.
V,: initial sedimentation rate, determined as an initial slope of the sedimentation
curve.
The following rheological parameters were determined (Table 5):

Slump value: the paste spread diameter as a result of the mini-slump test
10: yield stress of the paste
G' and G": elastic and loss modulus in the linear viscoelastic region, a "plateau"
value on the oscillatory rheological curves similar to those presented in Figure 2.
8: phase angle, a "measure" of the degree of elasticity of a sample (tan 15 = G"/G')
T]o: zero-shear viscosity, a finite value of complex viscosity at low frequencies in
frequency sweep measurements.
All these rheological parameters have been obtained in measurements carried out at very
low shear stresses, so they should be relevant to bleeding/sedimentation phenomena
which take place at low stresses, involving small deformations in the sample.
Rheological properties and stability of CaC01 and cement pastes
In a previous study <7J the authors concluded that calcium carbonate (CaC0 3) appeared as
the most relevant model mineral to elucidate the factors contributing to the stability and
the rheological properties of cement-based materials at short times (i.e., <I hour). CaC0 3
has surface properties and flocculation behavior comparable to slightly hydrated cement
particles, namely, an irregular spheroid shape, a low surface charge (zeta potential) in
water and a very low solubility, even at high pH (- 12-13) relevant to cementitious
systems. To further illustrate the similarity in the behavior of CaC0 3 and cement pastes,
the rheological properties and the bleeding-sedimentation behavior of the following
systems were examined: a CaC0 3 paste (LIS=O.S) and a cement paste (LIS=O.SS). These
LIS ratios were selected to yield stable pastes with similar fluidities.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Reological observations -- The rheological parameters derived from dynamic viscosity

measurements on the reference limestone and cement pastes are presented in Table 5. The
evolution in the elastic (G') and loss (G") moduli of these pastes as function of shear
stress is illustrated in Figure 2. The data confirm that the limestone paste (in water)
exhibits a rheological behavior nearly identical to that of the cement paste, indicating
similar particle-particle interactions, state of flocculation and microstructure in these two
pastes. Interestingly, when Ca(OH)2 is added at saturation to the CaC0 3 paste, the yield
stress and the elastic and loss moduli all increase substantially, indicating a more stable
(stiffer) microstructure. The paste zero-shear viscosity values (TJo) reflect a similar effect.
These observations are consistent with the known influence of Ca-z ions as a flocculating

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agent <7l. The phase angle data, on the other hand, indicates a slightly more solid-like
behavior i.e., lower phase angle, for the limestone paste, compared to the cement paste.
The paste rheology reflected in the minislump test results (Table 5) shows minor
differences in the paste fluidities, minislump spread values decreasing in the order :
cement> CaC0 3 > CaC03 pH 12.5.
Observations on paste bleeding and sedimentation -- Figure 3 illustrates the bleeding and
sedimentation behavior of the CaC03 and cement pastes obtained from the analysis of
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
conductivity measurements. As indicated by the limiting slopes of the curves, the initial
bleeding and sedimentation rates (respectively Q0 and V,) of the two pastes are identical
within experimental error. However, after approximately 90-120 minutes, the limestone
pastes exhibit a rapid increase in the bleeding and sedimentation rates, which are believed
to be associated with the formation of channels (Qch) (see discussion below). At the same
time, in the cement paste, the hydration reactions begin to play a dominant role in the
flocculation-sedimentation of the particles. The hydrating cement particles form a three-
dimensional network which inhibits the separation of the liquid and solid phases, as is
readily apparent from the data in Figure 3. Hence, the accelerated bleeding and
consolidation processes are not observed in the cement paste. In accordance with
observations on the rheological properties, the presence ofCa(OH) 2 stabilizes the CaC03
paste, reducing the initial bleeding rate (Q 0).
The remarkable similarity in the early bleeding and sedimentation behaviors of the
CaC0 3 and cement pastes confirms that the key physical effects responsible for bleeding-
sedimentation behavior in cement paste are adequately represented by those which occur
in the CaC0 3 paste. Consequently, the factors influencing the early migration of liquids
and solids in cementitious systems, and the influence of many types of chemical
admixtures on these processes, can be usefully investigated in model limestone pastes.
Likewise, observations on paste rheology confirm that investigations on the mode of
action of admixtures in limestone should provide information highly relevant to
cementitious systems.
Influence of surfactants on paste properties
The surface active compounds selected to elucidate the influence of air-entraining agents
(AEA) on the properties of cementitious systems comprised various types of molecules,
namely:
a foaming anionic surfactant typically used as an AEA, Sodium Decylsulfate
(DSSi' 5l
a foaming non-ionic surfactant of size comparable to DSS, Triton X-1 00
a low molecular weight ethylene glycol polymer (PEG) selected as a reference
organic polymer with little surface activity
a non-foaming low molecular weight propylene glycol polymer (PPG) representing
a surface active polymer
a block EG-PG-EG surfactant co-polymer with low foaming properties labeled as
L-61

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328 Mikanovic et at.
The choice of surfactants was designed to emphasize the influence of various surfactant
properties on the stability and rheological properties oflimestone and cement pastes (e.g.,
molecular weight, charge, hydrophobic character (HLB), foaming ability, etc.). The
molecular features of the surfactants used are given in Table 3 along with other data
relevant to the later discussion. To help distinguish the effect inherent to the presence of
the surfactants from the consequences of air entrained by the surfactants, some
experiments were performed under two different protocols: adding the surfactant at the
beginning of the mixing process for deliberate air entrainment, or gently introducing it at
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
the end of the experiment, hence avoiding air entrainment.
To further assist the interpretation of paste properties in the presence of surface active
compounds, the surface tension of saturated CaC0 3 solutions were determined as
function of increasing surfactant concentrations; the results are illustrated in Figure 4. As
expected from their relative hydrophobic character, PEG induces only a minor decrease
in the surface tension of water, while the other surfactants lead to a significant lowering
of the surface tension. In some cases, DSS, Triton and L-61, a significant slope change is
observed in the surface tension vs concentration curve; this signals the occurrence of
micellization, a surfactant aggregation process; the sharper the break in the surface
tension curve, the more cooperative the aggregation process (l 6l.
As with any concrete chemical admixture, the interaction of surfactant molecules with the
surface of the particles (CaC0 3 or cement) may play a role in their overall effect on these
pastes. To asses the significance of such effects, the binding of several surface active
molecules was investigated, and the adsorption isotherms obtained are presented in
Figure 5. The results indicate that CaC0 3 binds the L-61 quite strongly in a Langmuir-
type adsorption, while Triton X-100 shows a Freundlich type adsorption isotherm
(commonly known asS-type); DSS is only weakly adsorbed. On the other hand, the same
surfactants were only faintly adsorbed by cement particles.
Effect of surfactants on paste rheology -- The addition of (non or low foaming) polymeric
surfactants to either CaC03 or cement pastes has only marginal effects on the rheological
parameters of these pastes (Table 5). The values of <o, G' and G" all remain relatively
constant through the range of surfactant concentration investigated in CaC0 3 pastes at
equilibrium pH(- 10), or at pH 12.5, as well as in cement pastes. In CaC0 3 pastes at pH
12.5, a low concentration ofL-61 reduces the G' and G" values by approximately 10%,
but little effect is observed at higher concentrations, or in other pastes; although this
effect is marginal, it may be real, considering the important influence of L-61 observed in
other properties described below.
In the presence of the foaming surfactants DSS and Triton, but without entrained air, the
yield stress values of all the pastes is decreased significantly; the elastic and loss moduli
also decrease moderately with increasing surfactant concentration (the paste pre-shearing
operation may entrain some air, which will also contribute to decrease G' and G"
values). These results point to a light fluidifying influence of the surfactants, which is
also manifested by a modest increase ofthe minis lump spread areas. On the other hand, if
air entrainment is allowed, the DSS surfactant induces a low increase in the yield stress of

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CaC0 3 pastes; this is consistent with a reduction in the minislump spread values observed
for these pastes (Table 5), and as generally found with mortars and concrete. The elastic
modulus is, however, decreased slightly, while the loss modulus is substantially reduced.
The results examined above support the conclusion that, at short times, the rheological
properties of cement and limestone pastes are not significantly altered by the surfactants
in the absence of entrained air. Any influence of the surfactants on interfacial tension,
drag reduction, or particle-particle interactions does not appear to modify the dynamic
response of the pastes under shear stress. In the presence of entrained air, the fluidity of
pastes is decreased; a modest increase in the yield stress values of pastes having high air
content suggests that the surface tension forces merge boundary films of neighboring air
voids into a network, which contributes to stabilize the whole sample volume. This is
further supported by a decrease of the phase angle value in air-containing pastes,
indicating an increased solid-like behavior.
Influence of surfactants on bleeding and consolidation
The influence of surfactants on the migration of water and solid particles may be quite
complex, since in contrast to rheological properties measured at very short times after
sample homogenization, the bleeding-sedimentation experiments extend over several
hours, during which the paste properties evolve continuously. The time evolution of
particle-particle interactions and of flocculation-consolidation processes will affect the
mechanism through which the solids can sediment or consolidate in the sample column,
as well as the water transport through and out of the consolidating materials.
In studies on settling processes in cement-based systems, Loh et. al (I?J concluded that
channeling can occur when the governing process is sedimentation in the upper part of
the sample, while consolidation is taking place in the sedimented zone at the bottom;
however, if the settling is due to consolidation only, no channeling should occur. The
bleeding and sedimentation curves derived from paste conductivity measurements show
an initial period of constant bleeding and constant sedimentation rates (Figure I). Beyond
the initial period, sharp increases in the bleeding and sedimentation rates are observed;
this observation points to changes in the mechanism of the phase separation process,
which can be attributed to the onset of channeling.
The data collected in Table 4 provides some indication on the influence of surfactant
admixtures on bleeding sedimentation processes. These will be examined in the same
order as that followed for examination of the rheolgical properties.
A cursory examination of the cumulative bleeding volumes collected over CaC03 and
cement pastes shows that, in the absence of entrained air, surfactants tend to slightly
increase the total bleeding volume, except perhaps for the CaC0 3 pastes with lime. In
pastes with entrained air, the total bleeding is substantially reduced, as expected from
observations in mortars and concrete (ISJ_ The bleeding volume increase is likely due to
the reduction of the interfacial tension of water, which provides increased spontaneous
access through small capillaries in the porous mass of the solids during sedimentation and
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
consolidation. A more detailed breakdown of the processes involved can be accomplished
using the rate parameters Qo, Qch and V,.
Initial bleeding and sedimentation rates -- The presence of surface-active compounds in

the CaC0 3 or cement pastes does not markedly influence their initial bleeding and
sedimentation kinetics, as indicated by the relative Q 0 and V, values. This is not too
surprising since the pastes investigated were design to have reasonable stability, with
relatively high solids contents (LIS=0.5 for limestone pastes and LIS=0.55 for cement
pastes). In such conditions, and especially when flocculation is important, the solid
particles may initially sediment in a cooperative fashion, irrespective of their particle size
(so-called zone settling 09 l). Examining minor differences and trends in Q0 values, the
low foaming glycol polymers (PEG, PPG and L-61) tend to slightly increase the rate of
the initial bleeding process in the limestone pastes; the limited data available in cement
pastes indicate that L-61 reduces bleeding slightly. DSS and Triton, both without air
entrained, tend to decrease bleeding very slightly. The initial sedimentation rates (V,) are
only marginally affected, though no definite trend is noticeable.
Accelerated bleeding and sedimentation at later stages from Ooh values -- As noted
earlier, in calcium carbonate pastes, the bleeding rate increases substantially after - 90-
120 min, as shown by the Qch values; the latter represents the steep downward slope of
the bleeding curve shown in Figure l. The important change occurring in the bleeding
process, and the concomitant sedimentation· consolidation processes, are significantly
affected by the presence of surfactants. In all limestone pastes investigated in the absence
of entrained air, all surfactants increase the Qch values (except PEG which has low
surface activity), reflecting a destabilization of the paste. The magnitude of the effect
depends on the nature and concentration of the surfactant; the destabilizing effect
manifested by the Qch values exhibit sharp variations as function of surfactant
concentration.
The introduction of PPG in limestone pastes induce a slight increase in the Qch rate
parameters, the other surfactants strongly enhance the Qch values. The most important
effect is observed with L-61 for which the bleeding-sedimentation (consolidation) curves
in limestone pastes are illustrated in Figure 6. As can bee seen from the bleeding curves,
the L-61 surfactant enhances bleeding at low concentrations, but stabilizes the pastes at
the higher concentration examined. A similar but less noticeable effect is observed in
systems containing Triton or DSS. The bleeding and sedimentation curves presented in
Figure 7 shows the influence of L-61 on limestone pastes in lime-saturated water; in the
latter, L-61 stabilizes the limestone paste at all concentrations tested.
When sufficient air entrainment is allowed in the paste, as with DSS added at the
beginning of the experiment, the Qch value decreases markedly. This is consistent with
observations on paste rheology, i.e., the presence of entrained air improves the stability of
the paste.
The influence of L-61 on the bleeding and sedimentation curves obtained with cement
pastes is shown in Figure 8. As noted earlier, channeling effects were not observed in the

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cement pastes studied here; in this case, L-61 (and Triton) induce only a slight decrease
in the early bleeding rate.
Mechanistic aspects-- The bleeding rate enhancement observed in the 1-2 hour period is
believed to be related to the onset of channeling through the consolidating sediment
column. In this framework, the ability of surfactant molecules to promote channeling in
limestone pastes (pH~ 10) apparently increases in the following order: DSS <Triton<
L-61. This order may be dictated by the intrinsic molecular features and solution
properties of the surfactants, namely, HLB, surface tension reduction, water binding, type
of micellar aggregate, solution viscosities, etc. However, because the water migration in
bleeding processes and the movement of solids in the sedimentation-consolidation
processes are inherently coupled, the impact of surfactants may also be determined by
their interaction with the solid particles, and the consequences of these interactions on
interparticle forces, static (interaction potentials) or dynamic (drag).
With respect to surface tension, it was found that, although PPG induces surface tension
reduction comparable to L-61 (Figure 4), its effect on bleeding and sedimentation
phenomena is negligible. Also from the surface tension data in Figure 4, the order of
surface tension lowering at the CMC of the various surfactants is Triton > DSS > L-61;
since L-61 is most potent for accelerating the bleeding and sedimentation, effects other
than surface tension reduction must be involved.
The surfactant concentration, at which the rate of the solid/liquid phase separation is the
most atiected, appears related to the CMC values of these surfactants in CaC0 3 -
saturated solutions (Figure 4). The concentrations of maximum effect for L-61 and Triton
X-100 are respectively 0.01 and 0.025 wt% with respect to the solids; this corresponds to
solution concentrations of ~5x 10-3 and ~1.3 x 10-2% (neglecting adsorption), which is
close to the CMC values of these surfactants. Hence the role of a surfactant in the
acceleration of phase separation processes is related to its ability to form micelles,
although, once micelle formation occurs, the surfactant effect levels-off (in spite of the
fact that much more surfactant is present in the system).
The propensity of surfactants to form micelles should be related to their HLB values
(within the same family of compounds). Attempts to correlate the de-stabilizing effects of
the surfactants on limestone pastes to their HLB values, however, failed to show a
significant relation.
On the basis of the above observations, the accelerating influence of surfactants on the
bleeding-sedimentation processes does not appear dominated by their solution properties.
On the other hand, the surfactant-particle interaction, as evidenced by the adsorption
isotherms presented in Figure 5, can be seen to play an important role. The surfactant
binding affinity, illustrated by the shape of the adsorption curve (extent of adsorption at
low concentration), increases in the order DSS <Triton< L-61, as does the surfactant
effect on paste destabilization.
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From these combined observations, it can be suggested that the action of the surfactants
in limestone paste bleeding and sedimentation is to alter particle-particle interactions
(interaction potential and drag forces), in a way similar to the action of a dispersant, i.e.,
deflocculating the particles, liberating water from the floc and allowing particle
sedimentation. Trends in bleeding rate variations observed as function of surfactant
concentration could then be explained as follows. At low surfactant concentration, the
reduced surface tension decreases capillary forces and facilitate water migration to
accelerate bleeding. As the surfactant concentration is raised, the solution viscosity
increases, reducing the migration rate of the liquid phase; moreover, glycol-type
molecules can bind water molecules and ions (particularly Ca+2), further reducing the
overall water mobility <20l. Hence, at high concentrations, the surfactant can act to reduce
bleeding and sedimentation, much as viscosity-enhancing admixtures. The use of
polyglycol-based admixtures has indeed been reported for that purpose <21 ).
CONCLUSION
The results derived from the present investigation indicate that surfactants, at
concentrations typical of concrete admixture dosages, can exert complex influences on
some of the properties of cementitious or model limestone pastes, even in the absence of
entrained air.
For a group of surfactants having widely different properties, detailed paste rheological
measurements demonstrated only marginal surfactant effects in the absence of entrained
air, up to 0.1 wt% dosages. Similarly, surfactants have little influence on the initial
bleeding and sedimentation of stable cement and limestone pastes. However, at longer
times, typically > 1 hour, surfactants can enhance the bleeding and sedimentation
processes associated to channel formation in the consolidating sediments; the magnitude
ofthe rate enhancement depends on the properties and concentration of the surfactants.
At low concentration (e.g., O.Olwt%), surfactants substantially increase channel

bleeding and consolidation rates, leading to a marked paste destabilization; a block co-
polymer non-foaming surfactant p(EG-PG-EG) is particularly effective in this respect.
This surfactant effect was attributed to a light dispersion action, similar to that of
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
plasticizers. At higher concentration, various other solution and interfacial interactions

compensate for the initial dispersing effect and channeling effects become similar to
those observed in the absence of surfactants.
The surfactant effects were observed mostly in limestone pastes; in the cement pastes
investigated here, the hydration reactions and products hinder the bleeding-consolidation
process after 1-2 hours, i.e., before channel bleeding becomes significant. Clearly,
however, in less stable cementitious systems (higher w/c, presence of retarders), channel
bleeding will likely set-in before the paste microstructure develops to stabilize the
systems. Surface active admixtures could then significantly alter the properties and
behavior of these materials.

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The usefulness of model limestone pastes to investigate the type of situation envisaged
here is readily apparent. Since it is hardly feasible to investigate all possible situations in
which cementitious systems will exhibit borderline stability, the limestone paste provides
background information on the influence of admixtures on a system which is not
stabilized by hydration effects.
REFERENCES
1. Jolicoeur, C., Nkinamubanzi, P.-C., Simard, M.-A. and Piotte, M. "Progress in

Understanding the Functional Properties of Superplasticizers in Fresh Concrete",
Proceedings of the 41h CANMET/ACI International Conference on Superplasticizers
and Other Chemical Admixtures in Concrete, Montreal, Canada, 1994, Malhotra,
V.M. (Ed.), ACI SP-148, pp. 63-88.
2. Pierre, A., Mercier, R., Foissy, A. and Lamarche, J.M. "The Adsorption of Cement
Superplasticizers onto Mineral Dispersions", Adsorpt. Sci. Technol., Q, 219-231
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Titanium Dioxide", J. Colloid Interface Sci., 96,275-287 (1983).
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du ciment sur le carbonate de calcium", Cern. Concr. Res., 19, 692-702 (1989).
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Molecular Parameters and the Effect of Comb-Type Superplasticizers on Self-
Compacting Concrete: A Comparison of Comb-type Superplasticizer Adsorption
onto a Basic CaC03 Medium in the Presence of Sodium Sulphate", Proceedings of
the 71h CANMET/ACI International Conference on Superplasticizers and Other
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Chemical Admixtures in Concrete, Berlin, 2003, Malhotra, V.M. (Ed.), SP-217-13,
pp. 195-209.
6. Sakai, E., Atarashi, D., Kawakami, A. and Daimon, M. "Influence of Molecular

Structure of Comb-Type Superplasticizers and Inorganic Electrolytes on the
Dispersion Mechanisms of Limestone Powder", Proceedings of the 71h
CANMET/ACI International Conference on Superplasticizers and Other Chemical
Admixtures in Concrete, Berlin, 2003, Malhotra, V.M. (Ed.), SP-217-25, pp. 381-
392.
7. Mikanovic, N., Jolicoeur, C., Khayat, K. and Page, M. "Model Systems for
Investigation of the Stability and Rheological Properties of Cement-Based
Materials", Proceedings of the 8'h CANMET/ACI International Conference on
Recent Advances in Concrete Technology, Montreal, Canada, 2006, Malhotra, V.M.
(Ed.), SP-235-22, pp. 323-356.

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```,-`-`,,`,,`,`,,`---
8. Mikanovic, N., Page, M. and Jolicoeur, C. "Aqueous CaC03 Dispersions as
Reference Systems for Early-Age Cementitious Materials", Colloids and Surfaces A:
Physicochemical and Engineering Aspects (in print).
9. Jolicoeur, C., Khayat, K.H., Pavate, T. and Page, M. "Evaluation of Effect of

Chemical Admixture and Supplementary Cementitious Materials on Stability of
Cement-Based Materials Using In-situ Conductivity Method", Proceedings of the 6th
CANMET/ACI International Conference on Superplasticizers and Other Chemical
Admixtures in Concrete, Nice, 2000, Malhotra, V.M. (Ed.), SP-195-29, pp. 461-483.
10. Pavate, T.V., Khayat, K.H. and Jolicoeur, C. "In-Situ Conductivity Method for
Monitoring Segregation, Bleeding, and Strength Development in Cement-Based
Materials", Proceedings of the 6th CANMET/ACI International Conference on
Superplasticizers and Other Chemical Admixtures in Concrete, Nice, 2000,
Malhotra, V.M. (Ed.), SP-195-33,pp. 535-559
11. Mikanovic, N. "Methode conductometrique pour !'etude des phenomt'mes de

ressuage et de sedimentation dans les materiaux cimentaires", Ph.D. Thesis,
Universite de Sherbrooke (Canada), 2006 (in preparation)
12. Saak, A.W., Jenning, H.M. and Shah, S.P. "Influence of Wall Slip on Yield Stress
and Viscoelastic Measurements of Cement Paste", Cern. Caner. Res., 11. 205-212
(2001).
13. APHA Standard Methods, 19th ed., p. 5-15, method 5220 D (1995).
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Paste. A Miniature Slump Test", Cern. Caner. Aggr., f. (2), 95-102 (1980).
15. Jolicoeur, C., To, T.C., Nguyen, T.S., Hill, R., and Page, M. "Investigation of
Physico-Chemical Aspect of Air Entrainment in Cementitious Systems",
Proceedings of the 7th CANMET/ACI International Conference on Superplasticizers
and Other Chemical Admixtures in Concrete, Berlin, 2003, Malhotra, V.M. (Ed.),
SP-217-39, pp. 595-619.
16. Shaw, D.J. "Introduction to Colloid and Surface Chemistry", 2"d Edition,
Butterworth & Co. Publishers Ltd., England, 1970.
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Bleeding and Channelling of Cement Paste and Mortar", Adv. Cern. Res., .ill( l ), 1-
16 (1998).
18. Powers, T.C. "The Properties of Fresh Concrete", John Wiley & Sons, Inc., New
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19. Fitch, E.B. "Sedimentation Process Fundamentals", Transactions of the American
Institute of Mining, Metallurgical and Petroleum Engineers, 223, 129-137 (1962).
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Soc. Cosmetic Chemists, _U, 201-213 (1962).
21. Mailvaganam, N. "Miscellaneous Admixtures". Concrete Admixture Handbook, 2nd

edition, Ramachandran V.S. (Ed.), Noyes Publication, Park Ridge, NJ, 1995, Chapter
15.
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Table 1 --Properties of Portland ~ement
Composition(%)
Chemical analysis
CaO 62.9
SiO, 21.0
AhO, 4.2
Fe,O, 3.1
MgO 2.3
so, 2.7
Na,Oeq. 0.76
Loss of ignition
Mineralogy
c,s(%) 52
c,s(%) 21.5
c,A(%) 5.7
C.AF(%) 9.5
Physicall!r!ll!erties
% passing45 ~ 96
Specific surface BET (m2/kg) 1200
Specific surface Blaine (m2/kg) 345
Table 2 -- Physical properties of selected CaC03 reference mineral and cement
Material Source Specific surface Average particle size

(m'/g) (!Jlll)
CaC0 3 OmyaCanada 1.2 10
Cement St-Laurent 1.2 20-30
Table 3 -- Physicochemical properties or selected surfactants
CMCat Ross-Miles
Surfactant Fonnula
Mw 25°C HLB foam height
(g/mol)
(o/om/v) (!nmj'
n-decyl
n-C 1oH21 0S0 3Na 260.3 0.8 40 150
sulfate Na
CsH 1,CJ{;O
Triton 625 1.5xl0"2 13.5 110
(CH,CH,O)..,ofl
HO(CH2CH20),·
Pluronics
(CH2CH(CH3)0)y- 2000 1.4xl0-3 3 10
L-61
(CH2CH20).H
PPG HO(CH2CH(CH3)0).H 1025 . 7.3 .
PEG HO(CH,CH,Ol,H 2000 . 25.3 .
* 0.1% solution

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Table 4- Stability of CaC03 and cement pastes
System stability
(~)
System Admixture Air Bleeding Qo Vs
(%) Jml)_ _(cm!h} Jcm!h}
<1.1 42. w us 4..0
0.01% DSS 2.9 35.5 0.15 0.4 3.0
0.025%DSS' 9.3 29.5 0.1 0.15 2.6
0.05%DSS' 16.2 17 0.04 - 2.45
0.01%DSS 0.4 44 0.35 0.95 4.0
0.05%DSS" 0.4 43.5 0.3 0.75 4.5
o.t% oss" 0.5 45 0.25-0.3 0.8 4.5
a
u..
0.005% Triton
0.01% Triton
< 0.1
<0.1
43.5
43.5
0.25-0.3
0.35
0.9
0.85
3.7
4.4
0.025% Triton <0.1 43 0.3 1.15 3.8
~ 0.05% Triton < 0.1 46 0.35 1.05 4.3
a
e 0.005%L-61 <0.1 44 0.4 1.15 . 4.35
e. 0.0!%L-6l < 0.1 44 0.4 1.5 4.6
.,....
0
0.025%L-61
0.05% L-61
< 0.1
< 0.1
43.5
43.5
0.5
0.4
1.2
1.15
4.0
4.3
::J 0.1%L-61 <0.1 45 0.25 0.8 4.3
O.Ol%PPG <0.1 44 0.35-0.4 0.6 3.9
0.05% PPG <0.1 45 0.4-0.45 0.7 4.2
O.l%PPG <0.1 44 0.35 0.65-0.7 4.15
0.15% PPG < 0.1 44 0.3 0.5-0.55 4.0
O.OI%PEG <0.1 41 0.35-0.4 0.65 4.35
0.05%PEG <0.1 40 0.4 0.55 4.0
O.l%PEG <0.1 44 0.4 0.65 4.4
<:l.t 30 tJ.lS -~ :M'
e 0.0 I% Triton < 0.1 26 0.2 - 5.1
!"l 0.025% Triton <0.1 26.5 0.2-0.25 - 4.7
i-=~i
0.05% Triton <0.1 25 0.2-0.25 - 5.45
O.Ol%L-61 <0.1 28 0.3 - 5.5
::J 0.025%L-61 <0.1 28 0.25 -- 5.7
..
0.05% L-61 <0.1
'~:f.}'
27
u
0.25
... 5.2
tt;.;
~.!
. ..
Ei ..
0.01% Triton
0.1% Triton
<0.1
<0.1
8.5
9
''"
0.3
0.25-0.3
-
--
6.2
5.8
uc. 0.01% L-61 < 0.1 10 0.25 8.2
0.1% L-61 <0.1 II 0.25 - 8,4
' Admixture added at tbe beginning of the mixing procedure directly in liquid phase
" Admixture added at the end of mixing procedure manually. All other surfactants were
added at the end of mixing procedure.

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Table 5 -- Rheological properties of CaC03 and cement pastes
Rheological properties
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
System Admixture Slump ~0 G' G" 0 flo

(mm) (Pa) (kPa) (kPa) {kPas)
<;~:~> >::~:~;;1:: '~':jlt~i';; Jj/}}/)L"rl(;\ ::,lilit 1>'::-'lTi"c,{
0.01%DSS 82 5 25.7 17.5 34.2
0.025%DSS' 79.5 5.8 23.6 13.4 29.6
0.05%DSS' 78.5 - - - -
0.01% DSS 83.5 4.65 27.8 20.7 36.7
0.05%DSS" 85.5 - - - -
0.1% DSS" 88 4.85 20.4 12.2 30.9
0.005% Triton 83.5 4.85 31.0 22.3 35.7
6v
~
. 0.01% Triton
0.025% Triton
84.5
87.5
4.65
4.5
27.7
27.5
19.2
17.2
34.7
32.0
0.05% Triton 88 4.4 14.7 8.5 30.0
s 0.005% L-61 84.5 4.6 29.0 20.6 35.4
~.... 0.01% L-61 4.8 36.1
85 29.9 21.8
,..."' 0.025% L-61
0.05%L-61
85.5
85
4.7
4.6
26.9
28.9
20.9
22
37.8
37.3
~ 0.1% L-61 86 - - -
0.01%PPG 83.5 4.8 27.7 21.9 38.3
0.05%PPG 84 4.7 28.5 21.6 37.2
0.1% PPG 84 4.65 28.0 20.4 36.1
0.15%PPG 84 4.7 28.1 20.6 36.2
0.01%PEG 82 4.85 30.5 23.3 37.4
0.05%PEG 84 5.2 32.0 24.0 36.9
O.I%PEG 85.5 5.0 32.1 24.0 36.8
s 0.01% Triton 75.5 7.8 60.0 39.2 33.2

........
~"'
[><
"' 0.025% Triton 80 6.8 51.5 33.6 33.2
!ii 0.05% Triton 80 6.6 36.0 22.1 31.5
'"=
"8=-
~
0.01%L-61
0.025% L-61
77
77
7.35
7.3
56.1
57.7
39.3
43.9
35.0
37.3
0.05%L-61 77 7.3 55.3 42.4 37.5
..."' ... 0.01% Triton 96 5.05
,5}
18.4 16.9 42.6
'
20
s ~ 0.1% Triton 98,5 4.8 15.6 14.2 42.3 21
d Q, 0.01% L-61 96,5 5.2 18.4 17.6 43.7 22
0.1% L-61 94 5.15 18.9 19.1 45.3 17.5
' Admixture added at the beginning of the mixing procedure directly in liquid phase
" Admixture added at the end of mixing procedure manually. All other surfactants were
added at the end of mixing procedure.

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10~---------------------------------,
(a)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
4
Time (h)
JOW-------------------------------~30
>t~ + •• (b)
f:
X
=s 15
~.
Position of •
sedimentation front
-.
+X
+X
.x
Position of
bleeding front
)
29
28
g +------· +~">+ XX
.::: 10
...
= ••
• Sedimentationl 27
~5 ; +Bleeding
-~ASTM C23~-.
0-=·~----.----.----....-----+26
0 4 8
Time (b)
Figure 1 -- (a) Typical conductivity curves obtained in experiments with CaC0 3 pastes
at L/S= o.s (pH- to); and (b) Bleeding and sedimentation curves derived from
conductivity measurements.

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100000
<><>~.,
•
Gj'
e:,
t?
1000 •
10
0,1
(a)
I
<>. 10
Shear stress (Pa)
100000
~
'i'
e:,
G
1000 •
(b)
g.
10
0,1 I 10
Shear stress (Pa)
Figure 2 --Rheological properties of reference CaC0 3 paste (L/S=o.s. pH-10) and

cement paste (L/5 =o.ss): (a) Elastic modulus (G'); and (b) Viscous modulus (G").
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Figure 3-- (a) Bleeding; and (b) sedimentation curves for reference CaC0 paste
3
(L/S=o.s. pH-to) and cement paste (L/5 =o.ss).
80
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
e:z; 0 x ..
......... ....
.- ..
v. 0 0 0
! 60
.
~ ~
·!= ill.:" • .. •)(
.
=
~
~
!l 40 .
i! XDSS
.L-61 -:t·~·.1"-x~-:.x ·><
"'"' .l TritonX-100
+PPG(M.W.J025)
0 PEG (M.W.2000)
t "
I ..
DSS
Triton
20
-5 -4 -3 -2 -I
LogC(%)
Figure 4 --Surface tension of surfactants in saturated CaC03 solutions as a function

ofthe concentration.

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0,5,----------r===:====:::;r
XNaC!OS04
i1il .L-61
..
~ 0,3
04
' A Triton X-100
~
.'"
!
~ 0,2
0,1
z
0,05 0,1 0,15 0,2

C(%wlw)
Figure 5 --Adsorption isotherms for surfactant molecules on CaC0 3 (solid lines) and
cement particles (dashed lines).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
•Reference
! ... 0.005% !Ail
..
."
-== 29
.0.01% L-61
X 0.025% !Ai 1
X0.05%L-61
1. •>¢Ill 0 •
00.1%!Ai1
·~ 0 • ----
'l; 28
•:u. • ::K • o 1M o
,g
~ (a)
27+------.----.----------~
0 6
Time (b)
30
Ez5
~
(b)
0
• • • ::1( 0 0
....
,g" 20 .X A 0 •Rc:ferc:ncc
... 0.005% L-61
e
115
.uo .0.01%L-61
lal(j.() X0.025% L-61
.....
:10
.. ~
X0.05%L-61
OO.l%L-61
~,. ~
(II:
0
a
0 4
Time (b)
Figure 6 -- Effect of the L-61 surfactant on the behavior of CaCO pastes

3
(L/S = o.s): (a) Bleeding kinetics; and (b) Sedimentation kinetics.

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!g
30
.... ~.
+Reference
.0.01%L-61
.
ol: 29,5
= ~~ :.;
& O.o25% L-61
X0.05%L-61
i
:;;; •
co
-~
29
• ·~•
l • I •
'
(a)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
28,5
4
Time (h)
!25
30
(b) • • •
X
X
;;
£20 •x •Reference
•o.oJ%L-61
:ae !5 ~
•x &0.025% L-6!
XO.OS~L-61
...
~
.,.
: 10
c
'!:
-~
=-
0
0
••- 4
Time (h)
Figure 7 -- Effect of L-61 surfactant on the behaviour of CaC0 3 pastes (L/S=o.s) in

saturated Ca(OH) 2 solution: (a) Bleeding kinetics; and (b) Sedimentation kinetics.

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30
e
~ •• i •.0.01% L-61
Reference
ij
..
0
-= 29,8 • .O.I%L--61
•!!!
....
..."
~ '·• .~
• t
'E 29,6
"
~
's:l • JJ ...
0
~ (a)
29,4
0 0,5 I 1,5 2,5
Time (h)
30
'""'
]Y
=
~ 20
(b)
ffi~ -I
eference
Ol%L--61
l%L-61
a
.... .......
115
...:w
0
<= •
• '
-~ 5
•
••
~
0
0 0,5 1,5 2,5
Time (h)
Figure 8 --Effect of L-61 surfactant on the behavior of cement paste (L/S=o.ss):

(a) Bleeding kinetics; and (b) Sedimentation kinetics.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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344 Mikanovic et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-23
Effect of Organic Admixtures on

Activation Process, Rheological
and Mechanical Properties and
Durability of Alkali-Activated Slag
Pastes and Mortars
by M. Palacios, F. Puertas, and P.F.G. Banfill
Synopsis: In the present work, the influence of two organic admixtures (a vinyl
copolymer and one based on polypropyleneglycol in the alkaline activation process
of blast furnace slag has been studied. The effect of these admixtures on the
rheological and mechanical properties, volume stability and durability ofwaterglass-
activated slag mortars has been studied.
The incorporation of these organic admixtures delays the activation
process of waterglass-activated slag pastes and, consequently, the initial and final
setting time. The presence of the admixtures also increases the total heat released
during the activation. Vinyl copolymer and shrinkage-reducing admixtures both
decrease the yield stress of waterglass-activated mortars during the first minutes
after mixing, and consequently, mortars with a lower liquid/solid ratio and higher
mechanical strengths are prepared. On the other hand, the incorporation of the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
polypropyleneglycol admixture decreases the shrinkage of the alkali-activated

slag mortars by up to 85%, however the vinyl copolymer increases the shrinkage
significantly at RH=so%. The addition of the organic admixtures does not improve the
durability of the alkali-activated slag mortars activated under carbonation. However,
the incorporation of organic admixtures does increase the residual strength of the
mortars after exposure to high temperatures.
Keywords: admixtures; alkaline cements; durability; rheology;

shrinkage; slag

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346 Palacios et at.
Marta Palacios holds a Dr. Sc. in Chemistry. She has been working at Eduardo
Torroja Institute on the effect of organic admixtures on the properties of
alkali-activated slag cements and mortars for several years.
Francisca Puertas holds a Dr. Sc. in Chemistry and is a Scientist Researcher at the
Eduardo Torroja Institute and she has been working on building materials for 20 years.
She is author or coauthor of more than I 00 papers and editor in chief of "Materiales de
Construcci6n".
Phil Banfill holds a Ph.D. in Construction Materials and has been Professor of
Construction Materials at Heriot-Watt University, Edinburgh since 1995. He is author or
coauthor of 2 books and over 50 papers on the rheology of cement based materials for
construction.
INTRODUCTION
The use of organic admixtures in the preparation of Portland concretes has become a
common practice during the last decades. Superplasticizers are the admixtures most
frequently used, and the resulting concrete has excellent rheological properties and a low
water/cement ratio, which ensures high strength and durability. Several authors (Mollah,
M. Y.A., et al, 2000; Berke, N. S. et al, 1997; Palacios, M. and Puertas, F., 2005) have
studied the mechanism governing the effect of these admixtures on Portland cement
systems, which consist of their adsorption on the cement particles, where the electrostatic
or steric repulsive forces generated prevent flocculation. Shrinkage-reducing admixtures
based on polypropyleneglycol, in turn, decrease the surface tension of the water in the
pores, reducing the capillary stress in the pore structure and, as a result, shrinkage when
the water evaporates (Berke, N. S. et al, 1997).
Nonetheless, very few studies have been conducted on the behaviour and properties
acquired by alkali-activated slag cements and mortars in the presence of these admixtures
(Palacios, M. and Puertas, F., 2005). Moreover, the results obtained vary widely due to
differences in the vitreous composition of the slag, the nature and concentration of the
alkali activator, and the type and dosage of the admixture used. Palacios and Puertas
(Palacios, M and Puertas, F., 2004; Palacios, M and Puertas, F., 2004-b) reported
substantially reduced fluidifying action by some superplasticizer admixtures, specifically
those based on polycarboxylates or vinyl copolymers, in alkali-activated slag systems as
a result of the modification of their chemical structure in highly basic media (pH> 13 ). By
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
contrast, a polypropyleneglycol-based admixture was found to be perfectly stable in such

basic media.
However, nothing is known about the effect that admixtures have on other properties of
alkali-activated slag (AAS) mortars. Consequently, the objective of the present study is to
analyze the influence of a vinyl copolymer superplasticizer admixture and a shrinkage-
reducing admixture based on polypropyleneglycol on the mechanical strength, shrinkage
and durability of AAS mortars.

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EXPERIMENTAL
Materials and mortar preparation
Spanish granulated blast-furnace slag and CEM I 42.5N Portland cement were used in
this study. The chemical composition of the two materials is shown in Table 1. The
fineness of the slag and the Portland cement were 325 and 360 m2/kg, respectively and
the vitreous content of the slag was 99%.
The blast furnace slag was activated with waterglass (Na20·nSi02 ·mH20 + NaOH)
solution with 4% Na20, by mass of slag, and a Na20/Si0 2 ratio in the range 1.0-1.2. I%
of a vinyl co-polymer (V) and I% of a shrinkage-reducing admixtures (SRA), by mass of
slag, were added to the alkaline solution.
Alkali-activated slag (AAS) and Portland cement mortars were prepared. The binder I
aggregate ratio used was 1:2 by mass. Spanish and European standard UNE-EN I96-I
sand with a Si02 (quartz) content of over 98% was used. The liquid/solid (Us) ratio used
was determined by the slump test described in Spanish standard UNE-80-1I6-86. The
composition of the different mortars prepared is shown in Table 2.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Tests conducted
- Mechanical strength
AAS and cement mortars (4 x 4 x 16 em) were prepared according to Spanish standard
UNE-I97-l. These waterglass-activated and cement specimens were cured for 48 hours
and 24 hours, respectively, at 20± 2 oc and 99% relative humidity (RH). They were
subsequently removed from the moulds and cured until the day of the strength test at 99%
relative humidity (RH).
The flexural and compressive strengths of the specimens were measured after 2, 7 and 28
days as specified in European standard UNE-EN 196-1.
- Mortar shrinkage
Prismatic specimens of waterglass-activated slag and Portland cement mortar measuring

2.5 x 2.5 x 28.7 em were prepared. The dosages of admixture incorporated to AAS were
1% of V and l% and 2% of SRA. The specimens were cured as described above and
placed in a humidity chamber at either 99% or 50% RH after removal from the moulds.
Shrinkage was determined as specified in Spanish standard UNE 80-112-89.
- Rheological behavior of the mortars
AAS and Portland cement mortars were prepared with a binder: sand ratio of 1:2. The
effect of 1% of the vinyl copolymer and the shrinkage-reducing admixure on the
rheological properties of the AAS mortars was studied.

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348 Palacios et al.
The 1/s ratio used to prepare the waterglass-activated slag and Portland cement mortars
were set at 0.58 and 0.42, respectively. The rheological behaviour of the mortars was
measured with a Schleibinger Gerate VISKOMA T NT rotational viscometer
(http://www.schleibinger.com (accessed 2711105))
The measuring procedure consisted of 5 cycles repeated at 4 to 22 minutes after mixing.

In each cycle the speed of rotation was increased from os· 1 to 3.3 s· 1 in 2 minutes, held at
3.3 s· 1 for 30s and then reduced to 0 s· 1 over another 2 minutes (Banfill, P.F.G., 1994).
- Durability
Cubic specimens (3-cm) of the mortars shown in Table 2 were prepared. The specimens
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
were kept in a moist chamber for 28 days, whereupon the respose to carbonation and
exposure to high temperature were studied.
Carbonation test
Mortars were placed in the carbonation chamber where the relative humidity was kept at
43.2% using a saturated K 2 C0 3 solution according to E 104-02 ASTM "Maintaining
Constant Relative Humidity by Means of Aqueous Solutions". The mortar specimens
were removed after four and eight months of exposure. Some of the specimens were
protected with insulating tape on all but one face. The chamber was COrsaturated by
filling it with the gas at atmospheric pressure twice a day.
The phenolphthalein test was used to measure the carbonation front on the side exposed
to C0 2 • Compressive strength, total porosity and average pore diameter, before and after
the carbonation, were measured.
High temperature test
Mortars were exposed for 2 hours to temperatures in the range 100°C-1 000°C.
Subsequently, the effect of the temperature exposure on the mechanical strength of the
mortars was determined.
RESULTS AND DISCUSION
Mechanical strength
The development of flexural and compressive strength of Portland cement and AAS slag
mortars, with and without admixtures, are given in Figure 1.
At 2 days of curing the mechanical strength of AAS mortars without admixtures are
lower than the mechanical strength of cement mortars. However, at 7 and 28 days of
curing the mortars present similar strength behaviour. The incorporation of organic
admixtures to the AAS mortars slightly increases the flexural and compressive strength
due to the decrease of the liquid/solid ratio that the admixtures induce.

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Shrinkage
Shrinkage of Portland cement and waterglass-activated slag mortars, with and without
admixture, under both curing conditions (99% and 50% RH), are given in Figure 2.
In both curing conditions, AAS mortars experience a shrinkage four times higher than the
cement mortars.
This difference in shrinkage is essentially due to two factors: on the one hand,
waterglass-activated slag mortars have a higher percentage of small pores (diameter<
0.01 ~-tm) (Shi, C. 1996; Shi, C., 1992), generating higher capillary stress in the pore
structure, and on the other, their C-S-H gel has a higher water content, which causes
greater shrinkage as water is lost during drying.
At RH=99%, the inclusion of 1% and 2% SRA reduced shrinkage by 50% and 85%,
respectively, with shrinkage values, in the latter case, similar to those recorded for
Portland cement. Shrinkage in waterglass-activated slag mortars containing the V
admixture was slightly smaller than in mortars with no admixture, although after 365
days the results were practically the same.
At RH=50%, the addition of 1% and 2% of SRA reduced drying shrinkage by 7% and

50%, respectively. Even so, these mortars shrank much more intensely than the Portland
cement mortars. Lastly, the inclusion of admixture V increased drying shrinkage by
nearly 50%.
The reduction of the shrinkage in waterglass-activated slag mortar in the presence of

SRA at both relative humidities is due, firstly, to the smaller amount of water used to
prepare the mortars and, secondly, the lower surface tension of the water in the pore
structure, which in turn facilitates its loss and reduces shrinkage by lowering the capillary
stress.
At RH=99%, admixture V reduces the shrinkage of waterglass-activated slag mortars

due to the slight reduction in the amount of water in the mix. However, at RH=50%
admixture V increases the drying shrinkage due to a refinement of the pore structure
caused by the superplasticizers that may increase capillary stress when the water
evaporates at RH=50% (Roncero, J et al, 2001). This would cause greater shrinkage than
in mortars with no such admixture.
Rheological behaviour of the mortars

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The flow curves (hysteresis loops) for waterglass-activated slag and Portland cement
mortars are given in Figure 3, and presented as torque on the impeller (proportional to
shear stress) and speed of rotation (proportional to shear rate).
There is a visible difference in the rheological behaviour of AAS and Portland cement
mortars. The curves for AAS mortars fit the Herschel-Bulkley curve (equation 1), while

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350 Palacios et al.
Portland cement mortars fit the Bingham model, and the downcurve (from the shear rate-
decreasing side of the loop is a straight line that fits equation 2 (Barifill, P.F.G., 1994).
't='to+ AfB equation I

1:=1:o+ J..lY equation 2
where 1 is the shear stress, 'to is the yield stress, J..l is the plastic viscosity , r
is the shear
rate and A and B are constants. The width of the hysteresis loop can be taken as an
indication of the extent of shear-induced structural breakdown during the test. This
appears to be more significant in the AAS mortars which suggests differences in the
water-binder interactions in the mortars.
A comparison of the yield stress values for the two types of mortar shows that this
rheological parameter is up to two times greater in Portland cement than AAS mortars.
This is an indication that the interactions between the floes formed are much stronger in
Portland cement mortars than in waterglass-activated slag mortars (Tattersall, G. H. and
Banjill. P. F. G., 1983). Taken with the comments on loop shape above this suggests that
further research on the rheology and structure of fresh AAS mortars is justified.
Fig. 4 shows that in waterglass-activated slag mortars, the admixtures initially reduced
the yield stress by up to 50%, although after 9 minutes, the presence of the admixture
induced no significant change in the value of this rheological parameter with respect to
AAS mortar without admixture. The loss of the fluidizying properties of the vinyl
copolymer in waterglass-activated slag systems is due to its instability in the highly
alkaline waterglass solution, which hydrolyses the admixture and changes its chemical
structure.
Durability
Carbonation
The phenolphthalein test showed that the carbonation front was no deeper than 1 mm in
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Portland cement. Carbonation was much more intense and deeper in the activated slag
mortars, however. The inclusion of admixtures V and SRA did not protect the interior of
the mortar specimens from carbonation.
Table 3 shows the strength values as carbonation advanced. Mechanical strength

increased in Portland cement mortar by 26% after 4 months of carbonation compared to
the 28-day values, although it remained virtually unchanged from four to eight months of
treatment.
In the absence of admixtures, the mechanical strength of waterglass-activated slag

mortars declined by 14% after 4 months of carbonation and remained unchanged through
the rest of the trial, i.e. to 8 months. The inclusion of admixtures V and SRA had no

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significant effect on the mechanical behaviour of mortar specimens subjected to
carbonation, although those containing admixture V showed higher strength values.
Table 4 gives the variation in total porosity and mean pore diameter for mortars A, B-1, C
and D at the three carbonation times. Total porosity declined slightly with carbonation
time in all cases, but most markedly in cement mortars. Whereas the mean pore diameter
increased significantly with carbonation in waterglass-activated slag mortars, it declined
substantially in cement mortars.
According to the phenolphthalein test, carbonation was deeper and more intense in
waterglass-activated slag than in Portland cement mortars, and this concurs with results
reported by other authors (Bakharev, T. et al, 2001). In Portland cement mortars, the
portlandite is carbonated first, quickly reacting with the C0 2 to form CaC0 3 •
Subsequently, as the amount ofportlandite begins to decline, the C-S-H gel is carbonated,
generating a mix of C-S-H gel with a low Ca content and silica gel. The precipitation of
CaC0 3 crystals in the pores reduces total porosity and mean pore diameter, obstructing
C0 2 diffusion through the mortar while at the same time increasing mechanical strength.
Conversely, as Bakharev (Bakharev, T. et al, 2001) concluded, in waterglass-activated
slag mortars the C-S-H gel is carbonated directly. The decalcification of this gel as a
result of carbonation causes a loss of cohesion in the matrix, owing to the increase in pore
diameter and causing a drop in mechanical strength. The presence of admixtures does not
appear to affect the carbonation resistance of waterglass-activated slag mortar.
High temperature treatment
Figure 5 shows the residual strength of the mortars after the high-temperature test.
Mechanical strength was significantly higher in Portland cement than waterglass-
activated slag mortar at all test temperatures except 1000 oc, where it was lower. The
inclusion of admixtures SRA and V increases the residual mechanical strength of AAS at
all the test temperatures.
The loss of mechanical strength in the mortars is due firstly to the elimination of free
water between I 00 and 200 oc (Georgali, B. et al, 2005). The loss of chemically bonded
water begins at around 250 °C, prompting the disintegration of the C-S-H gel. The a->P
transformation in the quartz comprising the aggregate takes place at around 550 °C, in
conjunction with the expansion of this mineral that causes deterioration of the mortar. In
Portland cement mortars, in tum, the portlandite dehydroxylation that takes place
between 400 and 500 oc entails an increase in porosity and therefore a greater decline in
mechanical strength than in waterglass-activated slag mortars, which have no portlandite.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
CONCLUSIONS
The main conclusions to be drawn from the present study are as follows:
1.- The inclusion of admixtures SRA and V in waterglass-activated slag mortar enhances
its strength slightly as a result of the minor decrease in the liquid/solid ratio induced.

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352 Palacios et at.
2.- Waterglass-activated slag mortar is slightly less stiff than an equivalent Portland
cement mortar and shows more complex shear-dependent rheology.
3.- SRA decreases waterglass-activated slag mortar shrinkage by up to 85% in specimens
stored at 99% relative humidity, and by up to 50% in samples stored at RH=SO%.
However, admixture V increases shrinkage in specimens stored at RH=SO%.
As far as durability is concerned, carbonation, with the consequent decline in mechanical
strength, is more intense and deeper in waterglass-activated slag than in Portland cement
mortars. The presence of admixtures does not appear to affect carbonation resistance in
waterglass-activated slag mortar. By contrast, the inclusion of admixtures SRA and V
raises the residual strength of activated slag mortar after high-temperature treatment.
ACKNOWLEDGEMENTS
The authors wish to thank the Ministry of Science and Technology for the funding for
project MA T200 1-1490, without which this study would not have been possible. The
authors wish to thank A. Gil and J. L. Garcia for their collaboration in the durability test.
M. Palacios also wishes to thank the Comunidad de Madrid for the fellowship awarded.
REFERENCES
Bakharev, T. et al, 2001; "Resistance of alkali-activated slag concrete to carbonation"

Cern. Co ncr. Res. 31, 1277-1283
Banfill, P.F.G., 1994; "Rheological methods for assessing the flow properties of mortar
and related materials", Constr. Build. Mater. 8, 43-50.
Berke, N. S. et al, 1997; "New Developments in Shrinkage-Reducing Admixtures"

CANMET/ACI S'h International Conference on Superplasticizers and Other Chemical
Admixtures in Concrete. Supplementary Papers. Ed. Malhotra 971-998
Georgali, B. and Tsakiridis, P-E., 2005; "Microstructure of fire-damaged concrete. A

case study". Cern. Concr. Comp., 27, 255-259
Mollah, M.Y.A. eta!, 2000; "A review of cement-superplasticizer interactions and their
models". Adv. Cern. Res., 12 (4) 153-161
Palacios, M. and Puertas, F., 2004; "Estabilidad de aditivos superplastificantes y

reductores de Ia retracci6n en medios fuertemente basicos" Mater. Construcc. VoL 54
(276) 65- 86
Palacios, M. and Puertas, F, 2004-b. "Effect of organic admixtures on the mechanical
behaviour of alkali-activated slag mortars". 8th CANMET/ACI International Conference
of Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete" Supplementary Papers
(Las Vegas) 497-511
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Palacios, M. and Puertas, F., 2005; "Effect of superplasticizer and shrinkage-reducing
admixtures on alkali-activated slag pastes and mortars" Cern. Concr. Res., 35, 1358-
1367
Roncero, J. et a!; 2001; "Influencia de los superplastificantes y aditivos reductores de

retracci6n en el comportamiento diferido del hormig6n estructural". V simposium
ANFAH
Shi C. et a!., 1992; "Comparison of the microstructure and performance of alkali-slag

and Portland cement pastes". Proc. 9'11 Int. Congr. On the Chemistry of Cement (New
Delhi), 3, 298-304
Shi, C. 1996; "Strength, pore structure and permeability of alkali-activated slag mortars"
Cem.Concr. Res. 26, 1789-1799
Tattersall, G. H. and Banfill. P. F. G., 1983; "The Rheology of Fresh Concrete". Pitman,
London
http://www.schleibinger .com (accessed 27I 1/05)

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Table 1.- Chemical composition ofblast-furnace slag and cement

CaO Si02 Al203 MgO Fe203 sol· sl· Na20 K20 L.O.l R.I
Slag 41.37 34.95 13.11 7.12 0.69 0.04 1.92 0.27 0.23 2.02 0.11
Cement 64.41 19.97 5.17 2.64 3.85 2.64 - 0.39 0.78 0.78 0.29
..
* L.O.I.: Loss of1grution; ** I.R.: Insoluble residue
Table 2.- Mortars prepared

MORTAR COMPOSffiON US RATIO
A Cement 0.42
B Slag+ Waterglass 0.58
C-1 Slag+ Waterglass + 1% SRA 0.55
C-2 Sial!;+ Waterl!;lass + 2% SRA 0.50
D Slag+ Waterglass + 1% V 0.55
Table 3.- Mechanical strength before and after carbonation

MECHANICAL STRENGTH (MPa)
MORTAR 28 days of curing 4 months of carbonation 8 months of carbonation
A 83.0 104.8 107.1
B 78.3 67.2 70.2
C-1 70.95 67.9 66.9
D 82.0 79.3 82.0

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354 Palacios et at.
Table 4.- Total porosity and average pore diameter of mortars before and after
carbonat"wn
Total porosity (%) Average pore diameter (urn)
MORTAR 28 days 4months 8 months 28 days 4months 8 months
carbonation carbonation carbonation carbonation
A 12.85 8.65 9.15 0.0419 0.0287 0.0449
B 11.00 11.64 9.91 0.0125 0.0300 0.0267
C-1 10.25 9.36 10.33 0.0110 0.0270 0.0286
D 10.30 IQ.42 9.83 0.0127 0.0433 0.0400
2 days 7 days 28days 2 days 7 days 28 days

CURING TIME CURING TIME
Fig. 1.- Mechanical strengths of mortars.
RHaSO%
--A
--8
- ... C·1
....,.._C2
- ... D
.,.
~ w
~z
.. iii! o.
:z:
. .... • • •
0
_....., ___ .......__.__.---·-·-
100
DAYS
200 300
Ill
0,
0, 0 --- 100 200

DAYS
300 -400
Fig. 2.- Shrinkage percentage in AAS and cement mortars under different curing
conditions: a) RH = 99%; and b) RH =so%.
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`,,,,```,-`-`,,`,,`,`,,`---
a) b)
WATERGLA5S-AC11VATED SLAG MORTARS
0_ 2 ;-------~C=EM=ENT::..:..:..._ _ _ _ _, 02,-----------------,
e CYCLE1
~ 0.1
!
! CYCL£2
CYCL£3
CYCLE4
cYCLE!
2 4
Speed of rotation (s·'l Speed of rotation (s''l
Fig. 3.- Rheological behavior of: a) cement; and b) AAS mortars.
0,06,--------.====;----,
0,05
---..._l~gl
£0,04
j., 0,03
·---.___ •
.... ...__
~ 0,02
0,01 ~l;;.;;~-::.:r:::"·""-""b:::----.!
10 15 20 25
Tlma (minutes)
Fig. 4.- Evolution of yield stress of cement and AAS mortars.

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356 Palacios et al.
-A
-- ·- B-1
......... c
---~-- D
~ ~ ~ ~ ~ ~ ~ ~ ~ m
1'emperatln r'C)
Fig. s.- Residual strength of cement and AAS mortars after high
temperature treatment.
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SP-239-24
Interaction between Cements and

Superplasticizers
by H. Lorn bois-Burger, L. Guillot, and C. Haehnel
Synopsis: The interaction between CEM I type cements and PolyCarboxylates

with PolyEthyleneOxide side chains superplasticizers was examined to clarify the
origin of incompatibility problems. Particular care was devoted to the possible role
of a competition between sulphates and superplasticizer in these issues. Both
laboratory and industrial cements were examined so as to analyze the influence of
set regulator amount and/or nature, and of alkali level. The study mainly focused
on the ionic composition of the aqueous solution, the consumption isotherms
of the superplasticizers and the rheology of cement grouts. The results showed
a major influence ofthe alkali sulphates of the clinker: the higher the latter, the
higher the concentration of sulphates in the aqueous solution and the lower the
superplasticizer consumption. The yield stress was correlated to superplasticizer
consumption: it decreased when the consumption increased. On the other hand, the
amount and nature of the set regulator appeared to induce a second order effect on
the aqueous phase composition and on the superplasticizer consumption.
Keywords: adsorption; aqueous phase; cement; interaction;

incompatibility; PEO side chains; polycarboxylate; rheology; sulphates;
superplasticizer
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358 Lorn bois-Burger et al.
H. Lombois-Burger, doctor engineer, is in charge of superplasticizers at technical centre
of Italcementi Group, Guerville, France, since 2003. She has been involved for three
years in research on extrudable cementitious formulations.
L. Guillot, as responsible of admixtures research team in "Materials, Technologies and

Admixtures" laboratory of French Italcementi Group Technical Centre (CTG),
coordinates development activity concerning organic products (superplasticizers,
thickening agents for concrete and mortars. At the same time, he has been strongly
involved in photocatalytic binders' research programs.
C. Haehnel is research laboratory responsible at technical centres of ltalcementi Group

since 2003. He is in charge of the development of new technologies, cements and
admixtures.
1 INTRODUCTION
Superplasticizers, and especially those made from PEO side chains grafted on a
PolyCarboxylate backbone (named PC-PEO afterwards), have greatly contributed to the
development of high performance concretes (HPC) and/or high fluidity concretes as Self
Compacting Concretes (SCC). These polymers adsorb onto cement grains surface. Thus,
they induce particles deflocculation, releasing the water trapped in cement floccs. Hence,
superplasticizers enable a reduction of the water required to reach a given fluidity level,
so that strength and durability are enhanced. Alternatively, superplasticizers can increase
the fluidity at constant water content, which confers a better flowability for the placing
and laying.
Superplasticizers should usually fulfill two requirements: their addition at reasonable
dosages (about 0.05 to I weight percent of dry matter with respect to cement) should
induce, in the cementitious formulations, both a good initial fluidity and a low fluidity
loss during the processing (fluidity retention for 1 or 2 hours). ln addition, it is required
that a given superplasticizer be active with the largest number of cements. Now, the
interaction between cements and PC-PEO depends on both PC-PEO molecular
architecture (backbone molar mass, side chains molar mass and grafting degree), and
cement composition. In fact, PC-PEO action is the result of a steric repulsion between the
side chains of the polymers adsorbed on the surface of cement grains. Superplasticizers
with high affinity for the surface of cement grains are bound to give good initial fluidity
(superplasticizer is rapidly adsorbed on cement grains) but important fluidity loss (little
superplasticizer remains in the aqueous phase to cover newly hydrated surfaces). On the
other hand, PC-PEO with low affinity for cement particles show a rather limited initial
fluidity (the coverage of grains by adsorbed layers of polymer is insufficient) but a rather
low fluidity loss since the aqueous phase behaves as a polymer reservoir for later
adsorption on newly hydrated surfaces.
Incompatibility issues are a well-known concern; they include poor initial fluidity for
usual superplasticizers amounts, as well as excessive fluidity loss during concrete
processing. The literature on this subject has mentioned various hypotheses to rationalize
the behaviors observed. Among these, the idea that part of the superplasticizer would be
lost by incorporation into organo-mineral phases should not be the explanation for PC-
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PEO, since very few PC-PEO is so used [1], contrary to polynaphtalene sulfonates [2-4].
The competition between sulphates and superplasticizer in adsorption process seems to
be the key factor [5-6]. Now, what matters is not the dry sulphate content but the
sulphates solubility rates [7-8]. In this respect, the solubility rates of clinker's alkali
sulphates are much more important than the solubility rates of set regulator's calcium
sulphates [7-9]. This factor might explain why alkalis have long been considered as the
key factor for cements I superplasticizers incompatibility since they probably govern the
amount of soluble sulphates conditioning the adsorption competition with
superplasticizer.
This work studies the influence of alkali sulphates content and set regulator content
and/or amount on the interaction between superplasticizers and cements. We analyzed the
aqueous phase composition, the superplasticizer consumption by cement and the
rheological behavior of cement grouts in order to clarify the conditions of cements I
superplasticizers interaction.
2 EXPERIMENTAL STUDY
2.1 Materials
Two Axim-Italcementi Group PC-PEO superplasticizers (named SPl and SP2, main
characteristics in Table 1 ) designed to show low fluidity loss (generally used for ready
mix concrete) were tested respectively with six laboratory CEM I type Portland cements,
and six Ciments Calcia-Italcementi Group industrial CEM I type cements. The laboratory
cements were prepared so as to control cement composition (that it be clinker's chemistry
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
or set regulator nature and amount) and Blaine specific surface area. In this respect, it
was chosen to analyze, at constant Blaine specific surface area, the influence of alkali
sulphate level, while the nature of set regulator was fixed but its amount was varied.
However, these laboratory cements only present two alkali levels. The six industrial
cements were then selected so as to increase the number of different alkali levels
considered. However, the use of industrial cements allowed to control neither Blaine
specific surface area, nor set regulator's nature nor amount.
The 6 laboratory cements were obtained by grinding two Ciments Calcia-Italcementi
Group clinkers (named K1 and K2) with various amounts of a quite pure industrial
gypsum (more than 93 weight%) to reach a 4000 cm2 /g Blaine specific surface area. The
two clinkers were selected for their quite similar contents in silicate and aluminate phases
(respectively C3S+C2S and C3A+C4AF molar %), but varying alkali amount and
C3A/C 4AF molar ratio (Table 2). In these clinkers, the values of the molar ratio (Na20 +
K20)/S0 3 suggest that most of the sulphates are under the form of alkali sulphates in Kl
(the ratio is about I) [7], whereas in K2 the sulphates exceed the stoichiometric quantity
of alkalis available. According to H. F. W. Taylor [7], calcium langbeinite
(2CaS04.K2S0 4) should then form. Gypsum content was varied to obtain, for each
clinker, three cements of S03/C weight ratio respectively optimal in terms of strength, or
inferior or superior of about 0.5 weight % to this optimal value (Table 3). These ratios
were respectively named Opt, Opt- and Opt+.
The 6 CEM I type industrial cements studied with SP2 are referenced from Cl to C6.
Their main characteristics are listed in Table 4. The molar percentages of silicate and
aluminate phases determined with Rietveld analysis from XRD diagrams are calculated

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360 Lombois-Burger et al.
with regard to the 4 major phases (CJS, C2S, C3A and C4AF), and the composition of set
regulator is calculated using results of Rietveld analysis from XRD diagrams and
Differential Scanning Calorimetry. Alkali contents increase from C 1 to C6. Among the 4
major phases, the main difference is brought by the variation of C3A/C 4AF molar ratio.
The proportion of gypsum, hemihydrate and anhydrite in the set regulator differs for the
six cements considered. The Blaine specific surface area is about 4000 cm2 /g with the
largest deviation shown by C4.
For both laboratory and industrial cements, grouts of constant water content (W/C=0.44),
and varying PC-PEO content (SP/C), expressed as the weight percentage of
superplasticizer's dry matter with regard to cement, were studied.
2.2 Experimental techniques

Cement grouts were obtained mixing the liquid (water + superplasticizer) with the solid
during 3 min with a helix Bioblock Scientifix mixer. The contact between liquid and
solid was taken as time origin. Two time scales were explored: 15 min as representative
for initial behavior (beginning of grout manipulation) and 90 min to assess fluidity loss
on a time-scale typical of a usual processing window.
Aqueous solutions were extracted from grouts by a 10 min centrifugation at 4000 rpm
with a 5804R centrifuge from Eppendorf.
Ionic concentrations in the aqueous solution were measured by Inductively Coupled
Plasma - Atomic Emission Spectroscopy (ICP-AES) at 1150 Watts with an Iris
Advantage radial from ThermoEiectron. For each cement, measurements were performed
on aqueous solutions extracted after 15 and 90 min from either plain grouts (SP/C=O%)
or from grouts with SP/C=0.40%. Analyses were performed after dilution and
acidification at 5 volume % of HN03 at 65% of the aqueous phases. Only the major
species concentrations, that is to say Ca, K, Na and S, were measured.
PC-PEO isotherms were measured at room temperature, after 15 or 90 min, using the
Chemical Oxygen Demand technique. The latter enables one to measure the
concentration of species, oxidizable by Cr2ol-, from the titration of excess bichromate.
This requires, first, to calibrate the "oxidability" by Cr20/- of the PC-PEO considered.
Moreover, for a given time, the Cr20/- consumption of the aqueous solution extracted
from plain grout was subtracted from the measurement on the aqueous solutions extracted
from grouts containing superplasticizer. The superplasticizer consumption was deduced
from the reduction of PC-PEO concentration in solution following contact with cement. It
was interpreted as an adsorption in the following. Contrary to "usual" adsorption
isotherms, we do not proceed to an equilibrium measurement. Cement is an evolving
system, but this measurement, at a given time, is representative of the conditions
experienced by the system. Isotherms plot the weight of superplasticizer consumed by
gram of cement, Qcons (in milligrams of superplasticizer per gram of cement) versus the
concentration of superplasticizer in aqueous solution extracted from the grout, CAs
(expressed in grams of superplasticizer per gram of aqueous solution).
Rheological measurements were performed on an AR 1000 N controlled stress rheometer
from TA Instruments, with a non-conventional, Couette-equivalent, geometry of anchor
type. The latter is equivalent to a virtual cylinder with inner radius Ri = 19.40 mm and
height h = 44.0 mm, immersed in a Couette cell with outer radius R, = 25.0 mm. Every
15 min, the grout was submitted to a I min pre-shear (to remix the sample and cancel its
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mechanical history) followed by a 1 min rest and then a stress sweep from 7.8 10--4 to 768
Pa in 7 min 30 s, measuring 100 logarithmically spaced points per decade. This procedure
enables one to use a single measurement kinetic for all grouts, which would not be
possible with a stationary state measurement. Hence, the latter is ill-adapted for time
evolving materials like cements. Occasionally, yield stress value was confirmed with a
creep measurement performed in 1 min.
3 RESULTS AND DISCUSSION
3.1 Laboratory cements

All the experiments with laboratory cements were performed with the superplasticizer
SPI.
3.1.1 Ionic composition of the aqueous phase

As illustrated in Fig. 1 for sulphur, we observe for Ca, K, Na and S concentrations that:
./ the composition of the aqueous solution is very rapidly fixed since no significant
evolution is observed between 15 and 90 min;
./ the key parameter is clinker's chemistry since we observe major differences
between Kl and K2 cements, but no dependence on gypsum content (S0 3/C =Opt-, Opt
or Opt+) for a given clinker;
./ superplasticizer's addition induce no noticeable effect since the results for grouts
containing 0.40 %of SP 1 are the same as those for plain grouts (SP/C = 0% ).
Under the experimental conditions explored (time- 15 or 90 min-, S03/C ratio for a
given clinker - Opt-, Opt or Opt+ -, and SPl content - SP/C = 0 % or 0.40 %) no
significant variation of Ca, K, Na and S concentrations was found. We thus selected one
among them (explicitly S03/C = Opt, 15 min, SP/C = 0%) for which we plotted the
concentrations in the aqueous solution versus the amount of Na20 equivalents in the
clinker, named Na20eqck (Fig. 2). [Na] and [K] increase with Na20eqck: the higher the
alkali content in the clinker, the higher the alkali concentrations in the aqueous solution,
as expected below saturation conditions. Correspondingly, the sulphur concentration
(assimilated to sulphate content) increases. This validates the idea that the sulphate
concentration in the aqueous solution is mainly driven by the alkali sulphates of the
clinker. These results are in agreement with those of L. Nachbaur [10]. He measured
sulphate concentrations in portlandite saturated solutions (which were or not saturated
with respect to calcium sulphate), which increased with [K]. Fig. 3 plots the molar ratio
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
([Na]+[K])/(2.[S]) of concentrations measured by ICP-AES in the aqueous solutions

versus the weight ratio S03/C of the cements. This ratio is constant for the six studied
cements, and exceeds 1. Nevertheless, the value of about 1.6 found can be due to
sulphates precipitation to form ettringite (AF,) [7]. The fact that part of the alkalis
originates from inclusions in silicate and aluminate phases is doubtful. Indeed, such
inclusions only appear [7] if clinker contains more alkalis than the quantity required to
combine to the whole S03, what is not the case for the two clinkers considered (Table 2).
Finally, the concentration of calcium ions decreases with Na20eqc\ what could be
considered as linked to the correlative increase of potassium ions. As a matter of fact, L.
Nachbaur [10] measured [Ca] concentrations, in portlandite saturated potassium

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solutions, which decreased when [K] increased from 0 to 0.5 mol/kg. These
concentrations were in agreement with the ones calculated using the software PHRQPITZ
[11] which uses Pitzer's equations to calculate activity coefficients for very high ionic
force environments.
3.1.2 Superplasticizer consumption

As shown in Fig. 4, SPl isotherms are of type II [12] for all the cements considered. In
fact, for low CAs (typically, CAs < 0.005 g SP I g AS), the SPl affinity for cement is
moderate (the curve's initial slope is non-infinite). At higher CAs (CAs > 0.005 g SP I g
AS), curves go on increasing with a positive slope which suggests the progressive
constitution of multilayers. The interaction energy between layers is similar to the
interaction energy between the cement surface and the first monolayer. In cements I PC-
PEO systems, it can be expected that these two interaction energies be similar since both
interactions involve calcium ions. In fact, the first monolayer adsorbs on cement grains
through an ionic bond between carboxylates and calcium ions in the double layer of
cement grains. Similarly, calcium ions from the aqueous solution can bridge polymer
molecules by an interaction with two carboxylate sites.
Because of their type II form, these isotherms can be fitted by a BET-type equation:
Q = Qo.K.CAs
cons (1-CAs).(l+(K-l).CAs),
where Q0 is the superplasticizer weight involved into the first monolayer and K is an
affinity constant. The fit was performed on the linearization of BET equation, that is to
say the plot of CAS versus CAs which, for a BET law, leads to a line with
Qcons·(l-CAs)
slope (K-l)I(Q 0 .K) and a y-intercept li(Q0 .K). While Q 0 determination, essentially linked
to inverse slope's value, is quite precise, K determination is much more uncertain because
small y-intercept variations lead to huge K-variations. These uncertainties are integrated
into error bars on the values obtained. These parameters are plotted versus SOiC ratio for
K I and K2 cements in Fig. 5.
We observe that Kl cements, whose aqueous solutions are more concentrated in
sulphates than those of K2 cements, show a higher adsorption (higher Q0 than that of K2
cement for equivalent K value for Opt cements; a reverse situation is observed for Opt-
and Opt+ cements).
In addition, adsorption by Kl cements increases more between 15 and 90 minutes than
the adsorption by K2 cements.
Finally, gypsum content variations through SOiC ratio influence, even though weakly,
the adsorption (Q0 is maximum and K minimum for Kl Opt cements, the K-situation is
reversed and Q 0 more or less constant for K2 cements), whereas sulphate concentration in
the aqueous solution is not affected. On the whole, it seems that the higher the sulphate
concentration in the aqueous solution, the lower the SP 1 adsorption because of a
competition with sulphates, since the S031C ratio is a second order parameter as
compared to clinker's chemistry. Nevertheless, a complete balance of the sulphates (in
aqueous phase, or integrated in mineral phases as AF 1 for instance, or adsorbed) is
required for a better correlation between the sulphate concentration in aqueous solution

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on the one hand, and the quantity of sulphates adsorbed onto calcium sites of the double
layer to the detriment of SPl on the other hand.
3.1.3 Rheological behavior of the grouts

As shown for Kl Opt cement in Fig. 6, the yield stress, ty, decreases while SPl content
increases on the whole time-range explored. For high SPl's dosages, severe bleeding and
sedimentation occurred, so that rheological measurement on the grouts could no longer
be pursued (as it is the case at SP/C=0.36% after 30 min here). Moreover, Fig. 6 shows
that while ty increases with time for SP/C=O%, it decreases in the presence of SPI. This
fluidity time-increase is explained by an increase of SPl 's adsorption (more pronounced
for KI than for K2 cements as seen in 3.1.2) leading to a higher surface coverage by
adsorbed superplasticizer, which gives rise to more important repulsive forces between
cement grains.
The yield stress was plotted versus SP I 's calculated consumption, Ocons• at the same
time (Fig. 7). We observe a good correlation in the form of ty = A/Qcons between these
two quantities, with a common curve for all cements at each given time, 15 or 90 min
(R2 = 0.89 and 0.85 respectively after 15 and 90 min for the linear fit of l!ty as a function
of Qcons). Thus, the fluidity which is all the lower as the yield stress is higher, increases
with the SPl consumption. Finally, major bleeding and sedimentation were observed for
Ocons of about 1 mg/g, that is to say quantities below Q0 • This means that good quality
cement-based products require quantities of superplasticizer slightly inferior to Q 0 • They
will hence present an unsaturated first monolayer.
3.2 Industrial CEM I type cements

All the experiments with industrial cements were performed with the superplasticizer
SP2.
3.2.1 Ionic composition of the aqueous solutions

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The main conclusions are the same than for laboratory cements (3. I. I):
./ The composition of the aqueous solution is rapidly fixed by the cement
chemistry. Neither duration (15 or 90 min), nor superplasticizer dosage (SP/C = 0 or 0.40
%) modify (beyond experimental error) the values of theCa, K, Na or S concentrations
measured for one given cement.
./ Consequently, one of the experimental conditions, namely SP/C = 0 % and 15
min, is chosen to discuss the variations of calcium, alkalis and sulphate concentrations
(respectively noted [Ca], [Na]+[K] and [S]) versus Na20eq (Fig. 8)). Alkalis and sulphate
concentrations in the aqueous solution increase with Na2 0eq whereas calcium ions
concentration decreases. Calcium and sulphate concentrations in the aqueous solution
were plotted versus potassium concentration in the aqueous solution (Fig. 9): in
agreement with the results ofL. Nachbaur [10], we observe that [Ca] decreases while [S]
increases with [K]. Our interpretation is that the solubility ofportlandite is reduced in the
presence of increasing concentrations of potassium, and that most of the soluble sulphates
originate from alkali sulphates from the clinker phases.

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./ The molar ratio ([Na]+[K])/(2.[S]) (plotted versus Na20eq in Fig. 10) is about
1.6, except for Cl (points at the lowest Na20eq content). For C2 to C6, the alkalis are thus
in excess with respect to the sulphates, as compared for what would result from a
stoichiometric dissolution of alkali sulphates. Once more, this discrepancy might come
from the precipitation of ettringite. On the opposite, in C 1, alkalis are in excess with
respect to sulphates: part of the alkalis might come from inclusions in silicate and
aluminate phases [7].
As Na20eq on its own explains the 6 cements behaviors, it seems that, at least for the
materials here studied, neither the set regulator composition, nor its amount, should play
any first order role.
3.2.2 Superplasticizer consumption

The consumption isotherms of SP2 by the 6 CEM I type industrial cements after 15 and
90 min are represented in Fig. 11. We observe that Qcons decreases from Cl to C6, that is
to say the richer in alkalis is the cement, the lower is the adsorption. It is not clear
whether these isotherms show a positive slope at "high" CAs (CAs > 0.005 g SP I gAS) as
the laboratory cements isotherms (type II isotherms described in 3 .1.2, fitted with a BET-
type equation), or a plateau value (isotherms of type I fitted with a Langmuir-type
equation). Nevertheless, on the range of CAs considered (CAs < 0.020 g SP I g AS), the
difference between these 2 models (Langmuir and BET) is negligible. So, in order to
compare with laboratory cements, we chose to fit the isotherms of the 6 industrial
cements with a BET equation. The parameters of the latter, Q0 and K, after 15 or 90 min,
are drawn versus the sulphate concentration measured in plain grouts aqueous solution
after the same time, [S]As, in Fig. 12. Indeed, as superplasticizer content (0 or 0.40 %)
was shown not to modifY the sulphate concentration in the aqueous solution, the value
measured for plain grouts is judged representative of the whole SP/C range of
consumption isotherms (SP/C = 0 to 0.8 %). We find that Q0 decreases while [S]As
increases. This reinforces the idea of a competitive adsorption between sulphates and
superplasticizer, with a number of adsorption sites occupied by sulphates instead of PC-
PEO all the more important as the concentration of soluble sulphates (those available in
the aqueous solution) is higher. In addition, Q0 increases from 15 to 90 min. For what
concerns the affinity, K, as a function of [S]As, we observe a bell-shape curve with a
maximum affinity for an intermediate sulphate concentration in the aqueous solution,
what we are not able to explain yet.
The fact that [S]As seems to be the parameter controlling the adsorption reinforces the
idea that the set regulator composition, or the amount used, are irrelevant in the
interaction between SP2 and the 6 industrial cements considered.
3.2.3 Rheological behavior of the grouts

Only the results after 15 min will be considered here, and no measurements were done
with C4. As expected, for each cement, the yield stress decreases while SP/C increases
(Fig. 13). In addition, for a given SP/C value, the yield stress increases from Cl to C6
while adsorption (Qcons) decreases, which we interpreted as a result of the competition
with sulphates.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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For each cement grout, the SP2 consumption, Qcons. corresponding to the weight ratio
SP/C of the grout was calculated. We defined a reduced yield stress value by
dividing the yield stress of the superplasticized grout, ty sPtc, by the plain grout yield
stress value of the same cement, ty0%. This relative yield stress was plotted versus the
normalized superplasticizer's consumption, Qcons/Q 0 (Fig. 14). For a given value of
Qcon/Qo, the relative yield stress increases from Cl to C5: the lower the Na20eq ratio, the
lower the sulphate concentration in the aqueous solution, the larger the decrease of
relative yield stress. Moreover, the relative yield stress decreases for a "critical" value of
Qcon/Qo which is all the lower as Na20eq ratio is lower. This means that what matters is
not only the percentage of adsorption sites of SP2 which are occupied for the
superplasticizer content considered, but also the total number of adsorption sites of SP2,
Q0 . We have evidenced that the latter directly depends on the competition with sulphates:
for a more or less constant initial Blaine specific surface area, the larger the amount of
available sulphates (those which are in the aqueous phase), the lower is the total quantity
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
of adsorption sites for SP2.
4 CONCLUSION
The results on laboratory and industrial CEM I type cements illustrated the influence of
cement composition and especially clinker chemistry. As a matter of fact, the quantity of
sulphates present in the aqueous phase is governed by the alkali level: the rapidly soluble
sulphates are the alkali sulphates of the clinker. In addition, the higher the sulphate
concentration in the aqueous solution, the lower is the superplasticizer's adsorption. For
laboratory cements, the distinction, between the respective influence of the number of
adsorption sites and their affinity, in the variations of superplasticizer's adsorption is not
yet explained. Nevertheless, the yield stress level is governed by the superplasticizer
adsorption (for a given time, we obtain a common curve for the 6 laboratory cements
considered). For industrial cements, the number of adsorption sites of the superplasticizer
decreases while the sulphate concentration in the aqueous solution increases. This
reinforces the idea that this species is in competition with superplasticizer from an
adsorption point of view. Correspondingly, for a given superplasticizer dosage, the yield
stress of the grout is all the higher (and so the fluidity all the lower) as the number of
adsorption sites for superplasticizer is lower. Finally, we evidenced that set regulator
composition and its amount were, in the cements considered, at most second order
parameters. Indeed, concentrations in the aqueous solution (especially sulphate
concentration), adsorption level and thus yield stress value of the grouts were mostly
governed by clinker's chemistry.
5 REFERENCES
[1} Fernon, V., Vichot, A. et al., Interaction between Portland cement hydrates and
polynaphtalene sulfonates, 51h CANMET, SP173, 225-248 (1997).
[2} Flatt, R., Houst, Y, A simplified view on chemical effects perturbing the action oj
superplasticizers, Cement and Concrete Research, 31, 1169-1176 (2001).

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366 Lombois-Burger et at.
[3] Uchikawa, H, Sawaki, D., Hanehara, S., Influence of kind and added timing oj
organic admixture on the composition, structure and property of fresh cement paste,
Cement and Concrete Research, 25, 353-364 (1995).
[4] Yamada, K., Hanehara, S., Interaction mechanism of cement and superplasticizers -
The roles of polymer adsorption and ionic conditions on aqueous phase, Concrete
Science and Engineering, 3, 135-145 (2001).
[5] Yamada, K., Ogawa, S., Hanehara, S., Controlling of the adsorption and dispersing
force of polycarboxylate-type superplasticizer by sulfate ion concentration in aqueous
phase, Cement and Concrete Research, 31, 375-383 (2001).
[6] Jiang, S., Kim, B., Artcin, P. C., Importance of adequate soluble alkali content to
ensure cement I superplasticizer compatibility, Cement and Concrete Research, 29, 71-78
(1999).
[7] Taylor, H F. W, Cement Chemistry, 2"d ed, Thomas Telford ed (1997).
[8] Prince, W., Espagne, M, Ai"fcin, P.C., Ettringiteformation: A crucial step in cement
- superplasticizer compatibility, Cement and Concrete Research, 33, 635-641 (2003).
[9] Tagnit-Hamou, A., Artcin, P.-C., Cement and superplasticizer compatibility, World
Cement, 38-42 (2003).
[10] Nachbaur, L., Etude de /'influence d'electrolytes sur l'hydratation et Ia prise du
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
silicate tricalcique, composant principal du ciment Portland. Caracterisation des
interactions al'origine de Ia prise, PhD thesis, Universite de Bourgogne (1 997).
[11] Plummer, L. N., Parkhurst, D. L., Flemming, G. W., Dunkle, S. A., A computer
program incorporating Pitzer's equation for calculation of geochemical reactions in
brines, U.S. Geological Survey, Water Ressources Investigations Report 88-4153 (1988).
[12] Sun, L.-M, Meunier, F., Techniques de l'Ingenieur, Adsorption, Aspects theoriques,
12-730, 1-16 (2003).

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Table 1: characteristics of the two superp1asticizers.
SP 1 SP2
Bakbone composition methacrylate methacrylate and acrylate
(75/25 n!n)
Grafting degree (% nln) "30 "40
Length ofPEO side chains (number of "so 2lengths: "40 and"' ISO
unit monomers}
Mw{g/moll 15.000 100.000
Po1ydispersity index (M.IMw) not 2.7
determined
Table 2: characteristics of the two clinkers.
Technique Quantity Kl K2
C3S+C2S 85.4 88.9
XRD, Rietveld analysis C3S/C2S 2.2 2.5
(n/n %) C3A+C.0,F 11.2 7.1
C3A/C.0,F 0.7 1.3
Na20-= 0.24 0.61
XRF (w/w%)
sol 0.32 1.35
XRF(n/n) Oia20+K20_2/ SOl 0.97 0.59
Table 3: values of SOJC weight ratio for the six laboratory cements measured with a
sulphur analyzer.
SO)IC Opt- Opt Opt+
Clinker
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Kl 2.3 2.9 3.3
K2 2.8 3.6 4.0
Table 4: main characteristics of the CEM I type industrial cements.

Technl
que
Quantity Unit Cl C2 C3 C4 cs C6
XRF Na,P.., % O.o7 026 0.37 0.53 0.74 1.07
Sulphur totalS~ w/w
2.8 2.6 1.7 3.3 3.7 3.2
anaivzer
XRD, C3S-+C,S %n!n 97.4 902 92.0 90.6 85.4 90.5
Rietveld C,A+C.AF 2.6 9.8 8.0 9.4 14.6 9.5
analysis CJS/~ n!n 2.9 2.4 3.9 2.1 9.1 22
~C-tAf (X) 0.5 02 0.2 8.5 0.6
Set reguiatnr %~
4&23/30 8410126 33122/44 018192 77/23/0 79/21/0
composition (gypsum eq
I hemihydrate I
anhvilrne)
Blaine specific surface cm2/g 4100
4300 4400 4800 3850 3950
area
Median diameter !liD 10.9 10.8 9.1 10.2 13.1 12.8

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125 K2tpt- K2 tt K2 fpt+
~~;o:===~=~==;~;::••=f
100
K1 K2
--- -B- SP/C = 0%, 15 min
----- - e- SP/C = 0 %, 90 min
-4--- -A- SP/C = 0.40 %, 15 min
--+-- - +- SP/C = 0.40 %, 90 min
25
U U U U ~ U M U U U
SOsfC (wiw%)
Figure 1: Sulphur concentrations in the aque~us phase versus 50/C ratio of

laboratory cements w1th SP1.
.--..
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~E
E
....... 100
·~
~
cl.
0
II
if
</)
g
10
0.25 0.30 0.35 0.~0 0.45 0.50 0.55
Na 20eqc (wlw %)
Figure 2: Concentrations in the aqueous solutions of plain grouts (SP/C = o%) after
15 min versus the weight ratio Na 2 0eq of the clinker.

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~ 2.0
l
~
~
1.5
1.0
f----W-+1---i
K1 K2
~
• 0 SP/C = 0%,15 min
0.5 •• 0 SP/C = 0 %, 90 min
+
'iii' .. I>
<)
SP/C = 0.40 %, 15 min
SPIC = 0.40 %, 90 min
~ 0.0 I I I
2.4 2.8 3.2 3.6 4.0
S01C (w/w%)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 3: ([Na]+[K])/(2.[5]) molar ratio measured by ICP-AE5 in the aqueous solutions

versus 50/C weight ratio of the cements grouts containing SP1.
2.0
cCD I
E
CD 1.5
0
0
~
c.. 1.0
(/)
"'
.5 0.5
§
0
0.0
0.000 0.005 0.010 0.015 0.020 0.025
CAS (gSP/gAS)
Figure 4: Consumption isotherms of 5Pt by Kt cements after 15 min.
3.0 600
2.5 500
~
2.0 400
.5 1.5 I 300
0
0 1.0 200
0.5 100
0.0 0~~--~~~--.-~
2.25 2.75 3.25 3.75 4.25 2.25 2.75 3.25 3.75 4.25
SOjC(wiw%} SOiC (wiw%)
Figures: Q, (left) and K (right) parameters of the BET fit of 5Pt

consumption isotherms.

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,,```,-`-`,,`,,`,`,,`---
0 15 30 45 60 75 90
t (min)
Figure 6: Evolution of yield stress with time for K1 Opt grouts and various
SP /C ratios of SP1.
15min 90 min
10
K1
•
K2
A .
K1
A
K2
Opt-
•• 0
0
Opt
Opt+
5 & 7 8 9
0.1
Qcon;mm (mg SP/g of cement)
Figure 7: Yield stress versus superplasticizer's consumption after 15 or 90 min for SP1
containing grouts.

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70 600
,.......
60 500 zIll
-::1 50 +
~
400
'5 40
E
Q
!. 300
ro 30 $
2. 200
20 33
0
100
10
E
0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Na20eq (wtw %)
Figure 8: Concentrations in calcium, alkalis and sulphates versus Na 2 0,q for plain
grouts of industrial CEM I type cements (SP /C = o%) after 15 min.
eo
60
f • ~I
[Cal
c
0
A
<>
SP/C • 0'%, 15 min
=
SP/C O"k, 90 min
=
SP/C 0.40%, 15 min
SP/C = 0.40%, 90 min
it::
, "'
200
150
~
0
E
_#- ]l
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
..§. 40 100 33
-;;; g,
2. .!:::
20 50
·--
01-----.-----.----.----------~
100 200 300 400 500
[K) (mmol/1.)
Figure 9: Calcium and sulphate concentrations versus potassium concentration in the

aqueous solution.

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- ~
3.0 -
2.5 -
-l.
~
~
:::::..
2.0 -
1.5 - H-L._ ___j

sz
• •• SP/C
1.0 - = 0%, 15 min
SP/C =0%, 90 min
+
m 0.5 - A SP/C = 0.40%, 15 min
e 0.0 I
<> SP/C = 0.40%, 90 min
I I I I I
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Na2 0eq (wlw %)
Figure 10: ([Na]+[K])/(2.[5]) molar ratio measured by lCP-AES in the aqueous solutions
versus the weight ratio Na 2 0eq of the cements.
1.2 1.2
.,
"% "%
E
8
1.0 "'E
8
1.0
0 0.8 0 0.8
::?
"-
rn
0.6 -"'
a.
UJ
0>
0.6
.5."'., 0.4
.5. 0.4
c
8
0.2 "'c
8
0.2
X-~~-Z
0 0.0 0 0.0
0.000 0.005 0.010 0.015 0.020 0.000 0.005 0.010 0.015 0.020
CAs(9 SP I gAS) CAS(g SP/g AS)
Figure 11: Consumption isotherms ofSP2 by industrial CEM l type cements after
15 and 90 min.
1.2 4000
"%
"E 1.0
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
3000
8 0.8
0
~
a.
0.6 1 2000
~
Ch
0.4
! 0.2
1000
o· 0.0 0
0 40 80 120 160 200 40 ao 120 160 200
[S]AS (mmoVL) [SJAs (mmoi/L)
Figure 12: Parameters of the BET fit of the SP2 consumption isotherms(~ on the left,
K on the right) versus sulphate concentration measured in the aqueous solution after
the same time.

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0.0 0.1 0.2 0.3 0.4

SP/C (wlw%)
Figure 13: Yield stress versus superplasticizer (SP2) content of the grouts, SP/C.
0.0 0.2 0.4 0.6 0.8 1.0

Ocon.fOo(-)
Figure 14: Relative yield stress versus adimensional SP2 consumption, after 15 min.

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-25
Shrinkage-Free Mortars for Repairing

Damaged Concrete Structures
by S. Collepardi, G. Corazza, G. Fazio, S. Monosi,

and R. Troli
Sy_Qopsis: Shrinkage-compensating mortars are in general pre-mixed cementitious

materials which contain expansive agents among the various powder ingredients_
The role of the expansive agent, in the form of dead burnt calcium oxide (CaO) or
calcium sulfa-aluminate (CSA), is to produce a compressive stress in the repairing
mortar due to the restraint exerted by the metallic reinforcements or the friction
of the rough concrete substrate. To be successful, the mortar must be carefully
wet cured because the expansion can occur only in the presence of water due the
hydration of the CaO or CSA based expansive agent. ln the absence of careful wet
curing, the repairing work can be unsuccessful because there would not be any useful
precompression from restrained expansion.
The present work is devoted to study the behavior of mortars containing CaO
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
or CSA as expansive agents combined with a Shrinkage-Reducing Admixture (SRA)
in the presence and in the absence of wet curing. Due to the synergistic action of
the SRA with the expansive agent, the restrained expansion can occur even in the
absence of any wet curing. However, this action in much more effective when SRA is
combined with CaO rather than with CSA.
Keywords: expansive agent; repairing mortar; shrinkage-reducing .

admixture

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376 Collepardi et al.
Silvia Collepardi is a research civil engineer and director of the Enco Laboratory,
Ponzano Veneto, Italy. She is working in the field of concrete durability and
superplasticized concrete mixtures and has published numerous papers in this area.
Gianmaria Corazza is an industrial engineer specialized in cementitious materials. He
is responsible for tests on concrete in the Enco Laboratory.
Glenda Fazio is Doctor in Materials Science and she works in the area of analytical
chemistry.
Saveria Monosi is Professor of Materials Technology in the Civil Engineering Faculty
of the University of Ancona, Italy. She is author or co-author of numerous papers in the
area of concrete durability and chemical admixtures.
Roberto Troli is a research civil engineer and technical director of ENCO,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Engineering Concrete, Ponzano Veneto, Italy. He is author of numerous papers in the
field of concrete technology and in particular of chemical and mineral admixtures.
INTRODUCTION
Shrinkage-compensating mortars are in general used to repair damaged concrete

structures [1]. This characteristics is needed because the concrete to be repaired is old and
its drying shrinkage almost finished at the time of repair. The shrinkage of a new ordinary
repair mortar would cause a differential movement with respect to the substantially stable
concrete substrate. The restrained shrinkage of the mortar could result in the debonding
from the concrete substrate and then cracking (Fig. 1) when the tensile stress ( cr1)
becomes higher than the tensile strength, ft (Fig. 2).
On the other hand, when an expansive mortar is used in a repair material, the
restrained length change during early wet curing (Fig. 3) is transformed into an adequate
compressive stress (crc) which is gradually relaxed in the subsequent restrained drying
shrinkage so that, at the end, the resulting tensile stress ( cr1) cannot produce any cracking
since it remains lower than f1 (Fig. 4).
The success in repairing a damaged concrete structure is strongly dependent on the
care of the workmanship in the early wet curing of the repaired surface for at least 1-7
days depending on the type of the proprietary premixed mortar. In the absence of
adequate wet curing, the compressive stress (crc) could be very low and not enough to
compensate for the tensile stresses that develop during the subsequent drying shrinkage.
Consequently, the remaining tensile stress ( cr1) is still higher than the tensile strength (f1 )
and cracking can occur (Fig. 5).
SCOPE OF THE WORK
Recently it has been found that when a CaO-based expansive agent is combined with
a Shrinkage-Reducing Admixture (SRA), the expansion can occur even in the absence of
a wet curing [2].This effect would improve the robustness of a shrinkage-compensating

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mortar as a repair material for damaged concrete structures. This effect has been
confirmed by Maltese et a!. [3] who have found that the use of a CaO-based expanding
agent with a shrinkage reducing admixture allows to obtain mortars less sensitive to
drying. The main purpose of the present work was to study whether this effect can be
extended to other expansive agents such as those based on Calcium Sulfo-Aluminate
(CSA). Indeed, the combined use of CSA and SRA has been found to be successful as
patch material in repair work provided that a curing compound is used to prevent
moisture loss from the surface [4]. A second purpose of this work was to check whether
an early protection from air drying ,as that which would occur in grouting repairing
mortar placed into formworks before demolding, can provide sutlicient early expansion
to compensate the subsequent drying shrinkage. Finally, a third purpose of this work was
to check the influence of removing this early protection from air drying as would occur
when sprayed mortars on damaged concrete surfaces are exposed to air without any wet
curing and any early protection at all.
EXPERIMENTAL: MATERIALS, METHODS AND RESULTS
Two commercial expansive agents were studied : one based on dead burnt CaO and
the other on CSA. The expansion produced by CaO or CSA are related to the following
chemical processes:
CaO + H 20 ==> Ca(OH)2 (1)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
In general the recommended time of wet curing is 1-2 days for cementitious material
containing CaO and 5-7 days for cementitious materials containing CSA. This time is
related to the different hydration rates of the chemical processes.
The other ingredients used in the study are:
-portland cement (CEM I 42.5 R according to the European Norm EN 197-1;

- natural sand (maximum size: 5 mm);
- polycarboxylate-based superplasticizer;
-Shrinkage-Reducing Admixture based on propylene-glycol ether.
Table 1 shows the composition of the 6 mortars manufactured at a given workability.

The liquid-binder ratio was 0.50, where the weight of the liquid includes the amount of
the chemical admixtures (SRA and superplasticizer), and the weight of binder includes
the amount of the expansive agent (CaO or CSA).
Table 2 shows the compressive strength of the mortars demolded at two days and then
cured in the air at 20 °C with Relative Humidity (R.H.) of 60 %. There was no difference
in the 28-day strength values of the mortars, all at about 42 MPa. However, the mortars
containing SRA had a lower strength (20-25% less) at 1 day with respect to the
corresponding mortars without SRA.
The reinforced specimens, manufactured according to the ASTM test method C 878

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(75x75x254 mm), were demolded at 6 hours in order to measure the initial length of the
metallic bar (5 mm in diameter and 293 in length). Then the specimens were cured at 20
°C in the following three ways:
i) by immersing permanently under water;

ii) by wrapping the specimens with a plastic sheet for 2 days followed by exposure to
air (R.H.= 60%);
iii) by immediate exposure to air (R.H.= 60%).
Curing procedure i) is intended to measure the maximum potential expansion by

permanent immersion under water. Curing procedure ii) is to determine the behavior of
the reinforced specimens according to the realistic demolding at 2 days and then exposure
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
to open air. Curing procedure iii) is intended to simulate the behavior of reinforced
structures exposed immediately to open air as sometimes occur with sprayed mortars
without any protection and wet curing.
The restrained length change of the reinforced specimens was measured as a function
oftime up to 2 months. The results are shown in Fig.6-10.
Figure 6 shows the behavior of the control mixture and that of the "SRA mortar"
following curing procedure ii): there was no length change in both mortars during the
first two days when the specimens were wrapped with plastic sheet; then, when the
specimens were exposed to the air at R.H. of 60%, the "SRA mortar" shrank at a lower
rate with respect to the control mortar: about 50% less at early ages and about 30% less at
later ages. So, the effect of the chemical admixture SRA used in this work is similar to
that recorded by others in the technical literature [5].
Figure 7 shows the behavior of the "CaD" mortar when tested according to the three
curing procedures: the restrained expansion reached in about two days the level of 800
microstrains under permanent wet curing with little change at later ages; when the
specimens are protected from drying by the plastic sheet the initial expansion of 600
microstrains is gradually relaxed by the subsequent shrinkage and it is completely lost in
one month; in the absence of the early protection, the initial expansion in the reinforced
specimens is only 300 microstrains and it is lost in about two weeks.
The combination of SRA with the CaO-based expansive agent (Fig. 8) gives a
synergistic effect with respect to the mortar with only SRA (Fig. 6) or only CaO (Fig. 7).
First, the expansion on the "CaOISRA" mortar according to curing procedure ii) is the
same as that of the same mortar permanently kept under water: the restrained expansion
is 800 microstrains at about 2 days regardless of the curing. Second, the shrinkage of the
"CaO/SRA" mortar after removing the plastic sheet is much less with respect to that of
the corresponding mortar with CaO without SRA (Fig. 7); therefore, the initial expansion
after the demolding is relaxed by the subsequent shrinkage to a lower extent so that there
is still a restrained expansion even after the exposure of the specimen to air with R.H. of
60% for two months. Third, even when the restrained specimens are exposed
immediately to the air with R.H. of 60%, the reduction of the expansion due to the
subsequent shrinkage is lost only at two months; this means that cracking in the
"CaO/SRA" mortar would be unlikely: only when the tensile stress, after two months, is
higher than the tensile strength of the mortar.
Figure 9 illustrates the restrained length change of the "CSA" mortar according to the

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,,``````,,,,```,-`-`,,`,,`,`,,`---
above mentioned three ways of curing. The behavior of this mortar is very different from
that of the corresponding 11 Ca0 11 mortar. The restrained expansion of the 11 CSA 11 mortar
permanently kept under water is very slow and it takes about 10 days (versus about 3
days for the 11 Ca0 11 mortar) to reach the maximum value of600 microstrains (versus 800
microstrains of the corresponding 11 Ca0 11 mortar).The maximum expansion of the 11 CSA 11
mortar specimens protected by the plastic sheet is only 230 microstrains and it is lost
completely in about 1 week by the subsequent shrinkage. Even less effective is the
behavior of this mortar when immediately exposed to air (R.H. = 60%): the small
restrained expansion of about 100 microstrains is completely lost in about 5 days.
The combination of SRA with the CSA expansive agent (Fig. 10) does not change the
restrained expansion compared to the 11 CSA 11 mortar (Fig. 9) when the specimens are wet
cured under water. However, there is an increase in the initial restrained expansion (400
versus 230 microstrains) due to the addition of SRA when the specimens are protected
two days by the plastic sheet: the early restrained expansion of 400 microstrains is
completely lost in about one month when the 11 CSAISRA 11 mortar is exposed to air; in the
11
Ca0/SRA 11 mortar (Fig. 8) the restrained length change of the specimens exposed to the
air after a protection of two days is much higher with respect to the "CSA/SRA" mortar,
and a restrained expansion of200 microstrains is still available after two months. Finally,
the restrained expansion of the 11 CSAISRA 11 mortar is lost in about three weeks when the
specimens are cured immediately in the air with R.H. of 60%.
As far as the combined action of CaO with SRA is concerned, there are two distinct
effects as illustrated in Fig. II:
- the ~ effect which resultsg in a lower shrinkage due to the expected influence of the
SRA on the shrinkage behavior;
- the a effect due to the un expected higher expansion of CaO related to the presence
ofSRA.
X-ray diffraction analysis (Fig. 12) did not show any influence of SRA on the CaO
hydration in terms of the Ca(OH) 2 peaks. The termogravimetric analysis (Table 3), again,
does not show any influence of SRA on the amount of Ca(OHh .Therefore, presently the
increase in the restrained expansion of CaO with SRA cannot be explained. Also
unexplainable is the influence of SRA on the restrained expansion is much more effective
with the CaO expansive agent (Fig. 8) than with the CSA agent (Fig. 10).
CONCLUSIONS
The combined action of SRA with an expansive agent such as dead burnt CaO or
calcium sulfa-aluminate (CSA) increases the restrained expansion in the absence of wet
curing. The effect is much more enhanced when SRA is combined with CaO than with
CSA.
In particular, the combined action of SRA with CaO will permit the manufacture of
shrinkage-free mortars as repair cementitious materials for damaged concrete structures,
when they are placed into formworks and exposed to air after two days: even after two

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months of pennanent exposure to air with R.H. of 60 %, there is remaining restrained
expansion that is capable of keeping the mortar under a compressive stress (crc).
In repair applications where mortars are sprayed on the surfaces of damaged concrete
structures, the mortars based on the combined action of SRA with CaO can keep their
advantageous crc for more than two months when exposed immediately to air. Under this
situation, mortar cracking would be avoided if the tensile strength (f,) is as high as 2.5
MPa and also higher than the tensile stress ( cr,) in the mortar following shrinkage at later
ages.
REFERENCES
[1] L. Coppola, "Concrete Durability and Repair Technology", Proceedings of the

Fifth CANMET/ACI International Conference on "Durability of Concrete", Editor V.M.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Malhotra, Barcelona (Spain), pp. 1209-1220,2000.
[2] M. Collepardi, A. Borsoi, S. Collepardi, J.J. Ogoumah Olagot, R. Troli, "Effects
of Shrinkage-Reducing Admixture in Shrinkage Compensating Concrete Under Non-Wet
Curing Conditions", Cement and Concrete Composities, 6, pp. 704-708, 2005.
[3] C. Maltese, C. Pistolesi, A. Lolli, A. Bravo, T. Cerulli and D. Salvioni,
"Combined Effect of Expansive AND Shrinkage Reducing Admixtures to Obtain Stable
and Durable Mortars", 12, pp 22444-2251,2005
[4] D. Bischoff and A. Toepel, "Laboratory Testing of Portland Cement Concrete
Patch Material, Modified to Reduce or Eliminate Shrinkage", Wisconsin Department of
Transportation Final Report, pp. 1-81.
[5] N.S. Berke, L. Li, M.C. Hicks, J. Bal, "Improving Concrete Performance with
Shrinkage-Reducing Admixtures", Proceedings of the Seventh CANMET/ACI
International Conference on Superplasticizers and Other Chemical Admixtures in
Concrete, Editor V.M. Malhotra, Berlin, pp. 37-50, 2003.
Table 1 -Composition of mortars in kglm 3 at the same workability

(spread table== 50%).
MORTAR CONTROL SRA CaO CaO/SRA CSA CSA/SRA

Cement 450 450 450 450 450 450
Expansive Agent ---- -- 45 45 45 45
Aggregate 1560 1560 1540 1540 1540 1540
Water 220 210 245 230 245 245
SRA ---- 9 ---- 9 ---- 9
Supe[JJlasticizer* 5 6 6 6 6 6
* 20% aq. solution

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Table 2- Compressive strength (MPa) of mortars demolded at 2 days
and then air-cured at 60% and 20°C.
TIME CONTROL SRA CaO CaO/SRA CSA CSAISRA

l 25 20 24 20 23 19
3 32 30 32 27 29 28
7 36 38 38 37 34 33
14 40 42 41 39 40 37
28 42 43 43 44 42 41
Table 3- Percentage of Ca(OB)2 in some mortars.
TIME CONTROL SRA CaO CaOISRA

I hour ---- ---- 6.0 6.1
3 hours ---- ---- 7.3 7.0
6hours 2.8 2.8 10.1 10.3
l day 11.3 10.6 21.4 21.6
DE BONDING
Fig. 1- Cracks in the repair material and debonding from the concrete substrate
adapted from[t].
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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.
,. "cracking
,;
...
.. ... .. 'Ot
,;
,,
,;
Time
Fig. 2- Cracking of the repairing mortar when (due to restrained shrinkage) is ot

higher than the tensile strength (f).
I"'LENGHT
INCREASE
FROM
EXPANSIVE
AGENT
(1-7 days)
~
Fig. 3 -Concrete substrate and reinforcements restrain the length increase of
the expanding repair mortar. The repaired portion of the structure accumulates
compressive stress (o), adapted from [1).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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, "'
............................................
'', ""
...... - ,"
"Gc
wetcurfna
expansion air d
Time
Fig. 4- Compressive stress (8J due to the restrained expansion compensates the
subsequent relaxation and tensile stress induced by drying shrinkage. The resulting
net stress is never higher than the tensile strength (f,).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
<Yt /
/
·············-~·-··························
air drying shrinkage
Time
Fig. 5- Due to inadequate wet curing, the compressive stress (8<) is very low and
then it cannot compensate the subsequent shrinkage: tensile stress 81 can reach the
tensile strength f, and cracking can occur.

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```,-`-`,,`,,`,`,,`---
1000 . - - - - - - - - - - - - - - - - - - - ,
.§ 800
l!1 600
~.:s 400
11.1 I! 200
g 0
::; -200 SRAmortar
jl-400
c -600 CONTROL mortar
1: -800
i5i -1000 .___ _.___ _.__ _,..,.._ __,.__ ___.__ _._______.
0 10 20 30 40 50 60 70
Time (days)
Fig. 6- Restrained length change of the control mortar and SRA-based mortar both
protected by plastic sheet for 2 days and then exposed to air (R.H. = 6o%).
1000~-----------------------------,
l ::?t; -
... .oKlO p!l 1!1,
wet curing - -
fl. IJ '- protected 2 days
~ zoo p '--.. lEI .... b.! plastic sheet
j
o ------------o,.:.:.-:--!'::.fk-;.;-.:.·::·----------------------
~ -zoo
E
· c-. . ~-
"It - - - - - -21
" -roo a1r cunng · -o- . -[
J-e ·600
R.H. = 60%
6j -BOO
-1000 ..___. . . ____.___ ___..___......_ . . . .____,
......~
0 10 20 30 40 50 60 70
Time (days)
Fig. 7 -Influence of the curing on restrained length change of the CaO based mortar.

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·!
g.
kl -400 D..,
t!l. , ~ protected 2 days
fl.~ !I~ by plastic sheet
.S zoo . ""'0. ~ - ~ - - -!1 - - 11- -!1-
i 0 •.....•••.•••.•.••••. :.r::!:-::: ..:..':7.:-::-•• .C::-:=::.IJ..:-e-.
·~ -200 air curing
1!1. -400 R.H. =60%
~ ·600
~ ·800
-1ooo..__ _.__ _.__ _.__ ___._ _,___ _,____.J
0 10 20 30 40 50 60 70
Time (days)
Fig. 8- Influence of the curing on restrained length change of the CaO/SRA

based mortar.
1000r-------------------------,
c 800
l
wet curin!l
.E 200
i... 0 _g_ .:,s.. ......... ---. ---·-.. -----·----· .. -------·.----·. ---·
'-' '!1.. protected 2 days
~ -200 ·[]-....::_... ... by plastic sheet
i -400 • ~ ~ - - - ~- - - - - - 1!:1
~c -600 LJ-. . - - IJ - - · --C
air curing
~ _
800
R.H. = 60%
-1000.___ _,___ _.__-J.._.....,I._ _ .___....___._~
0 10 20 30 40 50 60 70
Time (days)
Fig. 9- Influence of the curing on restrained length change ofthe CSA based mortar.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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1000r----------------,
c 800
1:
wet curing
i 200 [] ' 1!L

.. protected 2 days
~
1ft
'-......, - - - .-__ by plastic sheet
0 ___________ LJ.! .............. .&.I":.~----------------------------
e
.!:!-zoo
. . . o-- • ---------
-
E air curing
' -400 R.H. " 60%
~
'1:
-600
61 ·800
·10001......-_.__........_--'--.1.....-....&...-......1.---'
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0 10 20 30 40 50 60 70
Time (days)
Fig. 10- Influence of the curing on restrained length change of the CSA/SRA
based mortar.
1000
,.cc0 100
600
:1
~ 400
cao/SRA
.5 200
I!
'il 0 -----------------------
~-200
cao
j -400
~ -600
~ .-oo
·1000'----'--......L.---i--.1.....-....&...-......1.-__...l
0 10 20 30 40 50 60 70
Time (days)
Fig. 11- Restrained length change in "CaO mortar" and "CaO/SRA mortar" exposed
to air (R.H. = 6o%) after 2 days of protection by plastic sheet.

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1200
1000
~800
S600
u
400
200
0.0
13.0 14.0 15.0 16.0 17.0 18.0 19.0
29
1200
1000
~800
8600
400
200
0.0
13.0 14.0 15.0 16.0 17.0 18.0 19.0
29
Fig. 12- X·ray diffraction analysis of the "CaO Mortar" (A) and "CaO/SRA mortar" (B).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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-`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-26
Changes in Cement Paste and Mortar

Fluidity after Mixing Induced by PCP:
A Parametric Study
by L. Regnaud, A. Nonat, S. Pourchet, B. Pellerin,

P. Maitrasse, J.P. Perez, and S. Georges
Synopsis: The interaction mechanism between polycarboxylate-type superplasticizer

(PCP) and cement hydration is not fully understood and incompatibilities between
concrete and additive are sometimes observed. In some cases, the fluidity tends to
increase ("over-fluidification") few minutes after mixing. This is a problem because
the over-fluidification leds to bleeding of the concrete which could be critical on job
site. Our study consisted first in highlighting the phenomenon of "over-fluidification"
by slump flow tests on mortar. Next, the time evolution of the rheological behaviour
of cement pastes in the presence of PCP was analysed thanks to a rheometry
protocol in order to quantify the phenomenon. Later on, a parametric study was
undertaken using this methodology. The operating conditions such as temperature
and mixing process were studied as well as the effect of PCP structural parameters
and the chemical characteristics of cement. In order to understand the origin of
the phenomenon, adsorption measurements of PCP on cement particles were
performed in the same conditions as those in the rheological measurements. Indeed,
the phenomenon of"over-fluidification" could be related to the rate of the initial
adsorption and the adsorption kinetics, both of which depend on the parameters of
the process, the PCP structure and the cement reactivity.
Keywords: adsorption; fluidity; over-fluidification; PCP; slump flow;

sulfate
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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390 Regnaud et at.
Laure REGNAUD - Laure Regnaud works for Chryso during his Ph.D in the University
of Bourgogne. His subject deals with interactions between polycarboxylate type
superplasticizers (PCP) and the early age of cement hydration in order to understand the
changes of fluidity induced by PCP after mixing.
Andre NONAT - Andre Nonat is a Research Director in CNRS at the University of
Bourgogne. His research is based on the reactivity of cement with a special interest in
studying the mechanisms of hydration reactions, the thermodynamical and microstructure
of hydrates and the mechanism of the setting.
Sylvie POURCHET - Sylvie Pourchet is an assistant professor at the University of
Bourgogne. His research is based on the reactivity of cement with special interest in
studying the mechanisms of hydration reactions in presence of organic additives.
LRRS (UMR5613)- Universite de Bourgogne DIJON, France
Bruno PELLERIN- Bruno Pellerin is CHRYSO's Research and Development Director.

His current research interests are mainly fluidity, strength development and durability for
normal concrete and self- leveling concrete.
Philippe MAITRASSE -Philippe Maitrasse is a Research Manager of CHRYSO. He's
mainly concerned by superplasticizers research, development and relationship with
concrete properties.
CHRYSO - Sermaises du Loiret, France
Sebastien GEORGES and Jean Philippe PEREZ - Jean philippe Perez and Sebastien
Georges work for Lafarge (LCR) as research engineers on organa-mineral interactions.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
LAFARGE-LCR- St-Quentin Fallavier, France
INTRODUCTION
Polycarboxylate -type superplasticizer has become popular because of its superior water-
reducing ability and fluidity retention ability. The interaction mechanism between
polycarboxylate polymers (PCP) and cement is not yet fully understood and the
dispersibility of PCP on cement particules can be affected by various conditions (1).
Indeed, it is assumed that PCP causes dispersion of cement particles by the steric
repulsive forces caused by the PCP adsorbed to the surface of solid particles (2).
It has been reported that the cement characters affecting the fluidizing ability of PCP
were the amount of alkaline sulphate, the kind and amount of calcium sulphate, and the
amount and activity of interstitial phases (3).
Some studies pointed out that the surface area on which PCP was adsorbed and the
adsorption amount were the most important factor based on the assumption that PCP
works after the adsorption on cement hydrates (4, 5). As for the PCP adsorption, the
sulphate ion concentration in solution phase was thought to affect it. The adsorption of
PCP decreases in the case of high sulphate ion concentration in aqueous phase because
the sulphate ion and PCP are adsorbed on cement particules competitively (6).
In actual placing of concrete, in which PCP was used, it is experienced in some cases that
the fluidity of concrete tends to gain few minutes after its mixing. We called "over-
fluidification" this phenomenon. This increase in fluidity makes it difficult to pour the

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concrete and in the worst case segregation appears. This significant variability in the
initial fluidity of the concrete and the stability of this fluidity over time can appear
according to the nature of cement, the temperature of the ground or the duration of the
mixing.
Our study was thus designed to better understand this phenomenon of "over-
fluidification". Our study first consisted in highlighting the phenomenon and quantifying
it on mortar and cement paste thanks to a rheometry tool.
A parametric study of the phenomenon was then undertaken. We studied the parameters
related to the manufacturing process, the parameters related to the PCP structure, and the
chemical composition of cement.
In order to understand the origin of the phenomenon, the evolution of the rheological
properties of cement paste is drawn in parallel with measurements of PCP adsorption on
cement particles.
Our study should allow the understanding of the origin of the phenomenon of super-
fluidification and the parameters which control the action of the PCP at the beginning of
the cement hydration in order to overcome the incompatibility problems.
EXPERIMENTAL
In the following sections, the characteristics of the material (polymers and cement) and
the details of the method used in the experiments of the present study are described.
1-Materials:
Polycarboxylate superplasticizers:
Industrial reference:
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The industrial HRWRA selected as reference is a standard PCP (called PCP,er) used for
ready mix applications, characterized by a charge amount ccoo· concentration/g of
polymer) of 0.94 m.eq/g. Some slump increases with time were reported when using this
HRWRA.
Model PCP:
In order to analyse the influence of the PCP structure, we worked with several PCP
model with different charge amount.
The PCP were synthesised by copolymerizing methacrylic acid (CA) and
methoxy(polyoxyethylene) methacrylate of Mw = 1100 g/mol (CE) at different molar
ratio.
We obtained a range of five PCPs with charge amount between 0.53 m.eq/g and 2.6
m.eq/g. The average molecular weights (Mw) of these polymers were about 45 000 g/mol
with a polydispersity index about 2,5. (Table 1)
All the polymers were neutralized with NaOH to a pH value of 7.

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392 Regnaud et al.
Cements and Clinker:
Cement:
Lafarge Portland cement named Cement H was used to study the influence of process
parameters and of PCP structure. It is characterized by a low tricalcium aluminate phase
and low alkaline sulphate quantity. (Composition in Table 2, Calcium sulphate : 2/3
gypsum, 1/3 hemi-hydrate)
Clinker:
In order to control the type of calcium sulphate added and the proportion of alkaline
sulphate, we used an industrial clinker containing low alkaline sulphate, namely the
clinker L. (Composition in Table 2)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
In order to investigate the influence of the type of calcium sulphate introduced, we added
a certain amount of calcium sulphate to the clinker in order to have 3.7% of total S03 •
Different kinds of calcium sulphate were used: gypsum only or a mixture of gypsum and
hemi-hydrate at different ratios. The calcium sulphate and the clinker were mixed in an
asymmetrical mixer during three days.
To investigate the influence of the proportion of alkali sulphate, we introduced Na2S0 4 or
K2S0 4 to the solution before mixing with the clinker powder.
11-Mixture proportion :
Most of the experiments were carried out on cement paste but we also worked with a
mortar in order to evaluate the results on the two different systems.
All manipulations were performed with a constant PCP dosage of 0.16% and at a
temperature of 20°C except the case of the temperature influence. The water content
varied with the nature of the mineral composition and admixture in order to retain the
same initial viscosity of about 2 Pa.s at 50 s- 1 for the cement paste and a spread of slump
flow of 280 mm for the mortar except in the case of the study of the process parameters
where the W/C remains constant. This adjustment guarantees to have the same initial
state for all the different conditions thus assuring reliable comparisons.
HI-Experimental procedures:
Slump flow of mortar
The fluidity of mortar was approximately evaluated by flow value. Cement and sand were
mixed for 30s in a mortar mixer. We added water mixed with superplasticizer and we
mixed everything for 1 min 30s at a constant rotational speed. The fluidity of the paste
was evaluated by the spread measured when a truncated cone (Abrams (7) of 0 100
mm and 0 50 mm and 150 mm of height) filled with the mortar was pulled away
vertically. In order to examine the change in the flow value over time, we measured the
flow value every 0, 15, 30, 45, and 60 minutes after initial mixing with a mixing of 30s
before each measurement. The slump flow on mortar highlighted the phenomenon of
"over-fluidification".

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Rheometry protocol on cement paste
In order to work with a simple system and to more precisely examine the phenomenon of
"over-fluidification", we developed a rheometry protocol.
This protocol permits to measure the apparent viscosity of the cement paste at 0, 15 and
30 minutes after mixing in the same conditions as the slump flow test.
As a cement paste is close to a Bingham fluid (8), its apparent viscosity T]app depends on
the shear rate applied y and on the yield stress cy, considering the law:
with f.lp : plastic viscosity

' : stress
We used an ARES rheometer with a rheo reactor geometry illustrated in Fig. 1. In order
to ensure good reproducibility (8), the cement paste was mixed in the rheo reactor.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Thanks to a vibrating spatula, the cement was progressively mixed with the solution
(water+ PCP) previously introduced in the tank. When all the powder is introduced the
cement paste was mixed for one minute at a shear rate of 80 s· 1• After that, the plastic
viscosity is measured at a shear rate ranging from 50 to 0.2 s· 1• To do so, the tank turns at
different rotation rates and the sensor measures the torque that the cement paste creates
on the agitator. After a rest of 15 minutes, the paste was again mixed for 30 sat a rate of
50 s· 1 and we again measure the viscosity. The same operation was repeated 30 minutes
later after initial mixing.
In this way we measured the variation in apparent viscosity versus shear rate at different
times after initial mixing.
In order to quantify the phenomenon of "over-fluidification", we calculated a"% of over-

fluidification" which corresponds to the percentage of decrease in viscosity between 0
min and 30 min after initial mixing, for each shear rate.
'lapp·(t = 3min)-'lopp (1 = 30min)J [1]

%over- jluidification, =
l '
llapp,
'.
(t = 3 mm)
*100
The results show that this % of over-fluidification corresponds well to slump flow
measurements for rates between 10 s· 1 and 50s· 1. Indeed, the scale of shear rates applied
on a fluid during gravitating flow is ls- 1 to 10s" 1 (9). During the slump flow on mortar,
the cement paste undergoes both the shear of the flow and the shear of the aggregates so
the scale of shear rates which correspond with rheometry protocol seems coherent.
Thus in order to make a comparison, we calculated the average of the % of over-
fluidification for rate between 10 and 50 s· 1:

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394 Regnaud et at.
L%over- jluidification1
%over- jluidificationm = --'1--- - - --.- - - - [2]
1
withj being the number of measurements made with shear rate between 10 and 50s· 1
and i being the shear rate between 10 and 50 s· 1
For each condition, the experiments were repeated 5 times and we calculated an average
of the results.
This protocol therefore results in a quantification of the phenomenon and in comparison
of this phenomenon in different operational conditions.
Measurement of adsorption
The dispersion created by the superplasticizer is caused by the adsorption of PCP on

cement particle (10). Therefore, along with the rheology study, we measured the
adsorption of the PCP during the 30 minutes after initial mixing. We took three
measurements of the adsorption at 0 min, 15 min and 30 min after the initial mixing of 1
min at a constant rate with a mixing of 30s before the measurements at 15 and 30 minutes
We thus retained the same operational conditions of mixing as in the rheology
measurement.
For each measurement, we worked with a cement paste at W/C = 0_5 mixed in a small
mortar mixer at a temperature of 20°C. After mixing, we took a sample of the paste. For
each sample, supernatant liquid was separated centrifugally at 3000 rpm from the paste.
Then the total organic carbon content of this liquid was measured using Shimadzu TOC-
5000 A, and the concentration of the superplasticizer remaining in the supernatant liquid
was obtained from a calibration curve prepared in advance. This yielded the amount of
superplasticizer adsorbed on the cement as the difference between the amount of
superplasticizer added and that remaining into the liquid.
For each condition, the measurements were repeated 3 times and we calculated an
average of the results.
So we obtained the evolution of the PCP adsorption during the thirty minutes after initial
mixing of cement paste. In order to interpret results, two parameters are calculated, the %
of PCP initial adsorption and the relative increase of the adsorption between t = 0 min
and t = 30 min.
RESULT AND DISCUSSION
1-The phenomenom of over-fluidification :
Figure 2 shows the results of the slump flow test with the use of PCP ref which leads to a
"over-fluidification". When PCP ref is used we can observe an increase of the spread of the
slump flow during the 30 minutes after initial mixing which is representative of the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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super-fluidification. With the rheometry protocol on cement paste, we are able to follow
this increase of fluidity over the time and quantify it precisely.
Figure 3 shows the measurement of viscosity of cement paste according to shear rates
over time using PCP,er when a phenomenon of "over-fluidification" is noted. For each
shear rate, we note that viscosity decreases between 0 and 30 min. The % of super-
fluidification calculated is therefore positive contrary to cement paste without PCP which
gives a constant viscosity over time and therefore no over-fluidification. (Fig. 4)
11-Parametric study
Rheology results:
Process parameters :
The influences of temperature and mixing were studied. We can note in Fig. 5 that the
higher the temperature, the lower the % of super-fluidification. This result is in
accordance with the observation that during winter more problems of super-fluidification
arise with use ofPCP(ll).
To measure the influence of mixing, two parameters were studied, the rate of the mixing
and the duration of the mixing. We can see in Fig. 6 and 7 that the longer the the mixing
duration and the stronger the mixing rate, the lower the over-fluidification. Since duration
and shear rate of mixing are proportional to the mixing energy, we can say that the higher
the mixing energy expended on the cement paste, the lower the over- fluidification.
Structural parameters of PCP:

We will now present results concerning the influence ofthe charge amount of the PCP.
Figure 8 documents the influence of the charge amount on the % of over-fluidification.
We see that the lower the charge amount up to 1.06 m.eq/g, the more marked the over-
fluidification. We can also observe that the lower the charge amount, the higher the E/C,
in accordance with the fact that the higher the PCP charge amount, the more it adsorbs it
and the more it generates a good dispersion (12). As regards, the charge amount of 0.53
m.eq/g, we can note that with this PCP we do not observe any over-fluidification. Besides
we can observe that with this PCP, the quantity of water needed is very high because this
PCP seems to have any dispersion effect.
Chemical composition of cement:

In Fig. 9, we can observe the influence of the type of calcium added to the clinker on
the % of over-fluidification. First, we remark that in the absence of calcium sulphate,
there is no fast setting of the clinker. This result is very surprising and can be explain by
the fact that the clinker contains an important amount of sulphate.
Then, we observe that the addition of 100% of gypsum generates a loss of fluidity over
time (% over-fluidification <0). Furthermore, we note that super-fluidification is created
and accentuated when a certain amount of hemihydrate is added. (In this case, more
than 40% of the total amount of the calcium sulphate added). This finding indicates that
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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396 Regnaud et al.
the presence of hemi-hydrate in certain quantities creates the phenomenon of super-
fluidification.
In Fig. 10, we can observe that with a constant dosage in PCP, the higher the quantity of
Na2 S0 4 in solution, the lower the over-fluidification. We can also observe that the water
needed to obtain the same initial fluidity increases with the Na2 S04 concentration. This is
in accordance with the fact that there is a competition in adsorption between PCP and
sulphates ions (6). We observe the same effect with the addition ofK 2S04.
Adsorption results:
Process parameters:
Figure 11 shows that the initial adsorption of the PCP varies with the temperature: The
higher the temperature, the higher the initial adsorption. We also observe that adsorption
increases with time and that this increase depends on temperature.
As regards mixing, the observation is similar (Fig. 12): The longer the mixing duration,
the higher the initial adsorption of PCP. We also observe that the evolution of PCP
adsorption over time depends on the mixing duration.
Structural parameters:
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
In Fig. 13, we can observe the adsorption results for the PCP model with different charge
amount. We observe that the higher the charge amount, the higher the initial adsorption.
This finding is in accordance with the fact that the higher the charge amount, the more
carboxylic groups contained in the PCP and the higher the adsorption on the cement
particles (13). Moreover, for each charge amount, adsorption with time increases and
seems dependent on the PCP charge content.
Chemical composition of cement:

In Fig. 14, when the clinker contains 50%m of hemi hydrate with respect to quantity of
gypsum, the initial adsorption of the PCP is low compared to results obtained with the
clinker containing gypsum only. We can also observe that the adsorption increase
depends on the type of calcium sulphate added. This result can be explain with the fact
that the kind of calcium sulphate added affects the initial value of sulphate concentration
in interstitial phase. When cement contains hemihydrate mainly, initial sulphate
concentration is higher (14) so PCP initial adsorption is lower.
As regards the influence of alkaline sulphate on the PCP adsorption, we observed that
increasing amount of alkaline sulphate leads to a strong decrease of the initial PCP
adsorption. So, there is no significant adsorption when alkaline sulphate is added during
the thirty minutes after mixing.
III- Parallel between adsorption and the phenomenon of over-fluidification :
In order to draw a parallel, we reported the % of initial adsorption and the % of the
relative increase in adsorption during the 30 minutes after the initial mixing as a function

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of the% of over-fluidification obtained with the rheology study for each parameter which
influence super-fluidfication. Results are reported in Fig. 15 for the temperature, Fig. 16
for the duration of mixing, and Fig. 17 for the charge amount of PCP and 18 for the kind
of calcium sulphate added.
First, we observe a link between the initial adsorption, the % of the relative increase in
adsorption and the % of over-fluidification. Indeed, for each parameter, if the % of over-
fluidification increases, the % of initial adsorption decreases and the % of relative
increase in adsorption increases. There is a single exception at a point which corresponds
to the PCP which has a charge amount of 2.6 m.eq/g (Fig. 17). With this PCP, the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
phenomenon of over-fluidification is very slight, its initial adsorption is high, but its
increase in adsorption is also high. We think that the evolution of adsorption for this PCP
has no effect on the fluidity of the paste because its initial adsorption is sufficient to
assure the maximal dispersion.
We can therefore conclude that there is a link between the phenomenon of over-
fluidification, and the evolution of adsorption of the PCP. The lower the initial adsorption
and the higher its relative increase with time, the more marked the phenomenon of over-
fluidification.
Ifwe compare the ratio A= ~% of over- fluidification and
~% of initial adsorption
the ratio B =
ll% of over- fluidification , we observe that A> B
ll% of relative increase of adsorption
for each parameter. Then, the initial adsorption seems to be the parameter the most
critical for the phenomenon of over-fluidification.
With regards to the alkaline sulphate, we have observed that the decrease in the
phenomenon of over-fluidification related to the alkaline sulphate concentration is linked
to a strong decrease in the initial adsorption of the PCP. This is caused by the competition
of adsorption between sulphate and PCP ( 5). So, assuming a constant dosage of PCP, the
increase in the amount of alkaline sulphate creates a major decrease in the adsorption of
PCP. In these conditions, the PCP becomes inoperative and loses all dispersion effect.
Consequently, the phenomenon of over-fluidification disappears because this
phenomenon seems to be the consequence of the PCP adsorption.
CONCLUSION
This study first highlights the phenomenon of over-fluidification by slump flow tests on
mortar. The rheometry protocol used here precisely quantifies this phenomenon on
cement paste. This protocol provides information in agreement with slump flow tests on
mortar.
Thanks to this rheometry protocol, we conducted a parametric study of the phenomenon
of over-fluidification. We have observed that the temperature, the mixing, the charge
amount of the PCP and the kind of calcium sulphate added have a significant effects on
the phenomenon of over-fluidification. A study of PCP adsorption in the same conditions
showed that when the phenomenon takes place, the adsorption of the PCP increases with

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398 Regnaud et al.
time. We observed a link between the phenomenon of over-fluidification, the initial
adsorption and the evolution of the PCP adsorption over time: the lower the initial
adsorption of the PCP and the higher the relative increase of this adsorption over time,
the more marked the phenomenon of over-fluidification.
We now need to study the causes of this low initial adsorption and this evolution of
adsorption over time. As regards the nature of the parameters which have an effect on the
phenomenon, we think that the PCP adsorption is related to the sulphate concentration of
interstitial phase and the reactivity of cement in the first instants of hydration.
REFERENCES
l. Altcin, P.-C., C. Jolicoeur, and J.G. MacGregor, Superplasticizers: how they

work and why they occasionally don't. Concrete International. 16(5): p. 45-52.
2. Uchikawa, H., S. Hanehara, and D. Sawaki, The role ofsteric repulsive force in
the dispersion of cement paricles in fresh paste prepared with organic
admixture. Cement and Concrete Research, 1997. 27(1): p. 37-50.
3. Matsuhisa, M., eta!., Effects of cement character on the fluidity ofcement paste
added with beta-naphtalene sulfonate type or polycarboxylate type
superplasticizers. Proceedings of the Japan Concrete Institute, 1998. 20(2): p.
67-72.
4. Negishi K., N.H., Sugaya H., Goto T., Fluidity ofpaste added with
polycarboxylate-type superplasticizers. Cement science and Concrete
Technology, 1998.52: p. 138-139.
5. Yamada K, H.S., Honma K. The effects ofnaphtalene sulfonate type and

polycarboxylate type superplasticizer on the fluidity of belite-rich cement
concrete. in Proceeding ofInt. Workshop on Self-Compacting Concrete. 1999.
6. Yamada, K., s. Ogawa, and S. Hanehara, Controlling of the adsorption and

dispersing force ofpolycarboxylate-type superplasticizer by sulfate
concentration in aquous phase. Cement and Concrete Research, 2001. 31: p.
375-383.
7. Saak, A.W., H.M. Jennings, and S.P. Shah, A generalized approach for the
determination ofyield stress by slump and slump flow. Cement and Concrete
Research, 2004. 34(3): p. 363-371.
8. William D.A., S.A.W., Jennings H.M., The influence of mixing on the rheology
offresh cement paste. Cement and Concrete Research, 1999. 29: p. 1491-1496.
9. Barnes H.A., H.J.F ., and All, An introduction to Rheology. 1989, Elsevier:

Amsterdam. p. 13.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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10. Uchikawa H, H.S., Sawaki D, The role ofsteric repulsive force in the dispersion
of cement particles in fresh paste prepared with organic admixture. Cement and
Concrete Research, 1997. 27: p. 37-50.
11. Yamada K, Y.T., Hanehara S. Influence oftemperature on the dispersibility of

polycarboxylate type superplasticizer for highly fluid concrete. in Proceedings
ofInt. Conf of Self-compacting concrete. 1999. Stockholm: RILEM.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
12. Comparet, C., Etude des interactions entre les phasesmodeles representatives
d'un Ciment Portland et des superplastijiants du beton. 2004, universite de
Bourgogne.
13. Yamada, K., et al., Effects of the chemical structure on the properties of
polycarboxylate-type superplasticizer. Cement and Concrete Research, 2000.
30: p. 197-207.
14. Nakajima Y., Y.K., The effect of the kind of calcium sulphate in cements on the
dispersing ability ofpoly -naphatalene sulphonate condensate superplasticizer.
Cement and Concrete Research, 2004. 34: p. 839-844.
Chorge omount
PCP
(m.eq/g)
Mw(glmol) lp
1 2.6 I I
2 1.43 45 777 2.59
3 1.23 47462 2.6
4 1.06 51471 2.65

5 0.53 I I
Table 1: Structural pllrtlmeters of PCP models
Si02 Al203 Fe203 CaO MgO K20 Na20 S03

Cement
20.47 4.77 1.75 65.78 1.04 0.144 0.263 3.7
H
Clinker
20.72 5.29 1.75 68.01 1.15 0.2 0.07 1.55
L
Table 2: Composition of Cement Hand Clinker L (mtiSs %)

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400 Regnaud et al.
Sensor
•
SOip~~:jl~ c c ,:he: ............
M
Cement paste
c:
Angular displacement
Fig. 1: Geometry rhea-reactor used.
Over -lluidification
340
320
300
I 280
a!
I! 260
".
240
220
200
0 10 20 30 40
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
time (min)
Fig. 2: Evolution ofthe spread of Mortar over time (slump flow tests),
PCP ref= 0.16%, W/C = 0.4, Cement H.
Oecrcasc::::: ~~~ over-tluid fication
0.1 10 100
shear rate (s-1)
Fig. 3: Evolution of Apparent Viscosity versus Shear rates over time after initial mixing
for a Cement paste with PCPref = 0.16%, W /C = 0.32, Cement H:
A decrease of viscosity is observed with time after mixing.

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60
50 I ---- PCP ref r
' ----
1:
I - ---- -without additiw
40
~
c: 30
'6
·s 20
- % super-tluidificationm representative of the
~CD slump flow test on mortar
10 -
~
;fl.
0
~.... 10 20 30
-
_40_____ @~
-10 --e., ___ ..
---
-20
shear rate (s ., )
Fig. 4: Comparison of the %of super-fluidification (see Equation 1) obtained for a

cement paste with PCP ref and a cement paste without additive: Shear rates between
10 and so s-1 are representative of the results obtained with slump flow test.
E
60
c::
0 50
~
c: 40
:2:I 30
~Gl 20
~ 10
?fl.
0
10 20 30
Temperature (°C)
Fig. s: Influence of the temperature on the% of over-fluidificationm (see Equation 2)

Cement H paste with PCP ref= 0.16%, W/C = 0-32, initial mixing: 1 min, 8o s-1.
30s reference 3 min

1min
Mixing duration
Rg. 6: Influence of mixing duration on the% of over-fluidificationm (see Equation 2):

Cement H paste with PCP ref= 0.16%, W/C = 0.3, shear rate of mixing= 8os-t, T = 20°C.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--
402 Regnaud et al.
80s-1 100s-1
shear rate applied for 3 min rnxlng
Fig. 7: Influence of the shear rate of mixing on the% of over-fluidificationm

(see Equation 2): Cement H paste with PCP ref= 0.16%, W/C = 0.3,
Mixing duration= 1 min, T = 20°C.
35,--------------------------,
W/C=0.32
I
E 30 +----------~-----!
25
, 20+----
=
~ 15+-----
5
'$.
10+----
0.53 1.06 1.23 1.43 2.6

Chai"J,le amount (m.eq/e;)
Fig. S: Influence of the PCP charge amount on the% of over-fluidificationm

(see Equation 2): Cement H paste with additive= 0.16%, W/C adjusted to get the
same initial viscosity, T= 2o°C, initial mixing: 1 min, So s·'.
W/C=0.3
60,-----------------------------.
e 50+-------------
C
~ 40+------~-----------
~ 30+-~~WL-------------
'6
·s 20
'Z
5 10
"$. 0
- 10 ..L---'c"Cal"-:ci""um"----""'-.>i
sulphate
kind of calcium sulfate added
Fig. 9: Influence of the kind of calcium sulphate added to Clinker Lon the% of over-
fluidificationm (see Equation 2): Cement paste with PCP ref= 0.16%, W/C adjusted to
·get the same initial viscosity, initial mixing: 1 min, So s-1, T= 20°C.

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W/C.,0.32
0 0.10% 0.25% 0.50% 1%

% of Na1S04 added
Fig. 10: Influence of the quantity of Na,SO 4 added on the% of over-fluidificationm

(see Equation 2): Cement paste with Clinker L so/som gypsum/hemihydrate,
PCP ref= 0.16%, W/C adjusted to get the same initial viscosity, Initial mixing: 1 min,
So s·t, T = 2o 0 C.
90 9
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
c
.2 80 8 c
e. i..
,..,.
0 70 7
0
60 6
0
. 50 5
i
~
.13
!
.5
40
.E
4 II.
30 3 ~
1 0
..,.
i0 20
10
2
1
..,.
0
10 20 30
Temperature ("C)
Fig. 11: Parameters representative of PCP adsorption evolution over time according to
temperature: Cement H paste, PCP ref= 0.16%, W/C = o.s, T = 20°C,
initial mixing: 1 min.

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404 Regnaud et al.
6
30s reference 1 min 3min

Mixing durarion
Fig. 12: Parameters relative to PCP adsorption evolution over time according to
duration of mixing: Cement paste, PCP ref= 0.16%, W/C = o.s. T = 20°C,
Initial mixing: 1 min.
50
40
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
:.< 30
20
10+-----
null
0·1-----
0.53 1.06 1.23 1.43 2.6
Charge amount (m.eq/g)
the PCP charge amount: Cement paste, Additive= 0.16%, W/C = o.s,
Initial mixing: 1 min, T = 20°C.

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wilhout calcium 100gypsum 75125m gypsum/ 50150m gypsum/

sulphate hemihydrate ttemlhydrate
the kind of the calcium sulphate added to Clinker L, Cement paste, PCP ref= 0.16%,
W/C = o.s, T = 20°(, Initial mixing: 1 min, 8os·'.
--+--% of PCP inHial adsorption

9 - % of relati'"' increase of adsorption 90
8
~
80 0 "
"'0
16
1i 5
7 '
',~
....... '
'
----- 70
60
50
""e-
.,...0
0
..
Ill
'1'1 '' \ !
.5 4 40 u
D.
!i
0 2
3 ------ --. "' .... '
''
- - 30
20
.:
Ill
.i!:
1!I!!
~ ''
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
' ... 10 0
~
0 0
0 10 20 30 40 50 60
% over-fluidificatior~m
Fig. 15: Parallel between% of over-fluidificationm, the% of PCP initial adsorption

and the relative increase in this adsorption over time with the results concerning the
effect of temperature.

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406 Regnaud et al.
6 100 c
... - 0
c 5 -- -- -- / 90 "&.
~
-/
0
~4..
'
--- 80 .....
70 '0
i '
--~
60 ..
~ 3
'
''
'' :: J
-
~
2
''
' ' ... 30 if
'51
~
l ~ -% of PCP initial adsorption
- % of relattw increase of adsorption
~
20
10 '0
~
0 0
15 20 25 30 35 40 45
% over-fluidificationm
Fig.16: Parallel between% of over-fluidificationm, the% of PCP initial adsorption

effect of time of mixing.
40
.. ,, 60
.~
35
30
-- --,_
'
~._
I
1 ----..,II
-, ,,
25
~ 20
CA_
.i
~ 15
~ }'\
~ \
''
~ 10 \
--a-% of relatiw increase of adsofl)tion '.

---1 --+--%of PCP initial adsorption
J
0 0
10 15 20 25 30 35
% over-fluidificatio!lm
Fig. 17: Parallel between% of over-fluidificationm, the% of PCP initial adsorption

effect of PCP charge amount.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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~-
~-
. ,
,--
' ,,
..................... /
I ~-~-%ofPCPinitialedsorption
~' - - - % ~frelativeincreaseo~d~orption
' -
p '
'
...<'
\
' - - - ------ ..
-10 10 20 30 40 50 60
% over-fluidification..
Fig. 18: Parallel between %of over-fluidificationm, the% of PCP initial adsorption
effect of the kind of the calcium sulphate added to clinker L.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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408 Regnaud et al.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-27
Rheological Behavior of
Fresh Cement Pastes: Interaction
between Superplasticizer and
Viscosity-Enhancing Admixture
by L. D'Aloia Schwartzentruber and J. Cordin
Synopsis: Self-compacting concrete (SCC) has high flowability and can be placed
without vibration. It is defined as concrete that exhibits high deformability and
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
good resistance to segregation. This kind of concrete is of great interest and has
gained wide use especially in the case of structures that presents difficult casting
conditions, such as heavily reinforced sections. From a rheological point of view, the
use of a viscosity-enhancing admixture (VEA) along with an adequate superplasticizer
(SP) content can ensure high deformability and stability. However, little is known
about the interactions between SP and VEA. Hence, a study on several cement pastes
formulated from the original paste of a typical SCC is proposed. One of the major
aims of this paper is to show that empirical tests, such as spread and flow time, are
suitable to characterize the rheological behavior of cement paste instead of more
complex ones. Rheological properties, i.e. viscosity and shear yield stress can be well
correlated with empirical test results in the range offlowable mixtures. Moreover, the
experimental program leads to emphasize the effects of the mixing procedure and
especially the introduction of the SP on the rhelogical properties of cement paste.
Finally, test results enable to underline the interactions between SP and VEA used in
designing SCC. VEA affects both viscosity and shear yield stress. However, its effect
depends on the SP dosage.
Keywords: cement paste; interaction; mix design; rheological behavior;

self-compacting concrete; superplasticizer; viscosity-enhancing
admixture

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410 D'Aloia Schwartzentruber and Cord in
Laetitia D'Aioia Schwartzentruber is a research engineer at the concrete department of
the Laboratoire Central des Pouts et Chaussees (LCPC) in Paris. She received her PhD in
1998 and is now in charge of a new research program on the "design of environmentally
friendly concrete". She is also involved in various projects related to self-compacting
concrete. Her research interests include mix design and early age behavior of concrete.
Julie Cordin is a civil engineer from the French national state school of public works
(ENTPE) in Lyon. She was temporary affected at the LCPC for her degree.
INTRODUCTION
Self-compacting concrete (SCC) is a highly fluid concrete that does not require
any vibration during the placement process. Thus, this kind of concrete is of great interest
from economical, technical and environmental points of view 1' 2' 3 • Fresh SCC must be
stable to ensure structure strength homogeneity and durability. However, several
problems like bleeding, settlement or segregation can occur, sometimes simultaneously,
on construction sites. Segregation can appear during placing (referred to as "dynamic
segregation") or afterwards, during the dormant stage (referred to as "static
segregation"t "Static segregation" consists in the sedimentation of the coarsest
aggregates of the suspension under gravity forces. A voiding segregation is a matter of
both cement paste rheology and granular skeleton 4 . The cement paste has to be
sufficiently fluid to ensure the high fluidity of the concrete and sufficiently "viscous" to
suspend coarse aggregates. In fact, whereas a non-zero shear yield stress enables to avoid
the initiation of segregation, the viscosity and the thixotropy enable to limit its effects 4 .
According to this point of view, a better characterization and understanding of the
rheological behavior of fresh pastes for sec is the first step to control the stability and
robustness of sec.
In this paper, the rheological characterization of several fresh cement pastes
obtained by varying the superplasticizer (SP) and the viscosity-enhancing admixture
(VEA) contents of a typical SCC paste, is reported. This enables to underline the possible
interactions between SP and VEA usually used in designing SCC. Moreover, possible
correlation between empirical tests like spread or flow time and rheological ones (i.e.
shear yield stress or apparent viscosity) has been investigated to simplify the rheological
characterization of flowable mixes. Finally, the influence of the mixing procedure on
rheometric measurements has been underlined.
Cement paste mix design
Cement pastes are designed from one of the SCC mixtures studied in the
framework of the French national project BAP. The 28-day strength of this SCC is about
40 MPa. Constituents include Portland cement (CEM I 52.5 N CE CP2 NF according to
the EN 197-1 5), limestone filler and aggregates, SP and VEA. The SP is a new generation
one with a modified polycarboxylate base and the VEA is a polysaccharide suspension in
vegetal oil. The cement paste referred to as "mixture 0" is the same paste as in the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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original SCC mixture. Eleven cement paste mixtures are formulated from "mixture 0" by
varying both SP and VEA dosages (Table l ). The solid fraction, defined as the solid
volume to total volume ratio and the filler to binder ratio, are kept constant (respectively
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0.45 and 0.27). The SP dosage has been limited to the «saturation value» whereas four
increasing YEA contents have been investigated. However, little is known about the
influence of the VEA dosage on "the saturation value".
Beyond "the saturation value", an increase in the SP dosage does not
significantly improve the flowability, i.e. spread or flow time (Fig. 1). "The saturation
value" is usually determined from flow time results even if spread measurements are in
good agreement with flow time ones 6 :
- flow time is measured for various SP dosages,
- the logarithm of flow time is plotted against the SP dosage, expressed in terms of dry
content of SP to binder ratio,
-the saturation dosage is the point of tangency with a straight line whose slope is 2/5.
By using this method, "the saturation value" is independent of the paste volume
used 6. Preliminary tests were performed and led to the conclusion that the "saturation
value" of 0.2%, is not affected by changes in the VEA dosage, whereas the rheological
behavior is clearly modified (Fig. 2). The greater the VEA dosage, the lower the fluidity.
Rheological characterisation of cement pastes
Empirical tests, namely spread and flow time, are performed on the twelve
cement pastes to characterize their rheological behavior just after mixing. Spread is
measured by using a mini cone (diameters: 10 and 7 em, height: 5 em). The truncated
cone mould is placed on a glass plate, filled with paste and lifted. The resulting final
diameter of the fresh paste sample is the mean value of two measurements made in two
perpendicular directions (Fig. 1). Flow time is measured by using a Marsh cone. Its
geometry and dimensions are specified in the European standard EN 445 7• The test
consists in measuring the time required for a given volume of paste (400 ml) to flow
trough the nozzle (diameter: 8mm). The initial paste volume poured into the cone is
800 ml (Fig. I).
Apparent viscosity and shear yield stress are also determined by using a rate-
controlled viscometer Haake VT 550. A rotational speed is imposed to the tool and a
torque is measured. Both rotational speed and torque are then converted to shear rate and
shear stress according to the tool geometry used and the calibration of the device.
Concentric cylinder geometry is first used. Both, the inner and outer cylinders
are covered with a rough paper to prevent any slip-surface to occur (roughness 100 11m).
A gap of 1.5 mm between the concentric cylinders is sufficient when the maximum
particle size is 100 jlm (Fig. 3). The whole test procedure is shown in Fig. 3. A pre-
shearing phase of 120 s at a shear rate of l 00 s·' is first applied to the cement paste (phase
1 and phase 2 of the test procedure). After this pre-shearing phase, each measurement is
8
carried out under steady state flow to avoid any bias • An increasing shear rate phase
followed by a decreasing one are then successively applied (phase 3 and phase 4 of the
test procedure).

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Cement pastes usually exhibit a shear-thinning behavior: viscosity decreases
with increasing shear rate during steady shear flow. Apparent viscosity is then defined for
a given shear rate value as:
v(r)= ~ (1)
r
Where r and f are shear stress and shear rate, respectively. For this
investigation, apparent viscosity V was defined at the end of the pre-shearing phase.
Two methods are used to determine the shear yield stress of each paste. The first
one consists in fitting the Herschel Bulkley model (Eq. 2) on flow curves obtained with
the concentric cylinder geometry: shear stress vs. shear rate during phases 4 of the test
procedure. Hence, the same test enables to determine both apparent viscosity and shear
yield stress. The Herschel Bulkley model is a three-parameter model typically used to
describe the behavior of cementitious materials 9 • This viscoplastic material exhibits a
yield response with a power law relationship between shear stress and shear rate above
the yield stress r0 .
(2)
Where r 0 , K and n are the parameters of the model. A second method is used
to determine the shear yield stress. The test consists of a mould filled with paste and a
Vane that rotates at a constant and extremely small speed. The generated torque evolution
is measured and is related to the shear stress. As shown in Fig. 4, the maximum value of
shear stress corresponds to the shear yield stress. Before the peak has been reached, the
sample deforms elastically. Then, as soon as the structure of the fresh material breaks
down, a maximum stress is obtained. The relevance of the testing procedure and the
definition of the experimental constraints (dimensions of the Vane compared to those of
the sample) have been already studied by Dzuy and Boger 10' 11 • This procedure has also
been applied to cement paste 12 • Measurements have been carried out for various times of
rest (ranging from 0 to 30 minutes) and hence, enable to characterize the evolution of the
yield stress r 0 • The thixotropy of the material can be quantified through the evolution of
shear yield stress with the time of rest, and the possible interactions between SP and VEA
can be evaluated accordingly. Moreover, both methods of shear yield stress evaluation
can be compared.
Repeatability has been carried out on a given cement paste in order to determine
the accuracy of each rheological parameter determination. At least five tests have been
performed in each case. The calculated accuracies are summarized in Table 2. These
values enable to give a better confidence to the analysis of results. For example, one can
notice that the accuracy of the shear yield stress determined by the Vane is better than
that extrapolated by the Herschel Bulkley model on flow curves. Both kinds of results are
in good agreement. However, the slight difference between Vane and coaxial results can
be attributed to the shearing conditions. Yield stress is measured at rest with the Vane
geometry and under steady shear flow in the case of the concentric cylinders. Yield stress
measured by the Vane will be referred to as "at-rest yield stress" in what follows.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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EXPERIMENTAL RESULTS
Definition of the mixing procedure
The rheological characteristics of two typical cement pastes have been

preliminary measured in order to better define the mixing procedure. The choice of the
type of mixer and that of the SP introduction have been investigated. The effect of
applying successive mixing times to the same paste was also evaluated. Only the results
linked with the SP introduction are presented in this paper. More details can be found in
reference 13. As expected, the main conclusion is that a given mixing procedure is
required as far as rheometric measurements are concerned. Moreover, a new batch has to
be made for each measurement to ensure the same initial rheological state of the fresh
cement paste when evaluating the effect of the time of rest on shear yield stress values.
SP can be introduced at the end of the mixing procedure or can be added
together with the water. The way to introduce SP has an influence on the empirical test
results as shown in Table 3. These results are in good agreement with those already
published 14• The introduction of SP at the end of the mixing procedure leads to a more
flowable paste. Finally, the mixing procedure adopted in this study is characterized by the
following points: Volume of the batch: 1.2 litres - Total duration of mixing: 6 minutes
with increasing power - YEA is first added to water - Cement and limestone filler are
introduced progressively - SP is introduced after 4 minutes.
Empirical test results
The empirical spread and flow time test results are summarized in Table 4 and
presented in Fig. 5. Tests have been performed just after mixing. As expected, the lower
the YEA dosage and the higher the superplasticizer dosage, the greater the fluidity, i.e.
the shorter the flow time and the greater the spread. However, the fluidity is all the more
reduced by an increase in YEA, since the superplasticizer dosage is low. This is more
apparent in observing the flow time results in Fig. 5.
Rheological parameters
At-rest yield stress and apparent viscosity at f = 100 s -I are presented in

Fig. 6 and 7 respectively. The results are summarized in Table 5.
One of the main results is that the shear yield stress values measured by the
Vane just after mixing are in good agreement with those extrapolated from flow curves
by the Herschel Bulkley model (Fig. 8). This can be attributed to the particular testing
procedures and more especially to the shear history. However, one can assume that,
whatever the testing procedure, both types of values are well correlated. However, for
shear yield stress values greater than 60 Pa, the Herschel Bulkley model gives lower yield
stress values than the Vane.
Shear yield stress values ranged from 0 to 80 Pa just after mixing and from 0 to
150 Pa after 30 minutes of rest. Regardless of the admixture content, shear yield stress is
shown to increase with time of rest. This is due to the structuration of the material.
Whatever the VEA dosage and whatever the time of rest, the higher the superplasticizer
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dosage, the lower the rheological parameters. Moreover, an increase in the VEA dosage
leads to higher rheological parameters. Hence, both viscosity and shear yield stress are
affected by the VEA. Whatever the time of rest, an increase of the VEA content has a
greater effect for the lowest values of the SP content. Finally, for a given dosage of SP,
the influence ofVEA content is greater for a higher time of rest.
From a rheological point of view, the use of SP seems to have an inhibitor effect
on the VEA action. When the SP dosage is close to the saturation, VEA does not
significantly modifY the rheological behavior of the cement paste. The VEA is shown to
be more effective to enhance the rheological parameters of cement pastes containing the
lowest SP content and subjected to the highest time of rest, i.e. when the action of the SP
is reduced or when it comes to an end more rapidly.
Correlation between empirical test results and rheological parameters
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The correlation curve between spread and at-rest yield stress just after mixing is
an exponential one. This can be verified by plotting the logarithm of spread against yield
stress. The correlation does not depend on the VEA dosage (Fig. 9). The relationship
between spread and shear yield stress can be written as follows:
ln(r 0 ) = -0.23 S + 8.0518

Ina= 8.0518
(3)
with
{
_!_ = 0. 23
fJ
Where r 0 and S are at-rest yield stress (Pa) and spread (em), respectively. A
similar analysis was applied to flow time and viscosity results. A linear correlation is
obtained between the viscosity measured at 100 s- 1 and flow time. It does not depend on
the VEA dosage (Fig. 10):
v (r = 100s- 1 ) = 49.354 Fit -302.68 (4)
Where v and Flt are apparent vi~cosity measured at f = 1OOs- (mPa s) and
1
flow time (s), respectively. Linear correlations can also be obtained between flow time
and viscosity defined at other shear rates ranging from 1S to 100 s- 1• The parameters are
shear rate-dependent, and a power law function enables to describe their evolution in
relation to shear rate (see reference 13 for more details).
Finally, these correlations lead to the conclusion that easier empirical tests can
be performed instead of more complex rheological ones, when determining the
rheological behavior of flowable cement pastes. They support the points of view of
several authors about the modeling of empirical tests 15 · 16 . However, according to other
published papers, weak correlations are obtained between empirical tests and rheological
parameters 17•18 . The only way to explain that good correlations have been established in
this study is to assume that the parameters of the models probably depend on the studied
binder, SP and VEA.

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CONCLUSIONS
In this study, twelve cement pastes have been designed from the paste of a
typical SCC mixture by modifying the SP and the YEA dosages. Their rheological
behavior has been characterized to evaluate the effect of variations of SP and YEA
dosages. Test results enable the following conclusions:
1 - The use of YEA affects both viscosity and shear yield stress. An increase of YEA
content leads to an increase of rheological parameters. However, the saturation dosage of
SP is not modified by the YEA dosage.
2 -For SP dosage close to the saturation point, the YEA does not seem to modify the
rheological behavior of the paste.
3 - The shear yield stress values obtained from the Vane Geometry are in good
agreement with those obtained from flow curves (extrapolation by the Herschel Bulkley
model).
4 -From a statistical point of view, significant correlations are obtained between spread
and yield stress, and between flow time and apparent viscosity. Hence, easier empirical
tests can be performed to characterize the rheological behavior of cement pastes for a
given set of constituents.
ACKNOWLEDGMENTS
This study was carried out in the framework of the French national project BAP,
supported by the RGCU (Reseau genie civil et urbain) and the DRAST (Direction des
affaires scientifiques et techniques), France. It also received the financial support of the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
French Ministry of Research as part of a special study dealing with the stability of
cementitious materials.
REFERENCES
1. Okamura, H.; and Ouchi, M., "Self Compacting Concrete. Development, present use
and future", in: A. Skarendahl and 0. Petersson (Eds), Self Compacting Concrete,
Proceedings of the first International RILEM Symposium, RILEM Publications, La Ferte-
Mace (France), 1999, pp. 3-14.
2. Skarendahl, A., "The present- The future", in: 0. Wallevik and I. Nielson (Eds), Self
Compacting Concrete, Proceedings of the third International RILEM Symposium,
RILEM Publications, 2003, pp. 6-14.
3. Walraven, J., "Structural Aspects of Self Compacting Concrete", in: 0. Wallevik and I.
Nielson (Eds ), Self Compacting Concrete, Proceedings of the third International RILEM
Symposium, RILEM Publications, 2003, pp. 15-22.

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4. Bethmont, S.; D'Aloia Schwartzentruber, L.; and Rossi, P., "Study of Self Compacting
Concretes stability - Quantifying the group effects of the granular phase". Proceedings oj
SCC 2005 The Second North American Conference on the Design and Use of Self-
Consolidating Concrete and the Fourth International RILEM Symposium on Self-
Compacting Concrete. Edited by Surendra P. Shah, V. 1, 2005, pp. 219-226.
5. NF EN 197-1 "Cement Part 1: Composition, specifications and conformity criteria for

common cements". February 2001.
6. De Larrard, F.; Bose, F.; Catherine, C.; and Deflorenne, F., "The AFREM method for
the mix-design of high-performance concrete", Materials and Structures, V. 30, No 201,
1997, pp. 439-446.
7. EN 445 "Grout for prestressing tendons -tests methods". 1996.

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
8. Geiker, M.R.; Brandl, M.; Thrane, L.N.; Bager, D.H.; and Wallevik, 0., "The effect of
measuring procedure on the apparent rheological properties of Self Compacting
Concrete", Cement and Concrete Research, V. 32, No 11, 2002, pp. 1791-1795.
9. De Larrard, F.; Ferraris C.F.; and Sedran, T., "Fresh concrete: A Herschel Bulkley
material", Materials and Structures, V. 31, 1998, pp. 494-498.
10. Dzuy, Nguyen Q.; and Boger D.V., "Yield stress measurement for concentrated
suspensions",Journal of Rheology, V. 27, No 4, 1983, pp. 321-349.
11. Dzuy, Nguyen Q.; and Boger D.V., "Direct yield stress measurement with the Vane
method", Journal ofRheology, V. 29, No 3,1985, pp.335-347.
12. Saak, A.W.; Jennings, H.M.; and Shah, S.P., "Characterization of the rheological
properties of cement paste for use in self compacting concrete", in: A. Skarendahl and 0.
Petersson (Eds), Self Compacting Concrete, Proceedings ofthe first International RILEM
Symposium, RILEM Publications, La Ferte-Mace (France), 1999, pp. 83-94.
13. D' Aloia Schwartzentruber, L.; Le Roy, R.; and Cordin J., "Rheological behavior of
fresh cement pastes formulated from a Self Compacting Concrete (SCC)". Accepted for
publication in Cement and Concrete Research, to be published in 2006, V. 36, No 7,
pp. 1203-1213.
14. Agullo L.; Toralles-Carbonari, B.; Gettu, R.; Aguado, A., "Fluidity of cement pastes
with mineral admixtures and superplasticizer - A study based on the Marsh cone test",
Materials and Structures, V. 32, 1999, pp. 479-485.
15. LeRoy, R.; and Roussel, N., "The Marsh cone as a viscometer: Theoretical analysis
and practical limits", Materials and Structures, No 38, January-February 2005, pp. 25-30.

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-
16. Saak, A.W.; Jennings, H.M.; and Shah, S.P., "A generalized approach for the
determination of yield stress by slump and slump flow", Cement and Concrete Research,
V. 34, No 3, 2004, pp. 363-371.
17. Ferraris C.F.; Obla, K.H.; and Hill, R., "The influence of mineral admixtures on the
rheology of cement paste and concrete", Cement and Concrete Research, V. 31, No 2,
2001, pp. 245-255.
18. Lachemi, M.; Hossain, K.M.A.; Lambros, V.; Nkinamubanzi P.C.; and Bouzoubaa,
N., "Performance of new viscosity modifying admixtures in enhancing the rheological
properties of cement paste", Cement and Concrete Research, V. 34, No 2, 2004, pp. 185-
193.
Table 1-- Mix design of cement pastes
Mixture (n°)_ Oj1 2 3 415 6 7 8 9 10 11

lksP (SP = ksP SPo)* 5 I4 3 2 1 I1 3 5 1 3 5 I
kVEA {VEA = kVEA VEAo)** I I1 1 1 1 I2 2 2 4 4 4 6
*: SP0 = 0.05% (dc/(c+f), The saturation dosage SP* is equal to 4 SPo=0.2%

**: VEAo = 0.104% (dc/(c+f),
with: de :dry content of SP and VEA and (c+f): binder content (cement and limestone
filler)
Table 2 -· Evaluation of measurement accuracies
Empirical tests Rheological Parameters
Vane Coaxial Geometry

Geometry
Spread Flow 'l'o
v 'l'HB
0
(em) time (mPa s)
(s)
(Pa) (Pa)
Avera2e value X 29.8 16.47 8.35 749 12.05

Standard deviation 3.20 1.02 1.29 44.6 3.14
s
Accuracy (± 1.96u) ±0.63 ±2.00 ±2.53 ±87 ±6.15
for p = 1- a = 0.95
Table 3 - Introduction of superplasticlzer: empirical test results
Portable mixer with a Spread (mm) Flow time (s)

Cowles-blade impeDer (400ml)
Model 337 5.5
302
Mode2
.. .. . 6.7
.
Mode 1: SuperplasUclZCI' ts mtroduced at the end of the mtxmg procedure .
Mode 2: Superplasticizer is introduced together with the water.

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418 D'Aloia Schwartzentruber and Cordin
Table 4 -- Empirical test results obtained on pastes formulated from SCC mixture
Mixture Flow time_00_ Spread (em)

0 9.8 36.8
1 10.7 35.4
2 11.1 33.4
3 11.6 29.6
4 16.3 23.9
5 20.4 21
6 11.6 30.6
7 10.6 34.7
8 • 17.5
9 14.7 27.3
10 14.1 30.2
11 No flow 16.3
*: A continuous flow was difficult to obtained for mixture n°8. The measured value is not
significant in this case.
Table 5 - Rheological parameters obtained on pastes formulated from SCC mixture
Shear yield stress: t'0 (Pa)

Appareat
Time of rest: viscosity:
Omin 5min lOmin 30min v
Mixture HB DB (mPas)
Vane Decreasing Increasing Vaae Vane Vaae
Phase phase f=lOOs- 1
0 0.7 - - 0.7 0.7 1 123
1 1 1.1 1.1 1 1.3 2.4 225
2 1.6 2.3 1.5 2.2 2.5 3.8 260
3 3.6 3.6 4.2 4 6 10.4 331
4 16.3 16.5 17 18.6 20 46.3 575
5 25 23.8 23.4 - 30 62.9 676
6 2.5 2 1.8 - 3.7 6.7 274.2
-
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
7 0.9 1.6 1.3 1.2 1.4 226.2
8 28.6 35.5 41.8 - 26.5 117 930
9 6.1 9.1 9.6 - 9.8 13.6 429.9
10 2.7 2 2 - 3.3 5.3 315.3
11 80.5 59.7 56.5 - 86 150 1170

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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
i :--- __' \ 7
\\ I
\
\1'
.
' '
' '
nozzle
ll~$-.snnn
,--c::-,ro;;;
- 7 \____/
= 400ml
Spread Flow Time
Figure 1 --Characterization of cement pastes: empirical tests.
t2 ;
i
~
.s
0.05 0.1 0.~ 0 025 0.3 0.35

~ Dry content of SP/blnder content{%)
Saturation Dosage : 0.2%
Figure 2 --Determination of saturation point according to VEA dosage.

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420 D'Aloia Schwartzentruber and Cordin
'Y(lls)
r1 ~I9mm
h~58mm
r, ~ 20.5mm
1e=r, -r1 =l.Smm
Coaxial Geometry Test Procedure:
Phases 1 and 2: pre-shearing at a
constant rate of !Oos· during 120 s,
Phases 3 and 4 : steady state flow:
decreasing and increasing shear rate.
Figure 3-- Determination of rheological parameters: Coaxial Geometry.
1<----~
Dv=4cm
D=9.9an
Fresh cen:tent paste sample: 850ml
Figure 4 --Determination of rheological parameters: Vane Geometry.

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 5 --Flow time and spread of pastes formulated from SCC mix.

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'""
100
time of rest: 0 min time of rest 10 min
time of rest: 30 min
Figure 6- At-rest yield stress evolution according to time of rest (Vane Geometry).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0150-300
11!!450-600
.750-900
VEAO X4
VEA
0.25
Figure 7 --Apparent viscosity of paste at y=1oo 1/ s.

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100
.,=;
0
E
i 80
~ • decreasing shear rete
o increasing shear rate
1
/
.....
"3
ID
~
v
.c 60
~·
e,!!:.
i.,
rn
~
:
.c
rn
40
20
v v •
0
20 40 60 80 100
At-rest Yield Stress (Vane) (Pa)
Figure 8 --Comparison between shear yield stress values determined on flow cuNes
(Herschel Bulkley model) and those measured by Vane.
100
80
"'
0"-,~
y = -0.23x + 8.0518 _
2
R = 0.9927
I 60 \
~
~
~ 40 "'-.
~
20 \ u·v~o
+vEAx2
""'- ""-
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
~
OVEAx4
-1 •vEAx6
10 20 30 40 10 20 30 40
Mini cone diameter
Spread(cm) Spread(cm)
Figure 9 --Correlation between at-rest yield stress and spread.
1000
H. J-- • VEAO X2
o VEAOX4
_y = 49.354x- 302.68
R2 =0925
I
. /"
~v
1/0
10 15 20 25
Flow time (s)
Figure 10 -- Correlation between flow time and apparent viscosity ( y=1oo 1/s).

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SP-239-28
Effect of Temperature on Rheological

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Properties of Superplasticized
Cement Mortars
by J. Golaszewski
Synopsis: The methodology and the results of the investigation into influence of
the temperature on the rheological properties of fresh mortars containing different
superplasticizers and cements are presented, and discussed in this paper. Influence
of temperature was studied using Two Point Workability Test (TPwn and modified
standard mortars ace. PN EN 196-1 which can be also considered as a model of
concrete. The following factors were taken into consideration: mix temperature (10,
20, 30oC), specific surface of cement (320, 370, 420 m2/kg), C3A content in cement
(2, 7, 12%), Na20e content in cement (0.3, 0.7, 1.1%), and superplasticizer type
(polyeter and polycarboxylate acid based superplasticizers with different molecular
weight and polymer structure).
The obtained results show that temperature strongly influences rheology of mortars
and that the nature and range of this influence changes in wide range depending
on the properties of cement and superplasticizer used. Basic effects of temperature
influence on rheological parameters of mortars in relation to mentioned above
factors are presented and discussed. These relationships can be applied to control
workability of fresh mortar and concrete. Discussion about the results covers also
mechanism of temperature influence on rheological properties of mortars. It is
concluded that compatibility of cement- SP system must be tested taking into
account temperature. TPWT made on mortars makes possible to select a cement
- superplasticizer system that is optimal in given temperature, and to collect data
necessary for control of fresh mortar and concrete workability in various temperature
conditions.
Keywords: fresh concrete; mortars; rheology; superplasticizer;

temperature; workability

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424 Golaszewski
Dr. J. Golaszewski, is the lecturer at the Department of Building Processes at the Facult
of Civil Engineering at the Silesian University of Technology, Gliwice, Poland. His main
research fields include the rheology of cement based materials, the use of admixtures in
concrete and the technology of high performance concrete.
INTRODUCTION
The influence of temperature on rheological properties of fresh superplasticized

concrete is a very important technological problem. A particular superplasticizer (SP)
used with a particular cement often gives different results depending on temperature
during making of concrete (1-3). It is mainly because that the rate of the cement
hydration process (determined by its specific surface, chemical and mineral composition)
and the effectiveness of superplasticizer action significantly changes with varying
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
temperature of the fresh concrete (1-3, 9-11). Knowledge of how the temperature
influences the rheology of fresh concrete with different in properties of cement -
superplasticizer systems is crucial for concrete mixture proportioning and placing. This
knowledge makes it possible to select an optimal cement - superplasticizer system, and to
control fresh mortar or fresh concrete workability in various temperatures. Unfortunately,
until now, the systematic experimental data on this topic has been limited.
Determining the influence of temperature on rheological properties by testing fresh

concrete is difficult and not practical. It was stated in (4-7), that mortars can be
considered to be a model concrete. The knowledge of influence of temperature on
mortars rheology may contribute to the understanding of behaviour of fresh concrete in
different temperatures, and may ultimately lead to the possibility of predicting the flow
properties of the later from small scale tests on mortars. Also, the rheology of fresh
mortar is important in determining the ease of use of the material in its own right - for
instance for floor levelling or repairing damaged concrete in different temperatures. Thus,
the results presented in the paper can be used in controlling the workability of both
mortars and fresh concrete.
The main objective of this paper is to explore the influence of temperature on the
rheological properties of fresh mortars containing different superplasticizers and different
cements. The effects of temperature on the rheological properties of mortars were
investigated using Two Point Workability Test (TPWT) (2, 7, 8).
EXPERIMENTAL
Rheological Model and Measurements of Rheological Parameters of Fresh Mortars
It is well documented that fresh mortar, like fresh concrete, behaves as Bingham
material, whose properties can be expressed by two fundamental rheological parameters,
the yield stress and the viscosity according the formula:
(1)

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where 't (Pa) is the shear stress at shear rate y (1/s), 'to (Pa) is the yield value and TJpi (Pa.s)
is the plastic viscosity (4-7). The physical interpretation of yield value is that of the stress
needed to be applied to a material in order to start flowing. When the shear stress is
higher then yield value the mix flows and its flow resistance depends on plastic viscosity.
Rheological parameters of fresh mortar, like those of fresh concrete, can be

measured by applying a given shear rate and measuring the resulting shear stress.
Because of the nature of rheological behaviour of mortar, the measurements should be
taken at no less than two considerably different shear rates. The rheological parameters
are determined by regression analysis according to the relation:
T=g+Nh (2)
where Tis the shear resistance of a sample measured at rotation rate Nand g (N.mm) and
h (N.mm.s) are constants corresponding respectively to yield value 'to and plastic
viscosity TJpi· By suitable calibration of the rheometer, it is possible to express g and h in
fundamental units. According to (7), in the apparatus like used in this work, 'to = 7.9 g
and TJpi = 0. 78 h, but all results are given below in terms of g and h. The principles of
TPWT and rheological properties of fresh cement mortars and concretes are presented in
existing literature (2, 4-8).
Testing program
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
In this research, the following factors were taken into consideration:
• mixture temperature 10, 20, 30°C;
• cement specific surface 320, 370, 420 m2/k:g;
• C3A content in cement 2, 7, 12%
• Na20eq content in cement 0.3, 0.7, 1.1%
• superplasticizer type PEl, PE2 and PC according to Table 2;
Superplasticizer dosage (2%) and w/c (w/c = 0,45) were kept constant in the tests.
Materials and mixes
Cements of CEM I type, laboratory prepared by Mineral Building Materials

Institute in Krakow, and commercial superplasticizers were used for the investigations.
Their main properties are presented in Tables 1 and 2. The sand used was EN 196-1:1994
CEN model sand. Its properties are presented in Table 3. The mixture proportions of
mortars were based on standard mortar proportioning according to EN 196-1:1994.
Mixture proportions are shown in Table 4. The superplasticizer dosage refer to the
complete product.
Mortar mixing and testing procedures
The mixer and mixing procedure were in accordance with EN 196-1:1994;

superplasticizers were added with water. After the end of the mixing the samples of
mortars were transferred to Viskomat PC (see Fig. 1) and tested according to the
procedure shown in Table 5. This procedure roughly simulates the process of transport of

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426 Golaszewski
concrete mix in a truck concrete mixer. Because the measurement at the constant velocity
of the impeller rotation enables only the investigation of shear resistance (which at a
given speed consists of yield value and plastic viscosity), at 10 and 60 minutes the
rotation speed was changed from 120 to 20 1/min to define the rheological parameters
from flow curves.
The influence of temperature on rheological parameters of SP PEl, PE2 and PC

mortars with cements of different specific surface, C3A content and Na20eq content are
shown in Figs. 2 - 7. The analysis of variance ANOVA of influence of temperature, SP
type and specific surface of cement Sse' C3A content in cement and Na20eq content in
cement on rheological parameters of mortars after I 0 and 60 min from the end of mixing
are presented in Table 6, 7 and 8 respectively. It can be seen, that temperature
significantly influences rheological parameters g and h of superplasticized mortars and
that the nature and range of this influence depends on SP type, specific surface of cement,
C3A and Na20eq content in cement.
Effect of temperature on rheology of mortars with cements different in soecific

surface
The value of g of mortars with cement of specific surface Sse = 320 m2/kg
insignificantly decreases with rising temperature; this effect is most distinct for SP PE2
mortars. At the temperature of 10°C, the g value of Sse = 320 m2 /kg cement mortars,
independently on SP type, is clearly higher then that of mortars with cements of specific
surface Sse= 370 and 420m2/kg.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
The value of g of SP PE I, PE2 and PC mortars with cements of specific surface Sse
= 370 and 420m2/kg increases with rising temperature. The effect of rising temperature
on g of mortars is clearly proportional to cement specific surface, the higher the cement
specific surface, the more g increases due to rising temperature. The effect of rising
temperature on g of mortars is greatest when SP PEl is used.
The value of h of mortars at the temperature of 20°C, independent of the type of

superplasticizer, decreases with increasing cement specific surface. The nature and range
of changes of the h value of SP PEl and SP PE2 mortars under the influence of cement
specific surface do not depend on temperature. However, in the case of SP PC mortars
the nature of influence of temperature depends on cement specific surface. The value of h
of SP PC mortars with cement of Swe =320m 2/kg decreases with increasing temperature,
while it increases for SP PC mortars with cement of Swe = 370 and 420 m2/kg. It is
worthy to note that at low temperatures, the influence of cement specific surface on h of
SP PC mortars is very strong. Mortars containing cements of lesser specific surface are
characterized by clearly higher h values. The influence of cement specific surface on h of
SP PC mortars disappears with elevating temperature.

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In general, the g value of superplasticized mortars increases with time. The rate of
this increase of mortars with cement of Sse= 320m2/kg do not depend on temperature. In
the case of mortars with cement of Sse = 370 m2/kg the rate of g increase with time is
highest at the temperature of 20°C and lowest at the temperature of 10°C. In the case of
mortars with cement of Sse= 420 m2/kg the rate of g increase with time increases with
rising temperature. The range of variations in rate of g changes in time due temperature
depends on SP type and is clearly highest when SP PEl, characterized by lowest
molecular weight and lowest length of side chains, is used. It is worth noting, that at the
temperature of 10°C, the rate of g changes with time for all SP mortars is independent of
cement specific surface.
Temperature only insignificantly influences the rate of h changes with time of

superplasticized mortars. Only in case of SP PC mortars with cement of Swe = 420 m2 /kg,
the rate of h decrease with time slightly increases with rising temperature.
Effect of temperature on rheology of mortars with cements different in C1A content
The value of g of mortars with 2% C3A cement, independent of the type of

superplasticizer, decreases with a decrease in temperature. This decrease is the highest in
the case of mortars with SP PE2. In the case of mortars with 7% C3A cement, changes in
g depend on the superplasticizer type. The value of g of mortar with SP PEl increases
with rising temperature, while g of mortars with SP PE2 and PC stays at the same level.
The value of g of mortars with 12% C3A cement, independent of superplasticizer type,
increases with rising temperature. This increase is the greatest for mortars with SP PEl,
and the least for mortars with SP PC. It is worth noting that the g parameter of mortars
with 2% C3A cement and some superplasticizers may, at temperature of 10 ° C, be higher
than that of cements richer in C3A.
The influence of temperature on h of mortars depends on C3A contents in cement

and superplasticizer type, yet in this case it is difficult to determine unequivocal trends.
The value of h ofSP PEl mortars with 2 and 12% C3A cements increases slightly, while
of SP PEl mortars with cement 7% C3A decreases slightly with rising temperature. The
value of h of mortars with SP PE2 initially increases, then decreases with increase in
temperature. The scope of these changes does not depend on the content of C3A in the
cement. The value of h of mortars with SP PC at the temperature of 10°C depends
strongly on C3A content; the higher C3A content the higher h of these mortars. Increase in
temperature causes an increase of h in SP PC mortars. This increase is clearly higher
when 2 and 7% C3A cements are used. Due to this differences of h in SP PC mortars
with cements different in C3A contents, disappear with increase in temperature.
The influence of temperature on changes in g parameter of mortars with time is

strongly dependent on the C3A contents in cement and on the type of superplasticizer.
The range of changes in g with time of SP PE and PC mortars with 2% C3A cement does
not depend on the temperature. The range of increase of g with time of SP PE and PC
mortars with 7% C3A cement is the highest at the temperature of 20° C. At the same time,
at the temperature of 10 and 30°C changes in g with time of mortars with this cement

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428 Golaszewski
may be considered negligible. The influence of temperature on the range of increase in g
with time is the most distinct for mortars with 12% C3A cements. In the case of these
mortars, the influence of temperature on the range of changes in g with time depend on
the superplasticizer type. In the case of SP PEl mortar, the range of increase in g with
time is higher when temperature is rising. In the case of SP PE2 and PC mortars the range
of increase in g with time is the highest at the temperature of 20°C. However, one should
note, that at the temperature of 30°C, the range of increase in g with time of these mortars
is considerably higher than at the temperature of 10°C.
Changes in h with time of mortars with SP PE 1 and PE2 do not depend on

temperature. In the case of SP PC mortars the range of changes in h with time varies
depending on the C3A contents in cement and temperature; however, it does not show
unequivocal tendencies.
Effect of temperature on rheology of mortars with cements different in Na2o ..!l

content
The influence of temperature on g of SP PE and PC mortars changes depending of

the contents of Na2 0eq in cement. At the same time, the contents of Na20eq in cement
does not considerably influence changes in h and the range of changes g and h with time
for these mortars taking place under the influence of temperature.
Value of g of SP mortars at the temperature of 10 °C does not depend on Na20eq

content in cement. The influence of N a 20eq content in cement on g of mortars emerges at
higher temperatures, and the nature of this influence is connected with the
superplasticizer type. In the case of SP PC mortars, g decreases (mortar with 0.3%
Na20eq cement), does not change (mortar with 0.7% Na20eq cement) or increases (mortar
with 1.1% Na20eq cement) with rising temperature. In the case of SP PE2 mortars, g
decreases (mortar with 0.3 % Na20eq cement) or increases (mortars with 0.7% and 1.1%
Na20eq cements) with rising temperature. In the case of SP PEl mortars, values of g
increase with the temperature rising from 10 to 20°C, but the range of this increase does
not depend on N a20eq contents in cement. Further increases in temperature causes g of SP
PE 1 mortars with 0.3% Na20eq cement to decrease, mortars with 1.1% Na20eq cement to
increase. The value of g of SP PEl 0 mortars with Na20eq cement does not change
with increasing temperature. In general, temperature influence on g of SP mortars is
stronger when the Na20eq content in the cement is higher.
Effect of temperature on rheology of mortars - interpretation of results
Test results and its statistical analysis show that the nature of the influence of
temperature on rheological parameters of mortars depend both on the superplasticizer
type and on properties of the cement (that is to say: specific surface of cement and
contents of C3A and Na20eq in cement). The influence of temperature on rheological
parameters of SP PE and PC mortars decreases when superplasticizers with polymers of
greater molecular weight and of longer main and side chains are used, as well as with
decreasing specific surface of cement, decreasing the C3A contents in cement, and with
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decreasing Na20eq contents in cement. In relation to the properties of cement, the
intensity of temperature influence on rheological parameters of mortars depends
successively on: contents of C3A in cement, cement specific surface, and contents of
Na20eq in cement.
Presented results and results discussed in (9, 10, 11) indicate, that the nature of
the influence of temperature on rheological parameters of superplasticized mortars and
the range of their changes in time are derived from the following effects: the rate of
cement hydration process, adsorption of superplasticizer polymers on cement particles
surface, length of side chains of superplasticizer polymers, reduction of water amount in
the mix by evaporation, and changes in the pressure of cohesion in the mix.
Adsorption of SP PC and PE polymers on the cement surface increases with

increasing temperature ( 11 ). Increased SP adsorption enhances the steric hindrance effect
and slows down cement hydration process due to efficient inhibition of nucleation and
growth of hydrate products. This effect contributes to the decrease of g of SP PC and PE
mortars and to the reduction of changes in g and h with time of these mortars with rising
temperature. However, attention should be paid that higher superplasticizer adsorption, in
connection with an underdose of superplasticizer, may result in a faster increase of g with
time for mortars.
Increase in temperature accelerate the cement hydration process considerably,

which contributes to the reduction of the amount of the free water in the mortar and faster
burying of superplasticizer in the layer of hydration products ( 1, 2, 9-11 ). Due to this, an
increase of g and h of mortars occurs and the range of changes in g and h in time
increases. Influence of temperature on rheological properties increases with increasing
reactivity of the cement. For mortars with cements with low specific surface and low C3A
contents it is minimal, it increases proportionally with increase of cement specific surface
and C3A contents in cement.
Rheological parameters of mortars with superplasticizers with polymers of longer

side chains are clearly less sensitive to temperature changes. At higher temperatures these
mortars are characterized by slower changes in g and h with time. This is because the
superplasticizer polymers are buried in the layer of cements hydrates and the length of
side chains decrease relatively. Due to this, the steric hindrance effect gradually decreases
with time. The shorter the side chains of superplasticizer polymer, the higher the
influence of the cement hydration process on changes of the mortar rheological
parameters with time. When the rate of cement hydration increases with rising
temperature, the influence of length of the superplasticizer also increases. The longer side
chains of superplasticizer polymers prevents, for a longer time, the burying of the
superplasticizer in the layer of cement hydrates even at elevated temperatures (10, 11,
12). It is worth noting, that in case of cements with high Na20eq contents, the efficiency
of PE and PC action decreases as a result of changes in conformation of its polymer ( 12).
This results in a greater effect of temperature on rheological parameters of SP PE and PC
mortars containing high Na20eq contents cements.
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430 Golaszewski
When temperature rises, water evaporation from the mortar also rises, which
reduces the volume of free water and leads to an increase in g and h of the mortars and
accelerate the rate of changes of g and h with time (1, 2, 4, 6). Additionally, rising
temperature causes an increase in the pressure of cohesion of the mix, which leads to an
increase in g ( 4). Influence of these effects is particularly strong for mortars with low
w/c, and/or with low degree of filling aggregate with the cement paste, and/or low
superplasticizer content. These effects may significantly intensify changes of rheological
parameters of mortars caused by effects described above (4).
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Generally, in the case of cements of low specific surface and low contents of C3A
(that is to say cements of low initial chemical activity), the influence of temperature on
rheological properties of the mix is less intensive, because the increase in temperature
does not cause an increase in the hydration process speed of such importance that would
outbalance increased adsorption of the superplasticizer. As a result, g of mortars with
such cements, is independent of temperature and in some cases it even decreases with
rising temperature. Relatively small variations of h that accompany it, are probably a
consequence of changes in amount of adsorbed superplasticizer. In the case of cements of
high C3A content and/or of high specific surface (that is to say: cements of high initial
chemical activity), at higher temperature the speed of cement hydration process prevails
over the effect of increased adsorption of the superplasticizer. In such cases, especially
when the amount of free water in the mix is small and/or the amount of unabsorbed
superplasticizer in the solution is small, and/or if SP PC and PE polymers has short side
chains, changes in g and h with time may take place very fast.
SP PC and PE mortars show the maximum of g in different temperatures,

depending, as it seems, on the activity of cement. The more active the cement, the higher
the temperatures at which this maximum occurs. Basing on the authors own tests and data
from the bibliography, it can be stated that for cements with low C 3A content this
maximum occurs at the temperature of 10 - 20°C, in case of cement with medium C3A at
the temperature of 15 - 25°C, and for cements with high C3A contents at the temperature
of above 25°C. However, this range may be subject to changes depending on the type of
superplasticizer used, or more precisely on molecular weight and the length of side chains
of its polymer.
CONCLUSIONS
The results presented in the paper show that temperature strongly influences
rheological properties of superplasticized mortars. Changes in rheological properties of
these mortars can vary in a wide range, showing ambiguous trends depending on
temperature, SP type, C3A and Na20eq content in cement, specific surface of cement and
interaction of these factors.
The relationships presented in the current paper can be used for control and
adjusting workability of not only mortars but also of fresh concrete. However, due to the
variety of cements and superplasticizers, the influence of temperature on workability
should be always experimentally verified.

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Temperature has a significant impact on assessment of the cement - SP system
interaction. Thus, compatibility of the cement - SP system should be tested taking into
account forecasted temperature during making of concrete. TPWT made on mortars
makes possible to select the optimal SP - cement system in given temperature and to
collect data necessary for control of fresh mortar and concrete workability in various
temperature conditions.
REFERENCES
[1] Aitcin, P-C. High Performance Concrete, EF&N SPON, London, 1998.
[2] Neville, A.M., Properties of Concrete (in polish), Polski Cement, Krakow, 2000.
[3] Ramachandran, V S. Concrete Admixtures Handbook. Properties, Science and

Technology. 2nd Edn, Noyes Publications, Park Ridge, USA, 1995.
[4] Szwabowski, J. Rheology of mixes on cement binders (in polish), Wydawnictwo

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Politechniki Slllskiej, Gliwice, 1999, 239 pp.
[5] Banfill, P F G. The rheology of fresh mortar. Magazine of Concrete Research.

Vol. 43 (154), 1991. pp 13-21.
[6] Golaszewski, J. Adjusting of fresh concrete workability using superplasticizers,

(in polish), Wydawnictwo Politechniki Slllskiej, Budownictwo z. 99, Gliwice,
2003,216 pp.
[7] Tattarsall, G H, Banfill, P F G. The Rheology of Fresh Concrete, Pitman Books

Limited, Boston, 1983.
[8] Workability and Rheology of Fresh Concrete: Compendium of Tests, Report of

RILEM Technical Committee TC 145-WSM Workability of Special Concrete
Mixes, Ed. Bartos P.J.M, Sonebi M. and Tamimi A. K., RILEM Report 24,
RILEM Publications S.A.R.L, 2002.
[9] Grzeszczyk, S., Sudol, M. The effect of temperature upon the efficiency of new
generation superplasticizers (in polish), Cement-Wapno-Beton, Vol. VIII/LXX,
2003, No 6, pp. 325 - 331.
[10] Jolicoeur, C., Sharmann, J., Otis, N., Lebel, A., Simard, M-A., Page, M., The
Influence of Temperature on the Rheological properties of Superplasticized
Cement Pastes, 5th CANMET/ACI International Conference "Superplasticizers
and Other Chemical Admixtures in Concrete", ACI SP 173, Ed. Malhotra V.M.,
Rome, Italy 1997, pp. 379-391.
[11] Nawa, T., Ichiboji, H., Kinoshita, M., Influence of Temperature on Fluidity of
Cement Paste Containing Superplasticizer with Polyethylene Oxide Graft Chains,
6th CANMET/ACI International Conference "Superplasticizers and Other

Daneshlink.com
432 Golaszewski
Chemical Admixtures in Concrete", ACI SP 195, Ed. Malhotra V.M., Nice,
France 2000, pp. 195- 210.
[12] Uchikawa, H., Function of organic admixture supporting high perfonnance

concrete, Proceedings of the International RILEM Conference "The Role of
Admixtures in High Performance Concrete", Ed. Cabrera J.G. and Rivera-
Villarreal R., Monterrey, Mexico, 1999, pp. 69- 96.
Table I. Cements composition and properties
Constituents f% Specific
Cement surface
Si02 CaO Ah03 F~03 Na,o.. so3 c3s c,s C3A C4AF
fm2 /kg
#I 22.4 66.6 4.3 5.5 0.7 3.0 60 19 2 17 370
#2 23.3 66.6 4.7 3.5 0.3 3.0 52 28 7 9 370
#3 23.3 66.6 4.7 3.5 0.7 3.0 52 28 7 9 370
#4 23.3 66.6 4.7 3.5 1.1 3.0 52 28 7 9 370
#5 23.3 66.6 4.7 3.5 0.7 3.0 52 28 7 9 320
#6 23.3 66.6 4.7 3.5 0.7 3.0 52 28 7 9 420
#7 20.3 65.8 6.6 3.1 0.7 3.0 58 15 12 10 370
Table 2. Properties of superplasticizers
Density Concentration
SP Base component
fg/cm3l f%1
PEl Ipolyeter (low molecular weight, short side chains) 1.09 18
PE2 Ipolyeter (high molecular weight, long side chains) 1.05 36
polycarboxylate acid (highest molecular weight,
PC . 1.06 40
longest main chain, shortest side chains)
Table 3. Particle size distribution ofCEN model sand
Sieve size fmml Total residue on sieve[%]

2.00 0
1.60 7±5
1.00 33+5
0.50 67±5
0.08 99±1
Table 4. Mortar composition (g!batch)
Table 5 -- Measuring procedure used in tests
Start of measurement- speed 120 rev/min held constant for 10 min.

• Measurement ofM at decreasing N = 120-100-80-60-40-30-20 llmin. Test time 70s.
• Speed held constant for 39 min at 60 rev/min.
• Increase of speed to 120 rev/min. Speed held constant for I 0 min.
Measurement ofM at decreasing N = 120-100-80-60-40-30-20 1/min. Test time 70s.
End of measurement. Total test cycle time- 3620 s.
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Table 6 -- Analysis of variance ANOVA of influence of temperature, cement specific
surface and SP type on g and h of mortars after 10 and 60 min after end of mixing
Source of _g_ after 10 min h after 10 min~ after 60 min h after 60 min
variation Sig. Sig. Sig. Sig.
F-ratio F-ratio F-ratio F-ratio
level level level level
A: Temperature 40.974 0.007 0.620 0.595 119.769 0.001 22.600 0.016
B: Cement
155.093 0.001 35.892 0.008 213.552 0.001 166.787 0.001
specific surface
C: SPtype 156.911 0.001 971.961 0.000 121.349 0.001 1387.864 0.000
AB 96.373 0.002 18.353 0.019 128.083 0.001 4.637 0.119
AC 18.296 0.019 25.041 0.012 22.645 0.014 14.496 0.027
BC 8.634 0.054 12.601 0.032 13.229 0.030 24.175 0.013
ABC 5.938 0.085 22.600 0.013 9.743 0.044 8.695 0.051
Table 7 --Analysis of variance ANOVA of influence of temperature, C3A content in

cement and SP type on g and h of mortars after 10 and 60 min after end of mixing
Source of g after 10 minh after 10 min g after 60 min h after 60 min

A: Temperature 24.150 0.014 113.173 0.001 1195.94 0.000 343.275 0.000
B: C3A content
1047.19 0.000 7.807 0.065 10509.1 0.000 268.419 0.000
in cement
C: SPtype 280.261 0.000 2286.20 0.000 1083.17 0.000 6847.246 0.000
AB 188.902 0.001 10.942 0.039 1279.38 0.000 29.718 0.010
AC 12.524 0.032 63.642 0.003 110.279 0.001 131.619 0.001
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
BC 31.424 0.009 61.961 0.003 203.411 0.001 170.769 0.001

ABC 17.273 0.020 7.261 0.065 91.706 0.001 19.308 0.017
Table 8 --Analysis of variance ANOVA of influence of temperature, Na20eq content in

cement and SP type on g and h of mortars after 10 and 60 min after end of mixing
Source of g after 10 min h after 10 min g after 60 min h after 60 min

A: Temperature 28.752 0.011 99.676 0.002 37.932 0.007 29.256 0.011
B: Na2 0eq content
241.39 0.000 65.273 0.003 65.076 0.003 44.962 0.006
in cement
C: SPtype 60.593 0.004 2370.83 0.000 1.126 0.431 750.808 0.000
AB 40.664 0.006 0.509 0.739 19.152 0.016 2.438 0.245
AC 4.689 0.117 52.889 0.004 8.556 0.054 9.727 0.046
BC 26.336 0.011 37.294 0.007 22.841 0.140 19.497 0.017
ABC 3.913 0.145 1.016 0.552 2.706 0.222 3.521 0.164

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434 Golaszewski
Figure 1 -- Viskomat PC and its measuring element.
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50 g after 10 rrin
SP PE1 ~ Swc- 320m2/kg
40
-lr- Sw c - 370 m2/kg
~ Sw c- 420m2/kg
E 30
E
z g after 60 rrin
ti 20
-+- Sw c - 320 m2/kg
10 ~ Sw c- 370m2/kg
- - - Sw c - 420 m2/kg
0
10 20 30
TBIM"ERA TlJRE, "C
50 g after 10 rrin
SP PE2 ~ Swc- 320m2/kg
40
-lr- Sw c - 370 m2/kg
E30 ~ Swc- 420 m2/kg

E
~~
z g after 60 rrin
ti 20
-+- Sw c - 320 m2/kg
10 ~ Swc- 370m2/kg
- - - Sw c - 420 m2/kg
0 +------r------r-----~
10 20 30
TBIM"ERAlURE. •c
50 g after 10 rrin
SP PC ~ Sw c- 320m2/kg
40
-lr- Sw c - 370 m2/kg
~ Sw c- 420m2/kg
~
E 30
E
z g after 60 rrin
ti 20
-+- Sw c - 320 m2/kg
10 ~ Sw c- 370m2/kg
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
- - - Sw c - 420 m2lkg
0
10 20 30
Te.IIPERA lURE. •c
Figure 2 --The effect of temperature on g of mortars with CEM I cements different in

specific surface Sse and with SP PC and PE.

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Figure 3 --The effect of temperature on h of mortars with CEM I cements different in
specific surface Sse and with SP PC and PE.
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`,,`,,`,`,,`---
50 g after 10 ITin
~C3A-2%
40
--tr- C3A - 7%
E 30 -a- C3A- 12%
E
z g after 60 ITin
o; 20 -+-C3A-2%
10 --+-C3A-7%
-C3A-12%
0
10 20 30
TBIIIPffiA lURE, °C
50 g after 10 rrin
SP PE2 ~C3A-2%
40
--tr- C3A - 7%
E 30 -o--C3A -12%
E g after 60 ITin
z
o; 20 -+-C3A-2%
10 --+-C3A-7%
-C3A-12%
0
10 20 30
TEMPERA lURE, oc
50 g after 10 rrin
SP PC ~C3A-2%
40
--tr- C3A - 7%
~
E 30 -a- C3A - 12%
E g after 60 rrin
z
o; 20 -+-C3A-2%
10 --+-C3A-7%
-C3A-12%
0
10 20 30
TBIIIPffiAlURE, oc
C A content and with SP PC and PE.
3

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`---
438 Golaszewski
30 h after 10 rrin
SP PE1 --¢-C3A-2%
~C3A-7%
20
-o-C3A-12%
"'
E
h after 60 rrin
E
z
~ 10
z rc;;j --C3A-2%
......... C3A-7%
---C3A-12%
0
10 20 30
11:M'ffiAlURE. •c
30 h after 10 rrin
SP PE2 --¢-C3A-2%
~
~C3A-7%
20 -o-C3A-12%
"'
E
h after SO rrin
E
z
~ 10 --C3A-2%
......... C3A- 7%
---C3A-12%
0
10 20 30
T8\11PffiATURE, OC
30 h after 10 rrin
SP PC --¢-C3A-2%
~
~C3A-7%
20
-o-C3A-12%
"'
E
E h after SO rrin
z
.: 10 --C3A-2%
......... C3A-7%
---C3A -12%
0
10 20 30
T8I.FERA TURE, OC
Figure 5 --The effect of temperature on h of mortars with CEM I cements different in

C3A content and with SP PC and PE.

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50 g after 10 nin
SP PE1 --Q- Na20e- 0,3%
40 ---lr- Na20e- 0,7%
~
E 30 -o-Na20e-1,1%
E
z g after 60 nin
.,;; 20
-+- Na20e - 0,3%
10 __.__ Na20e- 0,7%
-11-Na20e -1,1%
0
10 20 30
TEI.1PERA ~ •c
50 g after 10 nin
SP PE2 --Q- Na20e - 0,3%
40
---lr- Na20e- 0,7%
E 30 -o-Na20e -1,1%
E
z g after 60 nin
.,;; 20
-+- Na20e - 0,3%
10 __.__ Na20e- 0,7%
- I I - Na20e- 1'1%
0
10 20 30
TEMPmATURE, •c
50 g after 10 nin
SP PC --Q- Na20e - 0,3%
40
-t.- Na20e- 0,7%
~
E 30 -o-Na20e-1,1%
E
z g after 60 nin
.,;; 20
- - Na20e- 0,3%
10 __.__ Na20e- 0,7%
-11-Na20e-1,1%
0
10 20 30
TEI.1PERA TURE. •c

Na 2 0eq content and with SP PC and PE.
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440 Golaszewski
30 h after 10 nin
SP PE1 --<>- Na20e - 0,3%
- b - Na20e- 0,7%
..
E
20
-o-Na20e-1,1%
E h after60 nin
z
..; 10 -+- Na20e - 0,3%
i lil g .......... Na20e- 0,7%
---Na20e-1,1%
10 20 30
1Bv1PERAlURE, •c
Figure 7-- The effect of temperature on h of mortars with CEM I cements different in
Na 2 0eq content and with SP PC and PE.
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````,,,,```,-`-`,,`,,`,`,,`---
SP-239-29
Hydrophobic Admixtures to
Control Corrosion of Galvanized Steel
Reinforcement in Concrete
by F. Tittarelli, G.L. Valenti, and G. Moriconi
Synopsis: The influence of silane-based hydrophobic agents, added to concrete as

chemical admixtures, on the corrosion resistance of galvanized steel reinforcement
embedded in concrete was studied. Sound or deliberately pre-cracked concrete
specimens, with o.s or 1 mm wide crack, were manufactured with w/c of 0.45 and
0.75, both in the presence and in the absence of a silane admixture. The specimens
were exposed to wet-dry cycles in a 10% NaCl aqueous solution. The results, in
terms of electrochemical measurements, as well as visual and metallographic
observations carried out on the galvanized steel reinforcement removed from the
specimens, showed that the hydrophobic concrete is able to protect galvanized steel
reinforcement from corrosion even in the presence of cracks in the concrete cover,
especially when a high w/c is used.
Keywords: galvanized steel reinforcement; hydrophobic admixture;

reinforcement corrosion

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442 Tittarelli et at.
Francesca Tittarelli is a Chemist and has a Ph.D. in Materials Engineering; she holds a
permanent position as researcher at the Department of Materials and Environment
Engineering and Physics of the Technical University ofMarche, Ancona, Italy.
Gian Lorenzo Valenti is Professor of Materials Science and Technology at the

Department of Environmental Engineering and Physics, University of Potenza, Italy. His
main research interests are in the fields of cement and concrete technology, development
of special cements and utilization of industrial wastes and by-products. He is author of
more than 100 publications on international journals and conference proceedings.
Giacomo Moriconi is Professor of Materials Science and Technology at the Technical

University of Marche, Ancona, Italy and is the Head of the Department of Materials and
Environment Engineering and Physics. He is the author and co-author of numerous
papers in the field of cement and concrete technology, building materials performance,
and durability.
INTRODUCTION
Static, dynamic and cyclic loading as well as shrinkage, creep and thermal stress or even,
in precast concrete, mechanical shock and flexural stress induced during transportation,
lifting and mounting, can cause concrete cover cracking. Cracks greatly increase the
concrete surface permeability since they represent preferential paths for penetration of
aggressive agents such as chloride ions, which promote corrosion of steel ( 1-6). After the
initial induction period, the degradation process grows very rapidly, since the
deterioration mechanisms show a destructive expansive nature (7).
Traditional protection methods against corrosion, such as the reduction in the

water/cement, the use of pozzolanic additions, the use of corrosion inhibitor admixtures
and the surface coating of the concrete or the steel reinforcing bars, often fail when
cracks reach the steel reinforcement. Since the cost of repairing reinforced concrete
structures during the induction period of the corrosion process is generally much lower
than the rehabilitation cost during the propagation process (8), concrete technology is
continuously developing new methods to prevent the onset of deterioration in reinforced
concrete structures.
In this respect, it is evident that steel corrosion would not occur if water, which acts as
the main carrier for aggressive substances and the medium where corrosion reactions
develop, is permanently prevented from wetting the concrete porous structure. The water
in contact with a porous material such as concrete penetrates the material by means of
capillary forces following the Washburn equation, but the molecular attraction between
water and the concrete pore walls can be lowered by surface treatment based on
impregnation with hydrophobic agents, such as those currently named silanes and
siloxanes (9-21). Their alkoxylic groups are chemically bound to the concrete hydrated
silicates by a condensation reaction while their hydrophobic alkylic groups come out on
the pores surface (22).
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To optimize the effectiveness and durability of hydrophobic agents (23-34), they have
been recently introduced in the concrete mixture in order to make both the surface and
the whole concrete bulk hydrophobic (35-41). In this way, bulk hydrophobization could
cancel the detrimental effect, from a corrosion point of view, of concrete cover cracking.
However, experimental results have shown that the silane admixture is able to protect
steel reinforcement from corrosion only in sound concrete (42), while in cracked concrete
it can induce a catastrophic corrosion (39). This unexpected result has been ascribed to a
greater oxygen diffusion through an unsaturated hydrophobic cementitious matrix that, in
this way, can feed more quickly the cathodic reaction controlling the corrosion process
(37).
However, if galvanized steel reinforcement is used, in which case it has been already
demonstrated that passivation is mainly promoted by oxygen (43), it is easy to predict
that the hydrophobic admixture could effectively counteract the corrosion process.
Therefore, the present paper is aimed to verify the validity of this intuition by monitoring
the corrosion behavior of galvanized steel reinforcement embedded in sound or cracked
hydrophobic concrete exposed to chloride environment.
EXPERIMENTAL
Concrete mixtures with w/c of 0.45 and 0.75 were manufactured by using commercial
Portland cement type CEM IIIA-L 42.5 R with and without silane as a hydrophobic
admixture. The silane admixture was used in form of 45% aqueous emulsion of butyl-
ethoxy-silane at a dosage of 1% by cement weight. Natural sand and gravel with 6-mm
and 11-mm maximum size, respectively, were used as aggregate. The proportions of the
concrete mixtures are given in Table 1, where compressive strengths at 2, 7, and 28 days
are also reported. In the presence of silane admixture, a reduction in the concrete
compressive strength of about 18 and 23% was recorded with respect to that of non-
hydrophobic concrete when w/c ratio of0.45 and 0.75 was used, respectively.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
For each concrete type, nine prismatic specimens (70x70x280 mm in size) were
produced. These prismatic specimens were reinforced with a hot dip galvanized steel
plate (2IOx40xJ mm) embedded at mid depth from a specimen side. The zinc coating,
obtained by immersion in molten zinc, was 100-f..lm thick with an outer pure zinc layer
about 20-f..lm thick. An electric cable, isolated through a PVC sheath, was connected to
each steel plate by means of spot welding. The weld was protected by epoxy resin before
casting the concrete mixture. Steel plates instead of usual rebars were used in order to
facilitate the cracking of specimens and to modulate the crack width.
After casting, all the specimens were wet cured for 2 days and air dried for 1 month at
room temperature. Then, six specimens for each concrete type were deliberately cracked
by a flexural stress in order to open a crack 0.5 or 1 mm wide in the middle zone, with the
crack apex reaching the steel reinforcement. In order to localize the crack formation at a
predetermined point, a preformed V-notch, 10 mm deep and 14 mm wide, was produced
on these specimens by placing a plastic rod on the bottom surface of the mould. Once the
crack of required width, measured by an extensometer, was obtained its opening was

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444 Tittarelli et al.
maintained after the elimination of the flexure load by the insertion of small elements of
hard polymeric material of suitable thickness. In order to make the oxygen and chloride
flow unidirectionally and perpendicularly directed to the steel plate through the concrete
cover, all the other sides of the specimens but the one containing the crack apex were
epoxy coated.
Subsequently, the specimens were exposed to wet-dry cycles (2 days wet followed by 5
days dry) in a 10% NaCl aqueous solution for four months.
The corrosion risk of the reinforced concrete specimens exposed to the chloride
environment W!iS evaluated by free corrosion potential measurements .with respect to a
saturated calomel electrode (SCE) as reference, while the kinetics of the corrosion
process was followed by polarization measurements. The polarization resistance, in
inverse relation with· the corrosion rate, was measured through the galvanodynamic
method, using an external graphite bar as counter-electrode, by calculating its average
value between the anodic and cathodic zones. The electrochemical values reported in the
graphs are averaged among the ~easurements carried out· on three specimens of each
concrete type during the immersion period.
In order to validate and to complete the evaluation of the electrochemical behavior, the
galvanized steel plates were extracted by splitting the concrete specimens after 16 wet-
dry cycles in the chloride solution and the corrosion extent was assessed by visual
observation. Metallographic analysis was carried out on a cross section of the galvanized
steel plates in order to evaluate the decrease in the zinc coating thickness due to the
corrosive attack. A cross section 1 em from the crack apex was chosen in order to reflect
the effects of a real corrosive process, avoiding the extreme situation produced at the
crack apex by a strongly accelerated corrosion process in order to reduce experimental
times. Zinc corrosion products were identified by X-ray diffraction. Additionally, the free
chloride concentration derived by water extraction from the cement paste in contact with
the steel reinforcement in the same cross section was measured at the end of the exposure
time to the chloride environment.
Electrochemical measurements
Figure 1 shows the free corrosion potential values of galvanized steel plates embedded in
concrete specimens with w/c = 0.75 as a function of wet-dry cycles in the aggressive
environment. In non-hydrophobic concrete they assume active values of about -1000
mV/SCE reflecting a generally great corrosion risk and they keep constant for almost all
the test time. On the other hand, in bulk hydrophobic concrete, just after the exposure to
the aggressive environment the galvanized steel plates assume values of -800 mV/SCE in
the presence of concrete cracks regardless of the crack width, and -600 mV/SCE in sound
specimens. Moreover, the free corrosion potentials move towards more passive values,
indicating a very low corrosion risk, after a few wet-dry cycles. Cracks in the concrete
cover do not significantly affect the reinforcement potential.
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In the absence of concrete cracks, the polarization resistance (Figure 2) of the steel
reinforcement in hydrophobic concrete is even ten times higher with respect to that in
non-hydrophobic concrete, indicating a very low corrosion rate; moreover, this value
seems to further increase during the test time. In the presence of concrete cracks, the
difference between hydrophobic and non-hydrophobic concrete is moderate, but the
polarization resistance of steel reinforcement in hydrophobic concrete remains at least
three times higher with respect to that of non-hydrophobic concrete. Moreover, in this
case, cracked hydrophobic concrete behaves even better than sound non-hydrophobic
concrete, whatever the crack width; therefore, bulk hydrophobization seems to cancel,
from a corrosion point of view, the detrimental effect of concrete cover cracking.
The two different crack widths considered do not affect the corrosion results in non-
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
hydrophobic concrete specimens, due to the high porosity of the cement matrix, while, in
the hydrophobic ones, just a little bit higher corrosion rate is detected in the presence of
the wider crack.
A good quality concrete matrix with a w/c as low as 0.45 seems to partially hide the
beneficial effect of the hydrophobic admixture. The corrosion risk described by the free
corrosion potential measurements (Figure 3) is about the same regardless of the cement
matrix. However, the polarization resistance of steel reinforcement (Figure 4) is always
higher in the hydrophobic concrete specimens with respect to the corresponding non-
hydrophobic ones, even if the difference is not as evident as observed in the more porous
cement matrix. In particular, in this case, the hydrophobic effect was not able to cancel,
from a corrosion point of view, the detrimental effect of the concrete cover cracking as
previously observed in concretes with w/c = 0.75. Moreover, due to the low porosity of
the cement matrix, the crack width influenced the test results both in the presence and in
the absence of silane with corrosion risk and corrosion rates which increase with the
crack width.
Finally, by comparing the results obtained in concrete specimens with w/c = 0.45 and
0.75, it is evident that the hydrophobic admixture, even in the presence of concrete
cracks, decreases the corrosion rate monitored in very porous concrete, as that
manufactured with w/c = 0.75, to values comparable with those obtained in good quality
concrete, as that manufactured with w/c = 0.45. In other words, silane cancels the
detrimental effect, at least from the corrosion point of view, of a large porosity of the
cement matrix.
As reported in Table 2, the hydrophobic admixture is able to reduce chloride penetration

both in sound and cracked concretes of about 60%, especially when in the concrete cover
narrower cracks (0.5 mm) are present.
Visual evaluation
Visual and metallographic observations carried out on the galvanized steel plates
removed from the specimens after the aggressive exposure confirmed the electrochemical
measurements.

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The galvanized steel plates embedded in non-hydrophobic concrete with w/c = 0.45
(Figure 5a) showed a general corrosion state, where dark Fe-Zn alloys appeared on the
plate surface, meaning that total consumption of the pure zinc layer due to the corrosive
attack occurred, as also confirmed by metallographic analysis.
On the other hand, for the galvanized steel plates embedded in hydrophobic concrete
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
(Figure 5b), zinc grains were still well visible on the galvanized plate surface and close to
the crack apex a white surface deposit of adherent and compact zinc corrosion products,
later identified by X-ray diffraction as zinc oxides, hydroxides and calcium
hydroxyzincate, appeared. In particular calcium hydroxyzincate is a well known
passivating zinc corrosion product that, once formed, protects the underlying pure zinc
layer from further corrosion as metallographic analysis has well demonstrated.
Also the visual evaluations, in agreement with the electrochemical measurements,

confirm that the hydrophobic admixture is able to counteract galvanized reinforcement
corrosion especially in concrete with w/c = 0.75.
As a matter of fact, the galvanized steel plates extracted from non-hydrophobic concrete
(Figure 6a) showed a very deep general corrosive attack with red rust appearing on the
surface indicating that total consumption of the protective zinc layer had occurred.
On the other hand, the zinc layer on steel reinforcement embedded in hydrophobic
concrete (Figure 6b) appeared thicker, as shown by the metallographic section, in spite of
an apparently stronger corrosive attack with respect to that observed in hydrophobic
concrete with lower w/c ratio (Figure 5b), indicating that the corrosive attack is weaker.
It must be pointed out that this behavior was observed regardless of the chloride
concentration. This was measured close to the plates embedded in hydrophobic concrete
with w/c = 0.75 and it resulted in a concentration four times higher with respect to that
measured with w/c = 0.45 (Table 2). Such an observation confirms greater oxygen
diffusion, as that assured by more porous hydrophobic cementitious matrix manufactured
with higher w/c, can really favor galvanized reinforcement passivation.
CONCLUSIONS
The use of hydrophobic admixture can improve the corrosion resistance of galvanized
steel reinforcement in concrete specimens exposed to wet-dry cycles in a chloride
aqueous solution, even in the presence of concrete cracks, especially when a high w/c is
used.
Bulk hydrophobization reduces water absorption approximately 50% and, at least from
the corrosion point of view, cancels the detrimental effect of a large porosity of the
cement matrix as well as, in high porous concretes, of concrete cover cracking.
Galvanized steel in hydrophobic concrete not only assures the concurrence of the benefits
derived from the use of either steel galvanization or concrete hydrophobization, but it
could further provide a useful synergistic effect. As a matter of fact, hydrophobic

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concrete in repelling water, not only hinders the penetration of aggressive agents
inducing the corrosion process, but also favors faster oxygen diffusion through concrete,
thus making galvanized reinforcement passivation faster and easier, particularly when a
high w/c is used.
Therefore, it is concluded that the use of galvanized steel reinforcement in hydrophobic

concrete could be an optimal, innovative, relatively cheap and effective method against
corrosion of reinforced concrete structures even in the presence of concrete cracks.
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Publication No.183, pp. 556-566.
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31) Cleland, D.J., and Basheer, P.A.M., 1998, "Management and Maintenance of
Surface Treatments for Concrete", Corrosion of Steel in Reinforced Concrete
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Concrete under Severe Conditions: Proceedings of the Second International
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Spon, London, U.K., pp. 1341-1350.
33) Jones, M.R., et al., 1995, «Concrete Surface Treatment: Effect of Exposure
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34) Sauder, M., 1999, "Damage caused by water repellent agents- reasons and counter-
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35) Vivian, H.E., 1960, "Some Chemical Additions and Admixtures in Cement Paste and
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Cement, Washington, U.S.A., 1960, pp. 909-926.
36) Tittarelli, F., et al., 2000a, "Comparative Evaluation of Traditional and Innovative
Corrosion Protection Methods in Cracked Reinforced Concrete Exposed to Chloride
Environment", Durability of Concrete: Proceedings of the Fifth CANMETIACJ
International Conference, Barcelona, Spain, 2000 (SP-192), ed. V.M. Malhotra,
37) Tittarelli, F., et al., 2000b, "Influence of Silane-Based Hydrophobic Admixture on

Oxygen Diffusion Through Concrete Cement Matrix", Superplasticizers and Other
Chemical Admixtures in Concrete: Proceedings of the Sixth CANMETIACJ
International Conference, Nice, France, 2000 (SP-195), ed. V.M. Malhotra,
38) Mailvaganam, N.P., 1984, "Miscellaneous Admixtures", Concrete Admixtures

Handbook, ed. V.S. Ramachandran, Noyes Publications, pp. 518-524.
39) Fratesi, R., et al., 1997, "The Influence of Hydrophobic Concrete on the Corrosion of
Rebars", Superplasticizers and Other Chemical Admixtures in Concrete:
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(SP-173), ed. V.M. Malhotra, American Concrete Institute, pp. 105-122.
40) Alred, J.M., et al., 2001, "The effect of initial moisture content on water transport in
concrete containing a hydrophobic admixture", Magazine of Concrete Research, V.
53, No.2, pp. 127-134.
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41) Alshamsi, A.M., et al., 1997, "Hydrophobic materials, superplasticizers and
microsilica effects on setting of cement pastes at various temperatures", Magazine oj
Concrete Research, V. 49, No. 179, pp. 111-115.
42) Polder, R.B., et al., 2001, "Prevention of reinforcement corrosion by hydrophobic

treatment of concrete", Heron, V. 46, No.4, pp. 227-238.
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43) Tittarelli, F., et al., 1999, "The Role of Oxygen on the Passivation Mechanism of
Galvanized Steel Rebars", Infrastructure Regeneration and Rehabilitation -
Improving the Quality of Life Through Better Construction - A Vision for the Next
Millennium: Proceedings of International Conference, Sheffield, U.K., 1999, ed.
R.N. Swamy, Sheffield Academic Press, pp. 517-526.
Table 1 - Concrete mixture proportions (kg/m3) and related compressive strengths (MPa)
w/c = 0.45 w/c=0.75
Mixtures w/c= 0.45 w/c = 0.75
hydrophobic hydrophobic
Water 240 233 240 236
Cement 533 533 320 320
Silane - 11.8 - 7.1
Sand 639 639 949 949
Gravel 847 847 716 716
R.,at2 days 19.9 16.8 6.7 4.,9
Rc at 7 days 35.4 27.5 14.5 9.2
Rc at28 days 39.2 32.3 25.6 19.8
Table 2 - Chloride Ions Concentration(% by cement mass)

Concrete type no crack 0.5mmcrack 1 mmcrack
w/c = 0.45 0.8 1.1 1.8
w/c= 0.45
0.2 0.4 0.5
hydrophobic
w/c=0.75 3.4 3.9 4.5
w/c= 0.75
1.4 1.5 1.9
hydrophobic

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-!ZOO,-------------=---,------,------,
~no crack Don-hydrophobic
..... 0.5 mm crack non-hydrophobic
-UOO ..... 1 mm. crack noo-bydropllobic
8 10 12 14 16
Number of cycles
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 1- Potential of the galvanized steel plate embedded in concrete specimens
with w/c = 0.75 as a function of the number of wet-dry cycles.
1600.-------------------------,
1000
g 800 oo()oo-oo crack bydropllobic .... oo crack oon-bydrophobfc

rl v-o.s mm eratk hydrophobic ..... 0.5 mm crack non-hydrophobic
600 ~ 1 mm crack hydrophobic -&-] mm crack Don-hydrophobic;:
16
Nu.f.ber of c~cles
12 14
Figure 2- Polarization resistance of the galvanized steel plate embedded in cracked

concrete specimens with w/c = 0.75 as a function of the number of wet-dry cycles.
-!ZOO,------------------------,
~no crack hydrophobic .... no crack non-hydrophobic
-1100 ~0.5 mm crack hydrophobic . . . 0.5 mm crack oon-bydrnphobic
-i:P 1 mm crack hydrophobic _._ 1 m.m enclt .non-hydropbobk
-1000 t-----------------------1
~-~+---------------------~
~
~ ~00+---------------------~
!.
lilil -700
400L--~--~--~-----~-~--~-~
B 10 12 14 16
Number of cycles
Figure 3- Potential of the galvanized steel plate embedded in concrete specimens

with w/c = 0.45 as a function of the number of wet-dry cycles.

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1600
~DOC:l11C:kbydropltobk: ...... no c:ratk noa-llyclropboblc:
1400 -D-0.!!1 mm track bydropbobk -4-0.!!I mm crack nou-b:ydropbobic: -
-t:P-1 m~~:~ crack hydrophobic ...... 1 mm crack non--hydrophobic
!ZOO
1000 ....,
§:..., ~
r:l" ..,._/
~ .....- ~
/:..
400
... ......
~
zoo
-- ~ 'iF""'
0
0 8 10 1Z 14 16
Number of cycles
Figure 4- Polarization resistance of the galvanized steel plate embedded in cracked

concrete specimens with w/c = 0.45 as a function of the number of wet-dry cycles.
~no crack n
0.5 c1·ack (l ..5 it~

111111
, 111111 crac k 1 , ,
I mm crack ,
~
, 'v
.•.
.
'!', 4
'
'
< '
1 111m crack ~
:
t
' '
(a) (b)
Figure 5- Visual observation and metallographic section of the galvanized steel plate
embedded in cracked concrete specimens with w/c = 0.45 in the absence
(a) and in the presence (b) ofthe hydrophobic admixture.
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(a) (b)
Figure 6- Visual observation and metallographic section of the galvanized steel plate
embedded in cracked concrete specimens with w/c = 0.75 in the absence
(a) and in the presence (b) of the hydrophobic admixture
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-30
Influence of Cement and Plasticizer

Type on the Rheology and Reactivity of
Cementitious Binders
by H. Vikan, H. Justnes, and R. Figi
Synopsis: The interactions between six commercial cements and three types
of plasticizers, namely naphthalene sulfonate formaldehyde condensate (SNF),
lignosulfonate (LS) and polyacrylate grafted with polyether (PA) are investigated
using cement paste. PA was found to be the most efficient plasticizer of the three
tested even though it was found to present lower adsorption onto cement than SN F
and LS. SNF and LS brought about comparable results. PA was observed to induce
flow gain of pastes within 2 hours of rheological measurements, while pastes made
with SNF and LS exhibited flow loss as a function of time.
The adsorption characteristics were found to depend on the plasticizer type. The
plasticizer saturation dosages were, moreover, found to depend on cement surface
area (Blaine fineness), amount of cubic C3A and soluble sulfates.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Keywords: adsorption; cement; lignosulfonate; plasticizers;

polyacrylate; rheology; sulfonated naphthalene formaldehyde
condensate

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456 Vikan et al.
Dr. Hedda Vikan works as a scientist at SINTEF Concrete, Trondheim, Norway. Her
Ph.D. work at the Institute ofMaterials Technology, Norwegian University of Science
and Technology (NTNU) was based on the rheology and reactivity of cementitious
binders with plasticizers.
Dr. Harald Justnes is Chief Scientist at SINTEF Concrete, Trondheim, Norway. His field
of interest covers the chemistry of cement, concrete, admixtures and additives from
production, through reactivity, to durability. Dr. Justnes is Adjunct Professor in "Cement
and Concrete Chemistry" at NTNU, Trondheim.
Renato Figi is leader of the analytical chemistry group at EMP A Swiss Federal
Laboratories of Materials Testing and Research, Diibendorf, Switzerland.
INTRODUCTION
The performance of superplasticizers in cementitious systems has been found to

depend on cement fineness, cement composition, mode of introduction into the mixture,
as well as the type and chemical composition of the superplasticizer< 1' 2J. Electrostatic and
steric repulsion are the two main dispersion mechanisms for plasticizers(3J. Other effects
that may prevent agglomerate formation are depletion and tribology<4 J. It is not clear how
the molecules adsorb on the cement surface: The model of the grafted polymer dispersing
according to steric hindrance may be a simplification. It would then be necessary for all
the intramolecular bonds (van der Waal type, hydrogen bonds) to break and unwind the
polyether chains to let them stretch out into the water phase (even though the hydrophilic
nature of polyethers may aid in stabilizing such a configuration). Alternatively, the
molecules may stay unwound as polymeric balls or "miscelles" that equally well will lead
to steric hindrance. Andersen et al.(s) found furthermore that the most effectively adsorbed
polymer was not necessarily the one which gave the largest negative zeta potential. Thus,
the zeta potential depends probably both on the amount of polymer adsorbed and on the
fraction of electronegative charges that can be introduced into the Stem layer without
actually being adsorbed on the surface. They explained these findings by the "loop" and
"train" adsorption mechanisms. Polymer size has also been found to influence the
adsorption capacity and rheology of paste0 ' 6).
This paper investigates how the adsorption behaviour of the three superplasticizers
SNF, LS and PA depends upon various cement characteristics and how it affects
rheological properties of cementitious paste. These plasticizers represent different
adsorption mechanisms, and will therefore interact differently with the same cement. The
experimental work was done partly at EMP A and partly at SINTEF.
EXPERIMENTAL
Three different categories of plasticizers have been studied namely:

1. SNF in water solution with 42% solids. The number of structural units (n) in the
molecule was presumably between 10 and 20. The molecular weight is 2,350 for
n = 10 and 4, 700 for n = 20. A SNF dosage of 1.2% will according to the
producer reduce the water content a concrete need to obtain the same slump
flow as a concrete without SNF addition by 20 kg/m3 .
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2. Sodium LS in which the sugar content is reduced and the molecular size is
enriched by ultra filtration. The molecular weight of the polymer was 51,000.
The LS can according to the producer exhibit a water reduction of 8-18%
depending on dosage and concrete recipe.
3. Polyether grafted polyacrylate in water solution containing 18% solids and a
viscosifying agent (which is not specified by the producer). The molecular
weight was 220,000. A dosage of I% of this type of plasticizer will according to
the producer be responsible of a water reduction of 20 kg/m 3 •
The ultraviolet absorption spectrum of dilute aqueous solutions provides a method

for the detection of aromatic and other UV -active (conjugated bonds) groups in
superplasticizers. The UV spectra of different superplasticizers (SNF, sulfonated
melamine formaldehyde (SMF) and lignosulfonate) are quite different and can be used
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for chemical identification purposes(l,3l. Polyacrylate-type products generally do not

contain aromatic groups and do not show UV -adsorption in a readily accessible spectral
region, i.e.>200 nm(7l. The consumption of PA by cement was therefore measured as
Total Organic Carbon (TOC) left in the pore water with a Shimadzu TOC Analyzer
5000A.
The cementitious pastes were prepared using cements 1-5 described in Table 1 and
all three admixtures. Mixtures made with SNF and LS were prepared with w/c of 0.40.
The blending of the pastes was performed in a high-shear mixer from Braun
(MR5550CA) by adding solids to the water and mixing for 'li minute, resting for 5
minutes and blending again for 1 minute. The superplasticizers were either added with
the water first (immediate addition) or 5 minutes after water addition (delayed addition).
Rheological parameters were recorded 20 minutes after water addition by a parallel

plate (1 mm gap, upper plate serrated to 150 11m depth) rheometer MCR 300 produced by
Physica. The measurements were done isothermally at 20°C. A shear stress - shear rate
curve was measured with linear sweep of shear rate from 200 down to 2 s- 1 in 30 points
lasting 6 s each. Hysteresis, gel strength and oscillation sequences were included in the
measurement program, but will not be discussed further. The full measurement program
lasted 25 minutes and was repeated 4 times to monitor time dependencies.
The pastes were filtered through 0.45 11m-filters 20 minutes after water addition. The
pore solutions were diluted 50-200 times with a solution of"artificial pore water" (NaOH
and KOH with a KINa molar ratio equal to 2 and pH = 13.2). The amount of
superplasticizer in the water phase was read from the standard curve which had been
made with diluted series of SNF (290 nm) and LS (283 nm). The standard curve is thus
the relationship between the measured absorbance and the plasticizer concentration in the
pore water. The difference between the added and measured contents of superplasticizer
gave the consumed portion, i.e. plasticizer adsorbed onto cement grains and hydration
products and intercalated portion of the superplasticizer. The consumed amounts of
plasticizer are distinguished as adsorbed and intercalated since previous reports have
indicated that some of the plasticizer molecules will be embedded by the hydration
products<8'9>.

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458 Vikan et al.
PA is a much stronger superplasticizer than SNF and LS and may lead to segregated
cement pastes even at low PA dosage when the w/c is as low as 0.40. Cement pastes with
PA were, therefore, produced in the same manner as for SNF and LS, but with w/c in the
region 0.30-0.40 to ensure stability. Pore water was filtrated from the pastes as described
above, but this time filtrations were done every 25 minute to study the effect of elapsed
time. The pore water was diluted 1:10 with 0.1M HCl before TOC measurements. The
amount of plasticizer consumed by the cement was calculated as the difference between
the added and the measured content of organic carbon.
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Numerous rheological models have been proposed to describe cementitious

materials 00 ' 11 ' 12>. The Bingham model has become very popular due to its simplicity and
ability to describe cementitious flow. The model describes the shear stress ( r) as a
function of yield stress ( '[' y ), plastic viscosity ( J1 p) and shear rate ( r) as follows:
(1)
The concept of yield stress is sometimes a very good approximation for practical
purposes. The Bingham model applies, however, often only for limited parts of the flow
curve if the tested material has shear thinning or shear thickening flow behaviour. Shear
thickening flow behaviour may furthermore result in negative yield stress at high shear
rates. Such a negative yield stress has no physical meaning. There has been raised a
question whether or not a yield stress exists or whether all non-Newtonian materials will
exhibit a finite zero-shear viscosity. Barnes and WaltersC 13l states that the yield stress
concept is an idealization and that given accurate measurements, no yield stress exists.
They claim that even concentrated systems flow in the limit of very low stresses and that
these materials appear not to flow merely because the zero shear viscosity is so high.
Yahia and Khayat114> support this statement by finding that the yield stress correlated well
to the apparent viscosity at low shear rate (5 s· 1).
It was in this work decided to use the area under the flow curve (Pals) as a
measurement of "flow resistance" rather than describing the flow curve with the usual
Bingham model. The flow resistance was calculated as the area under the flow curve
using the trapezoidal rule:
(2)
The flow resistance could, of course, have been obtained at constant shear rate, but a
shear rate range of 43-8.8 s- 1 consisting of six measuring points relevant for mixing and
pouring concrete05 l was used in order to compare with parameters from the Bingham
model. The question is whether the area under the flow curve represents something more
"physical" than an "apparent" yield stress from Bingham modeling. In a parallel plate set-
up with shear area, A [m 2], and gap h [m] between the plates;

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t = FIA [N/m2 or Pa] (3)
(average shear stress over a shear rate interval)
~y = vlh (4)
(shear rate difference over an interval)
where F [N] is the force used to rotate the upper plate, and v [m/s] is the angular velocity.
The area under the curve= t·~ y = (F/A)-(~v/h) = F·~vN (5)
where V [m3] is the volume of the sample between the parallel plates.
The unit of the area under the curve can be expressed as N·mlm3·s, J/m3·s or W/m3 • It
is in other words, the power required to make a unit volume of the paste flow with the
prescribed rate in the selected range. The power, P [W], required to mix concrete for a
certain time interval is actually sometimes measured by simply monitoring voltage (U
[V]) and current (I [A]) driving the electrical motor of the mixer, since P = Uxl.
Graphs of consumed plasticizer and flow resistance as a function of added SNF

superplasticizer are depicted in Figure 1. The "saturation point" was defined as the
superplasticizer dosage where a further addition of superplasticizer did not significantly
reduce the flow resistance of the slurry. The consumption curve did, in some cases, reach
a plateau value at superplasticizer saturation. In case of adsorption, such behavior is
characteristic for high-affinity adsorption in which virtually all the available
polyelectrolyte binds to the adsorbent at specific surface sites until monolayer coverage is
attained (i.e. Langmuir adsorption). The length of the plateau indicates the difficulty of
formation of a second layer because of charge repulsion between the adsorbed plasticizer
molecules and those approaching from the solution< 16l. A plateau was however not always
easily detectable. Lower-affinity adsorption is characterized by curves in which the
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amount of polyelectrolyte adsorbed is always less than the polyelectrolyte dosage, with
the isotherm gradually tapering off with increasing polyelectrolyte concentration rather
than attaining a definite adsorption plateau07l. Such a linear isotherm is consistent with
conditions in which the number of adsorption sites remains constant throughout the
whole range of solute (plasticizer) concentrations until the pore water is saturated. This
means that the surface available for adsorption expands (due to dispersion and hydration)
proportionally with the amount of plasticizer adsorbed< 16l.
In some cases as seen for the delayed addition of SNF to Cement 1 (Figure 1) and
immediate addition of PA to Cement 2 (Figure 2) the consumption decreases after
reaching a maximum. This might indicate that surplus molecules in the water phase are
compressing the ionic double layer or that adsorbed molecules expand and hinder
molecules in the water phase to attach at the surface. A similar phenomenon was
discovered in the case of cement by Andersen et al.< 5l and Yoshioka et al. 08l. The
occurrence of a maximum is especially pronounced for the PA-isotherms. This is
probably caused by the high molecular weight of this superplasticizer which renders the

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460 Vikan et at.
adsorption more sensitive to changes in concentration than SNF and LS. It is known that
the adsorption of PA is sensitive to the length of the ethylene oxide grafted chains.
Materials with relatively short ethylene oxide chains tend to follow Langmuir-type
adsorption isotherms in which both the efficiency and the effectiveness of adsorption
decrease as the chain length is increased. Those with intermediate chains are found to
adsorb by multilayer formation, while the materials containing longer chains tend not to
adsorb at all< 19).
Experiments with delayed addition of polyacrylate were not performed since Vikan
and Justnes< 20 ) established that delayed addition of PA only causes marginal decrease of
flow resistance. Delayed addition of SNF plasticizer to Cement 1 (Figure 1) resulted,
however, in strong reduction of flow resistance and reduced amount of consumed
plasticizer. The main reasons for the decrease in flow resistance and amount of consumed
superplasticizer in the case of delayed addition may be reduced intercalation of the
plasticizer in the newly formed ettringite dominating a possible increased surface
adsorption. Furthermore, "free" or available excess superplasticizer in the interstitial
solution which do not intercalate or adsorb onto cement particles have also been found to
contribute to increased flow of the paste< 21 • 22 ).
The adsorption and flow resistance measurements illustrate that PA is a much

stronger plasticizer than SNF and LS since it is effective at much lower dosage. Cement 1
requires, for example, 1.20% SNF or 0.32% PA to obtain a flow resistance of
approximately 600 W/m3 • Similar results have been found by Golaszewski and
Szwabowski(23 ) and Hanehara and Yamada(2 4l.
It is not straight forward to analyze the adsorption data as a function of time since
the concentration of superplasticizer in the pore water might decrease by intercalation in
the hydration products or increase as the pore water is consumed by the hydration
process. The concentration of PA, LS and SNF in the pore water did, however, not
change noticeable with time. This observation is backed by Chiocchio and Paolini(lS) who
claimed that the adsorption of SNF and SMF is completed after only 1-2 minutes.
Change of flow resistance with time
It was found that flow change with time is dependent on the cement type and type
and dosage of superplasticizer. Flow loss was typical for pastes with SNF. Pastes with LS
generally developed lower flow loss than pastes with SNF and flow gain was observed
for several pastes. Similar results have been found by Uchikawa et al.<26) who found that
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LS forms complex salts with Ca2+ more easily than SNF. Thus, the complexation of ci+,
delays the saturation of Ca2+ in the pore water, which influences the morphology of
hydrate produced (e.g. larger [Ca3(Al,Fe)(OH) 6]X3 ·xH20 (AFt) crystals are produced
with LS than with SNF) and delays the setting time of cement.
Another noticeable feature for SNF is that the flow loss has a turning point at the
saturation dosage whereafter the flow loss rates increase noticeably. Nawa et al.< 27 ) found,

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on the other hand, that cement pastes with SNF and SMF superplasticizer had large flow
loss rates, but the flow loss rate decreased with a higher superplasticizer dosage.
Pastes with LS tended to transform flow loss to flow gain when the added dosages
reached supersaturation. Flow gain at supersaturation might indicate inhibited or reduced
hydration rate. Surplus LS molecules in the water phase might also adsorb onto the newly
formed hydration products enabling increased flow.
Flow gain was the general trend for most pastes with PA. These results which are
backed up by Nawa et al. (Z?l and Golaszewski and Szwabowskic23 l might be due to
delayed adsorption or preferred adsorption on hydration products.
No turning point for flow loss as a function of PA dosage has been detected which
might indicate that the grafted chains of the molecules are long enough to provide steric
stabilization even if the stem is adsorbed and covered by hydration products. Table 2
shows flow loss data for Cement 2 with different dosages of the three plasticizers studied.
Correlation of consumed olasticizer with cement characteristics

The consumed amounts of superplasticizer at saturation are given in Table 3. The
table and flow resistance - adsorption curves (Figure 3) show that the saturation dosages
of the superplasticizers depend mainly on the cement and to a lesser extent on the
superplasticizer type when SNF and LS are considered. PA has a lower saturation than
SNF and LS, but this plasticizer will not be discussed further due to the limited amount of
data.
Ranking of the adsorption capacity of the cements seems to depend upon the
superplasticizer dosage. SNF molecules adsorb somewhat stronger on cement than LS
below saturation while the opposite trend is found at saturation dosage. All in all, it can
be concluded that SNF and LS are adsorbed roughly to the same extent to the cements.
Cement 3 (cement with fly ash) consumes less superplasticizer than expected
regarding its relatively high surface (Blaine) as shown in Table 3. Experiments to study
the influence of fly ash on the superplasticizer adsorption were therefore performed.
Adsorbance of LS and SNF were measured on pastes of pure Cement 1, pure ground fly
ash (FA), pure FA with 2% by weight Ca(OH) 2 and pastes with 50% FA and 50%
Cement 1 measured by weight. The results given in Table 4 ·show that pure fly ash
adsorbs less superplasticizer than cement, while the amount of consumed plasticizer for
the cement-FA mix was found to be close to the results of pure cement. These results
seem to coincide with the work of Nagataki et al.C 28 l. Pure FA pastes with 2% Ca(OH)z
adsorbed approximately the same or slightly higher amount of plasticizer as pure cement
paste. This result seems to indicate that Ca2+ adsorbs on the FA surface and that the
anionic superplasticizer molecules adsorb on the positive charged sites thus created.
Jolicoeur and Simardc29l pointed out a similar effect after the observation of SNF being
adsorbed to a minor extent by silica fume slurry, but being equally adsorbed by cement
paste and cementitious paste with silica fume replacement.
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462 Vikan et al.
Correlations of saturation dosages of SNF and LS with the cement characteristics
Blaine, contents of total C3A, cubic C3A (cC 3A), soluble sodium equivalent (Na,qv) and
the products of some of the cement characteristics were attempted. The same procedures
were not performed for pastes with P A due to the limited amount of available data. The
regression coefficients, R2, in Table 5 indicate that the saturation dosage of SNF depends
strongly on the single cement characteristics Blaine and content of cubic C 3A. The cubic
crystal modification of C 3A seems, moreover, to have a stronger influence on the
plasticizer saturation dosage than the total C 3A content. This finding indicates, in
agreement with other publications, that the cubic crystal modification of C3A is more
reactive than the orthorhombic <30· 31 l.
Good correlations were found for the saturation points of SNF with the product of
Na.,qv and Blaine fineness as well as the product of Naeqv and cubic C 3A. The best
correlation was found for the product of cubic C3A and Blaine as illustrated by Figure 4a.
This is logical since high surface and aluminate content in the cement means high C3A
surface area enabling more intercalation.
The saturation dosage of LS seems to have a stronger dependency on the amount of

water soluble alkali than observed for pastes with SNF. This result might be caused by
the fact that LS form complexes in a higher degree than SNF as discussed above. Good
correlations were found between the saturation dosages with the single cement
characteristics soluble sodium equivalent and cubic C 3A. A good correlation was found
for the product of cC 3A with Blaine, but the best fits were found for the products
Na.,qv·Blaine and Na.,qv·C 3Acubic as seen by Table 5. Figure 4b shows an example of a
correlation of saturation dosages of LS with the cement characteristics Na equivalent
times cubic C3A for the five cements.
In the presence of superplasticizers, the influence of sulfate (water soluble alkali

sulfates) content is known to depend on the superplasticizer type. It has been found in the
presence of SNF type superplasticizers that addition of alkali sulfates (Na2 S04) can lead
to improvements in rheological properties of cement paste since the SO/ ions lead to a
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decreased adsorption (SO/ - superplasticizer competition) or intercalation of SNF

superplasticizer in early C3A hydrates, thus leaving more of the latter available for paste
fluidification< 32l. The data in Table 5 seem, however, to indicate that increased alkali
content will increase the saturation value of the superplasticizer indicating that more of
the superplasticizer molecules are being consumed by the hydration products. This
finding might be caused by accelerated early hydration of the clinker phases with
increasing content of easily soluble alkalis< 33 l.
CONCLUSIONS
PA was found to be a more effective plasticizer than SNF and LS, even though it
was consumed to a lesser extent by the cements. SNF and LS gave comparable results.
P A resulted moreover in flow gain as a function of time while SNF and LS resulted in
cement pastes with flow loss.

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The adsorption characteristics onto cement were found to depend on the plasticizer
type, and the plasticizer saturation dosages were found to depend on cement surface area
(Blaine fineness) and contents of cubic C3 A and easily soluble sulphates. The best
correlation, overall, was found for the product of cubic C 3A and Blaine. The
investigations indicated, moreover, increased plasticizer consumption with increased
soluble alkali content, which might be caused by accelerated hydration.
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Table 1-- Mineral composition(%) and soluble alkali content of

Portland cements obtained by QXRD and Plasma-emission-
spectrometry. The cement types are identified by the notation given
b)y EN 197-1
Cement no. 1 2 3 4 5
Cement CEMI CEMI CEMII CEMI CEMI
Type 42.5RR 42.5R A-V 52.5R- 42.5
42.5R LA R-LA
Alite 64.7 66.0 60.3 65.0 61.9
Belite 14.8 9.4 7.1 12.9 19.7
Ferrite 7.5 8.7 7.1 9.6 12.0
Cubic 5.9 3.4 3.1 0.5 0.4
Aluminate
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Orthorhombic 1.1 1.7 3.4 3.0 1.7
Aluminate
Lime 1.0 1.2 0.2 0.6 0.7
Periclase 1.6 1.2 1.7 0.3 0.4
Gypsum 0.0 0.2 0.0 1.4 1.3
Hemihydrate 1.8 2.0 2.1 1.5 0.4
Anhydrite 0.6 0.5 0.4 0.4 0.4
Calcite 0.5 4.6 0.6 4.0 0.7
Portlandite 0.3 0.4 0.5 0.3 0.2
Quartz 0.0 0.4 1.5 0.4 0.2
Arcanite 0.3 0.4 0.1 0.0 0.0
Mullite - - 2.6 - -
Amorphous - - 9.3 - -
Blaine 546 360 467 364 447
Fineness
(m2/kg)
K(mg/1) 920 880 580 320 360
Na (mg/1) 220 170 116 74 84
N!!eqv (mg/1) 760 690 458 262 296

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Table 2 -- Flow loss measurements of low shear rate range (43-8.8 s-1)
of pastes made with Cement 2 with SNF, LS or P A. The flow loss is
calculated as the alteration of flow resistance with time
Cement2 Flow Loss (%)
SPDose Time SNF LS PA
i%) (min)
0.16 20 - - -
45 13 7 -10
70 21 15 -14
95 25 19 -15
0.32 20 - - -
45 33 7 -7
70 65 17 -9
95 91 25 -11
0.48 20 - - -
45 64 -14 -5
70 154 -10 -6
95 255 -5 -7
Table 3 --Consumed (adsorbed and intercalated) superplasticizer at

saturation point for SNF and lignosulfonate. Consumed amounts are
caIculated as me super) IastictZer
· per m2 cement
Cement Blaine Cubic Consumed Consumed
2
fmeness C3A(%) LS (mg/m ) SNF (mg/m2)
(m 2/kg)
1 546 5.9 12.2 8.7
2 360 3.4 11.9 8.4
3 467 3.1 5.1 7.8
4 364 0.5 13.2 7.2
5 447 3.1 11.2 10.7
Table 4 -- Consumption (adsorbed and intercalated) LS

superplIastictZer used a t lo/co b1y mass of cement on FA and Cement 1
Adsorbant Consumed plasticizer
(%of added)
Pure FA 24.3
50150 Cement 1+ FA 67.4
Cement 1 69.2
Pure FA + 2% Ca(OH)2 69.3
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468 Vikan et at.
Table 5 -- Regression coefficients for correlations of superplasticizer
saturation dosaee with various cement characteristics
Cement Characteristic RT(SNF) R 2 (LS)
Blaine 0.82 0.45
C3Atot 0.60 0.54
C3Acubic 0.89 0.83
N!!eqv 0.56 0.83
C3Atot·Blaine 0.78 0.66
C3Acub·Blaine 0.97 0.84
Naeqv·Blaine 0.88 0.97
Na.,qv·C3Acub 0.85 0.99
Na.,qv·C3Acub·Blaine 0.88 0.98
Cement 1 • SNF
--FR
- • -FRO
--cons.
SNF
- • -Cons.
01---....,..=_ _ _ _ _ _-l SNF D
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0 0.5 1 1.5 2 2.5 3 3.5
Dosage of plasticizer
(% of cement)
- ---·---·-- -······-·--·-·-· --· --·-·--·---···--·-·-·----- ---·-··-····-····-·-----
Figure 1-- Flow resistance and consumed (adsorbed and intercalated)

superplasticizer content as a function of SNF plasticizer dosage for immediate and
delayed addition. Plasticizer is either added first with the water or 5 minutes after
water addition, D =delayed.
Cement 1 • PA2, wlc = 0.40
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

Concentration plasticizer(% by cement)
-. - - .. --
Figure 2 ·- Flow Resistance and amount of consumed (adsorbed and intercalated) PA

as a function of added PA cement 2.

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Lignosulphonate SNF
8000 - . - - - - - - - - - - ,
i
2l
6000
<='>
f
2l
6000
.§ 4000 ~ 4000
.,
·~ ·~
~ 2000 ~ 2000-
0
0
u: u:
0 0.1 0.2 0.3 0.4 0.5
Consumed Plasticizer Consumed Plasticizer (%
cement)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 3 -- Flow resistance as a function of consumed (adsorbed and intercalated) LS

(a) and SNF (b) plasticizer and cement type (numbered 1-5 according to Table 1).
SNF lS
1.6 1.6
0 R' =0.97 0 R' =0.99
/' V'
~~1.2 ~~ 1.2
·-"' ·-"'
03:
~~0.8 ~~ 0.8
""
oa>
:o::e <=e
~"'
~ ~0.4 ~ u 0.4
en <n
0 0
0 1000 2000 3000 4000 0.0 2.0 4.0 6.0
cC3A'Biaine Na(eqv)'cC3A
Figure 4 --Saturation point of adsorbed SNF (a) and LS (b) superplasticizer as a

function of cement fineness (Blaine) and cubic C3A (cC3A) and soluble alkalis
(sodium equivalent) and cubic respectively. Cl

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470 Vikan et al.
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SP-239-31
Effect of Advanced Hybrid Admixture on

High Strength Concrete
by K. Saito , M. Kinoshita , K. Okada, and T. Nawa
Synopsis: One-pack hybrid admixture (HSP) combining high fluidity, viscosity-

reducing property, and shrinkage-reducing capability for high strength concrete with
a target strength of 6o to 150 MPa was developed and examined.
HSP showed high fluidity and viscosity-reducing performance, as well as excellent
autogenous shrinkage-reducing effect to achieve a reduction in the autogenous
shrinkage of 21 to 44% with respect to that of concrete containing a conventional
high-range water-reducing admixture.
HSP was therefore found to be a simple and effective solution to shrinkage problems
for a wide range of high strength concretes.
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Keywords: admixture; autogenous shrinkage; high strength concrete;

hybrid; polycarboxylate; shrinkage reducing agent; viscosity

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472 Saito et al.
Kazuhide Saito, Chief Research Engineer of R&D, Construction Chemicals Division,
Takemoto Oil & Fat Co.,Ltd., 2-5 minatomachi, gamagori, aichi, 443-8611 Japan. His
current research interests are fluidity, strength and durability development for high
strength concrete.
Mitsuo Kinoshita, Dr. Eng., General Manager of R&D, Construction Chemicals

Division, Takemoto Oil & Fat Co.,Ltd., 2-5 minatomachi, gamagori, aichi, 443-8611
Japan.His current research interests are chemical synthesis of water-soluble functional
polymer and material science.
Kazuhisa Okada, Research Engineer of R&D, Construction Chemicals Division,

Takemoto Oil & Fat Co.,Ltd., 2-5 minatomachi, gamagori, aichi, 443-8611 Japan. His
current research interests are chemical synthesis of water-soluble functional polymer and
material science.
Toyoharu Nawa, Dr. Eng., Professor, Division of Solid Waste, Resources and
Geoenvironmental Engineering, Graduate School of Engineering, Hokkaido
University,Kita 13, Nishi 8, Kita-ku, Sapporo, 060-8628 Japan. His current research
interests are fluidity and shrinkage of concrete incorporated with mineral and organic
admixture and the utilization of recycle aggregate.
INTRODUCTION
High strength concrete has been increasingly used for high-rise reinforced concrete
collective housing, mostly in urban areas. Higher strength generally requires higher
binder content, leading to greater autogenous shrinkage of concrete. For this reason,
simple, effective, and low-cost measures for reducing the shrinkage of high strength
concrete have been anticipated in order to prevent early cracking. It is known that
shrinkage reducing admixture reduce autogenous shrinkage as well as drying
shrinkage[l],[2]. With this as background, the authors have developed one-pack hybrid
admixture (HSP) for concrete in the high and ultra high strength range with a target
strength measured on cylinders of 60 to 150 MPa that is having a water-cement ratio
(W/C) of 0.35 to 0.15, based on the investigation into items (1) to (3) given below with
the aim of developing a new-type admixture combining high fluidity, viscosity-reducing
property, and shrinkage-reducing property.
(1) Development of a water-reducing component having high fluidity,
viscosity-reducing property, and high compatibility with the shrinkage reducing
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
admixture to be adopted
(2) Selection of an effective shrinkage reducing admixture compatible with the
water-reducing component described in (1) above
(3) Investigation into optimum proportions of(2) and (3) above
This paper reports on the outline of the development of HSP and its properties on
concrete presenting a strength in the range of 60 to 150 MPa.

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EXPERIMENTAL PROCEDURE
Materials
Cement
Normal portland cement (N), low-heat portland cement (L), and silica fume cement
(SF C) were used. SFC is a premixed cement containing silica fume (SF) in place of 10
wt% of L cement. Their chemical and physical properties are given in Table 1 and Table
2.
Aggregate
Fine aggregates were land sand with a saturated surface dry (SSD) density of 2.58
g/cm3 and fineness modulus of 2.67 (S1) and crushed sand with a SSD density of 2.64
g/cm3 and fineness modulus of 2.67 (S2). Coarse aggregates were crushed stone with a
SSD density of2.68 g/cm 3 and solid volume percentage of60.0% (Gl) and crushed stone
with a SSD density of 2.66 g/cm3 and solid volume percentage of 60.0% (G2).
Procedures
Concrete proportioning
Table 3 gives the mixture proportions of concrete. The type of cement was changed
depending on the target strength while fixing the unit water content constant. N cement, L
cement, and SFC were used for compressive strength of 60, 80, and I 00 MPa or more,
respectively. Aggregate with high strength was used for the target strength of 150 MPa.
Concretes with W/C's of 0.35 and 0.25 were entrained with target air as 3%, whereas
those with W/C's of 0.20 and 0.15 were not air-entrained because previous study showed
that high strength concrete with lower W/C than 0.20 have sufficient freezing and
thawing resistance without entraining air[3].
Mixing concrete
Concretes were mixed using a forced-mixing-type mixer with a capacity of 55 liters
as follows: Dry-mix fine aggregate and cement for 15 sec. Add water and admixture and
mix for 60, 90, and 300 sec for W/C's of 0.35, 0.25 and 0.20, and 0.15, respectively. Add
coarse aggregate and mix for 120 sec. The test temperature was 20 °C. The batch size
was 30 liters. The air content was adjusted by the use of an air-entraining admixture or
defoaming admixture.
Test methods
Slump flow-- Slump flow was measured in accordance with JIS A 1150. The slump flow
was determined as the average diameter of the fresh concrete after spreading by
measuring in two directions at right angles.
L-flow velocity -- L-flow velocity (Lv) was measured by using L-flow meter [3] shown
in Fig. 1. The flow speed of concrete between 5 and I 0 em from the flow start line of the
L-flow meter was defined as L-flow velocity.
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474 Saito et at.
Changes in the fluidity of fresh concrete -- Changes in the fluidity of fresh concrete
versus time were measured immediately after mixing and after leaving concrete to stand
for 30, 60, and 90 min in a mixing vessel and re-working immediately before measuring.
Setting time -- Setting time was measured in accordance with JIS A 1147 by means of
penetration resistance measurements on mortar sieved from concrete.
Drying shrinkage test -- Drying shrinkage test was conducted in accordance with JIS A
1129. The specimens for length change molded in a size 100xJOOx400 mm were
demolded after 24 hours, cured in water until the age of 7 days and kept in a room with
temperature of 20 oc and 60%RH for 6 months. The base length of the specimen was
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measured at the age of 7 days.
Autogenous shrinkage test -- Autogenous shrinkage test was conducted following the
method established by JCI Research Committee for Autogenous Shrinkage[4]. the strain
was measured by the data logger using embedded strain gauges in the middle section of
the form shown in Fig.2, and the changes in the strain after initial setting were regarded
as autogenous shrinkage strain. The specimens molded in a size lOOx100x400 mm were
sealed and kept in a room with temperature of 20 oc until the age of 28 days.
Compressive strength test-- Compressive strengths were tested with 200x100 mrn
cylinder specimens in accordance with JIS A 1108. The specimens were water-cured
immediately after being demolded until compression testing at 7, 28 and 91 days.
Freezing and thawing resistance test -- Freezing and thawing resistance test was
conducted in accordance with ASTM C 666. the specimens molded in a size
1OOx 1OOx400 mm were taken out of the molds at the age of 24 hours and subjected to the
test after 28 days curing in 20 °C water. They were frozen in water at temperature of -18
± 2 oc and thawed at 5 ± 2 oc until 300 cycles.
Accelerated carbonation test -- Accelerated carbonation test were conducted in
accordance with JIS A 1153. The specimens molded in a size 100x100x400 mm were
demolded after 24 hours, cured in water with 20 oc until the age of 28 days and cured in
air with 20 oc and 60%RH until the age of 56 days before they are subjected to the test.
The specimens were exposed to an atmosphere containing 5% C0 2 with 20 °C and
60%RH. The carbonation depth was measured by applying phenolphthalein color
indicator on the fracture surface of freshly broken off fragment of the specimens at 1, 4, 8
13, 26 weeks after starting to be exposed.
DEVELOPMENT OF HYBRID ADMIXTURE
Water-reducing component
A polycarboxylic water-reducing component (SSP) configured by polymeric
molecular design having improved water-reducing performance in the high and ultra high
strength range, viscosity-reducing performance, and compatibility with shrinkage
reducing admixtures was used along with a conventional polycarboxylic high-range

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water-reducing admixture for ultra high strength concrete[5][6] (SP) for comparison.
Both were used with their solid concentrations adjusted to 30 %. Their chemical
compositions are given in Table 4.
Table 5 compares concrete test results with SP and SSP. Concretes were
proportioned with a W/C of 0.15 as given in Table 3. SSP achieved a slump flow
comparable to SP with a dosage slightly lower than that of SP. L-flow velocity with SSP
was approximately 2 times that obtained with SP, showing SSP's viscosity-reducing
effect.
Shrinkage-reducing component
A shrinkage reducing admixture presenting high compatibility with high-range
water-reducing admixtures was selected from five types, SRA1 to SRAS, having different
chemistry. Their chemical compositions are given in Table 4. The shrinkage-reducing
performance and compatibility of SRAl to SRA5 are given in Table 6.
The shrinkage-reducing effect was evaluated by conducting tests on concrete made
with W/C of 0.35 as given in Table 3 and calculating the percentage of shrinkage
reduction based on the drying shrinkage strain after 26 weeks with respect to that of
reference concrete containing no shrinkage reducing admixture. The dosage of each
shrinkage reducing admixture was 2 kg/m3 . SSP was used as the water-reducing
component in combination with the shrinkage reducing admixtures in all cases.
The compatibility of these shrinkage reducing admixtures was examined by
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
blending each type in SP or SSP at a ratio of 15, 33, or 50% and leaving to stand for one
month for visual judgment of the state of solution. In this test, SRA 1 to SRA5 were used
with their solid concentrations adjusted to 30 %. Uniform and clear solution was marked
"0," whereas solution with segregation and/or cloud was marked "x" in Table 6.
By overall judgment, SRA3 with a highest shrinkage-reducing effect and high
compatibility with SSP was selected as the shrinkage-reducing component for this study.
Determination of the proportion of shrinkage-reducing component

Concrete tests were conducted using admixtures made by blending SSP and the
shrinkage-reducing component SRA3 at weight ratios of 85:15, 67:33, and 50:50 (solid
concentration: 30%). In this test, SRA3 was used with its solid concentration adjusted to
30%. Concretes were proportioned with W/C's of0.35 and 0.15 as given in Table 3. The
shrinkage-reducing effect of the admixtures was evaluated by the percentage of shrinkage
reduction with respect to the shrinkage strain with 100 % SSP. Table 7 gives the test
results for each admixture.
As expected, the shrinkage reduction percentage tended to increase as the ratio of
shrinkage-reducing component SRA3 increased. The dosage of the hybrid admixture
increased with the proportion of SRA3 when W/C was 0.35; whereas with W/C 0.15, the
dosage of the hybrid admixture decreased when SRA3 proportions were 15% and 33%
but increased when it was 50 %.
The 28-day compressive strength was comparable to SSP 100 % when the SRA3
proportions were 15 % and 33 % but lower by approximately 6 % with a SRA3
proportion of 50 %. At an age of 91 days, the compressive strengths were nearly the same
regardless of the proportion ofSRA3.
It was therefore decided to adopt a SSP:SRA3 weight ratio of 67:33 in

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476 Saito et at.
consideration of the autogenous shrinkage-reducing effect because when the SRA3
proportion is 50 %, the total dosage increases by up to 2 times, setting time is retarded by
up to 1.2 hours and strength is reduced by approximately 6 % at the age of 28 days.
This admixture is hereafter referred to as a hybrid admixture (HSP).
PROPERTIES OF HYBRID ADMIXTURE

The fresh concrete test results are given in Table 8.
Fluidity and viscosity

Both HSP and SP in all mixes achieved the target fluidity. The L v of HSP was 1.1 to
1.8 times that of SP, proving to have a better viscosity-reducing effect than SP. Fig.3 and
Fig.4 show the changes in the slump flow and Lv versus time, respectively. The slump
flow and Lv of mixes containing SP rapidly decreased versus time, but those of mixes
containing HSP retained their high fluidity and viscosity-reducing effect.
Admixture demand and setting time

Fig.5 and Fig.6 show the dosage of admixture and setting times of all mixes,
respectively. The demand for HSP was found to be 1 to 1.5 times that for SP. The high
demand for HSP results from the reduction in the water-reducing component
concentration to 111.5 times that of SP due to the addition of the shrinkage-reducing
component and the increase in the HSP dosage to compensate for the loss in the
water-reducing capability. However, the difference in the admixture demand tended to
decrease with a W/C of 0.20 or less. With a W/C of 0.15, the HSP demand was
conversely lower than the SP demand by approximately 5 percentage points, suggesting a
possibility that the shrinkage reducing admixture may contribute to cement dispersion to
a certain extent in the ultra high strength range. It is known that slump can increase when
a shrinkage reducing admixture is added as an extra proportion while keeping the water
reducer dosage unchanged, but the present case is interesting because there have been
few reports that an addition of a shrinkage reducing admixture at an inclusive proportion
reduced the admixture demand to a level lower than that of concrete without it. The
mechanism of this phenomenon should be elucidated in the future. The setting times of
HSP were 0.5 to 1 hour longer than those of SP in all cases. It is generally known that
setting times tend to be longer with a shrinkage reducing admixture. However, the degree
of setting retardation of HSP is low, as the absolute amount of the shrinkage reducing
admixture in HSP ( 0.4 to 2.5 kg/m3 ) is as little! as 1/20 to 112 of those of normal
concrete containing a shrinkage reducing admixture.
Autogenous shrinkage and drying shrinkage

Fig.7 shows the changes in autogenous shrinkage test results. The autogenous and
drying shrinkage test results are summarized in Table 9.
Autogenous shrinkage
The autogenous shrinkage strain of concrete containing SP with W/C's of 0.35 (N),
0.25 (L), and 0.20 (SFC) was relatively small, in the range of215 to 315 x 10·6 at an age
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of 28 days, but that of concrete with a W/C of0.15 (SFC) was as large as 730 x 10·6 . On
the other hand, concrete containing HSP produced good shrinkage-reducing effect
regardless of the differences in the absolute shrinkage strain values due to differences in
the materials and mixture proportions. The percentages of shrinkage reduction with
respect to the autogenous shrinkage strain of concrete containing SP were 23.3 %, 40.0 %
21.3 %, and 43.6 % for W/C's of 0.35 (N), 0.25 (L), 0.20 (SFC), and 0.15 (SFC),
respectively. It was initially expected that a higher absolute amount of the shrinkage
reducing admixture would lead to a greater percentage of shrinkage reduction, but it
turned out that the percentage of shrinkage reduction was greater for a W/C of 0.25 than
0.20. It was therefore inferred that the autogenous shrinkage-reducing effect may vary
depending on the cement type.
Drving shrinkage
HSP produced a shrinkage-reducing effect of 7.6 to 8.8 % at an age of 26 weeks.
However, its effect of drying shrinkage reduction is weaker than its effect of autogenous
shrinkage reduction. Differences in the shrinkage-reducing effect due to proportioning
differences were also small.
Fig.8 shows the compression test results. No marked difference was observed
between the strength-development in presence of SP or HSP. Both achieved strengths
equivalent to the target strength by the age of 28 or 91 days, proving that the addition of a
shrinkage reducing admixture produces no adverse effect on concrete strength.
Freezing and thawing resistance

Table 10 gives the results of freezing and thawing test. The durability factors of
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concretes containing SP and HSP were 90 or more after 300 cycles of freezing and
thawing. Both were found to provide sufficient resistance to frost damage with an air
content of around 3% for W/C's of 0.35 and 0.25 and 2% or less for W/C's of 0.20 and
0.15.
Carbonation resistance
Table 11 gives the results of accelerated carbonation test. No carbonation was
observed in concretes containing SP and HSP at the end of an accelerated carbonation test
period of 26 weeks. These were therefore proven to be sufficiently resistant to
carbonation.
CONCLUSIONS
This study is summarized as follows:

(1) While all concrete mixtures containing either a hybrid admixture (HSP) or a
conventional high-range water-reducing admixture (SP) achieved the target slump
flow, the L flow velocity (Lv) of concrete containing HSP was 1.1 to 1.8 times that of
concrete containing SP, showing HSP's strong viscosity-reducing effect.
(2) Whereas the slump flow and Lv of all mixtures containing SP decreased versus time,
all mixtures containing HSP retained high fluidity and viscosity-reducing effect.

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478 Saito et al.
(3) Whereas the demand for HSP dosage was 1.0 to 1.5 times greater than that for SP
dosage, the difference tended to decrease with a W/C of 0.20 or less. Setting times
tended to increase as the dosages of both HSP and SP increased, but no significant
retardation was observed.
(4) HSP was proven to possess excellent shrinkage-reducing capabilities. The autogenous
shrinkage and drying shrinkage of concrete containing HSP were reduced by 21 to
44% and 8 to 9%, respectively, compared to those of concrete containing SP.
(5) The strength-developing properties ofHSP and SP were similarly excellent.
(6) The resistance to frost damage and carbonation of concretes containing HSP and SP
were sufficient within the range of the present study.
(7) Consequently, the hybrid admixture combining an effective shrinkage-reducing
component and a water-reducing component that provides high fluidity and viscosity
reduction having excellent compatibility with the shrinkage-reducing component was
found highly suitable for the production of high strength concrete.
REFERENCES
Referenced standards
Japanese Industrial Standards

JIS A 1150 Method of test for slump flow of concrete
JIS A 1147 Test method for time of setting of concrete mixtures by penetration
resistance
JISA 1129 Methods of test for length change of mortar and concrete
JISA 1108 Method of test for compressive strength of concrete
JISA 1152 Method for measuring carbonation depth of concrete
JISA 1153 Method of accelerated carbonation test for concrete
ASTM
C666 Test Method for Resistance of Concrete to Rapid Freezing and Thawing
Cited references
1. Folliard, K.J. and Berke, N.S., 1977, "Properties of High-Performance Concrete

containing shrinkage-Reducing Admixture," Cement and Concrete Research,
V.27(9), pp.l357-1364.
2. Berke, N.S. and Li, L., 2003, "Effectiveness of shrinkage reducing admixtures
inreducing total shrinkage," Advances in Cement and Concrete, Proceedings of a
conference held at Copper Mountain, Colorado, USA, pp.l01-109.
3. Mitsui, K.; Yonezawa, T.; Kinoshita, M. and Shimono, T., 1994, "Application of a
New Superplasticizer for Ultra high-Strength Concrete," Superplasticizers and Other
chemical admixtures in concrete: Proceedings of the Fourth CANMETIACI
International Conference, Montreal, Canada, 1994 (SP-148), ed. V.M. Malhotra,
American Concrete Institute, pp.27-46.
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4. JCI Committee, 2002, Report by Autogenous Shrinkage of Concrete Committee, Japan
Concrete Institute, pp.51-54.
5. Kinoshita, M.; Suzuki, T.; Yonezawa, T. and Mitsui, K., 1994, "Properties of an
Acrylic Graft Copolymer-Based New Superplasticizer for Ultra high-Strength
Concrete," Superplasticizers and Other chemical admixtures in concrete: Proceedings
of the Fourth CANMETIACI International Conference, Montreal, Canada, I994
(SP-148), ed. V.M. Malhotra, American Concrete Institute, pp. 281-299.
6. Kinoshita, M.; Suzuki, T.; Soeda, K. and Nawa, T., 1997, "Properties ofMethacrylic
Water-Soluble Polymer as a Superplasticizer for Ultra high-Strength Concrete,"
Superplasticizers and Other chemical admixtures in concrete: Proceedings of the Fifth
CANMETIACI International Conference, Rome, Italy, 1997 (SP-173), ed. V.M.
Malhotra, American Concrete Institute, pp.143-162.
Table 1 -- Characteristics of Cement
Phase composition(%) Surface

Density
'JYpe of cement area
(glcmJ)
C 3S CzS C3A C4AF (mz/kg)
N onnal portland (N) 52 23 9 9 325 3.16
Low heat portland (L) 27 58 2 8 335 3.22
Silica fume cement (SFC) L(90%) + SF(lO%) 560 3.08
Table 2 -- Characteristics of Silica fume
Surface Chemical composition(%)

Densi~ area
(glcm) c
(mz/kg) SiOz AhOJ FezOJ CaO MgO RzO LOI
2.20 14,100 92.2 0.60 0.70 0.27 1.00 1.50 0.49 2.20
Table 3 - Target strength and Mixture proportions of Concrete
Target Unit weight (kglm3)

Target Target
slump Fine Coarse
strength W/C air Cement
flow aggregate aggregate
(MPa) (%) Water
(mm)
N L SFC Sl S2 G1 02
so~
70
0.35 550±50 3±0.5 160 457 - - 880 - 868 -
70~
100
0.25 650±50 3±0.5 160 - 640 - 756 - 852 -
too~
120
0.20 650±50 2> 160 - - 800 624 - 852
120~
150
0.15 700±50 2> 160 - - 1067 - 412 - 846
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480 Saito et at.
Table 4 - Chemical Composition of Admixtures used in Experiment
Cone.
Symbol Type Admixture Composition and Properties
(%)
Methacrylic type polycarboxylate-based
SP Conventional 30
copolymer
New Maleic type polycarboxylate-based copolymer 30
SSP
copolymer
SRAl Low alcohol series 100
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
SRA2 Shrinkage Polyether series 100
SRA3 reducing Polyether derivative 100
SRA4 admixture Low alcohol alkylene oxide adduct 100
SRA5 Glycol ether derivative 100
Mixture with Maleic type
HSP Hybrid polycarboxylate-based copolymer 30
and Shrinkage reducing agent (SSP+SRA3)
Table 5 -- Comparison of concrete test results with SP and SSP
Target Target
Kind of Dosage Slump flow L-flow velocity
W/C slump flow air (Cx%)
admixture (mm) (cm/s)
(mm) (%)
SP 2.50 715 3.5

0.15 700±50 2>
SSP 2.40 730 6.3
Table 6 -- Shrinkage-reducing performance and compatibility of

SRAl to SRAS with water-reducing component
Percentage of compatibility with water-reducing component*

Kind of shrinkage
with SP with SSP
admixture reduction
(%) 15% 15% 33% 50%
SRA1 15.6 X 0 0 0
SRA2 18.2 X 0 0 0
SRA3 19.4 X 0 0 0
SRA4 15.8 X 0 X X
SRA5 14.9 X X X X
• Judgment of the state of solution :

0 Soluble (uniform and clear), x Insoluble (segregation and/or cloud)

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Table 7- Determination of the proportion of shrinkage-reducing component
Percentage of Compressive strength

Dosage shrinkage (MPa)
W/C SSP: SRA3
(Cx%) reduction*
28days 91days
(%)
100: 0 0.60 - 84.2 94.3
85: 15 0.70 2.6 84.1 93.7
0.35
67: 33 0.90 5.3 84.6 94.0
50: 50 1.20 7.8 82.3 92.8
100: 0 2.40 - 158 182
85: 15 2.25 19.8 159 186
0.15
67: 33 2.35 42.3 156 187
50: 50 2.95 53.7 148 185
*In case ofW/C of0.35,the percentage of shrinkage reduction ts calculated based
on drying shrinkage strain after 26 weeks.
In case ofW/C of0.15,the percentage of shrinkage reduction is calculated based
on autogenous shrinkage strain after 28 days.
Table 8 -- Properties of Fresh Concrete
Weight Setting time

Slump Air L-flow
Kind of Dosage of unit (hours)
W/C flow content velocity
admixture (Cx%) volume
(mm) (%) (cm/s)
(kg/m3) initial final
SP 0.60 570 3.3 11.4 2358 5.2 7.0
0.35
HSP 0.90 560 3.2 12.4 2360 6.3 8.2
SP 0.65 690 2.9 8.3 2410 6.9 9.7
0.25
HSP 1.00 675 3.0 10.5 2409 8.2 10.3
SP 0.90 690 1.2 10.1 2455 9.5 10.8
0.20
HSP 1.20 680 1.4 12.4 2452 9.8 11.0
SP 2.50 720 1.4 3.6 2500 12.4 16.9
0.15
HSP 2.40 750 0.9 6.5 2508 13.3 17.8
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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482 Saito et at.
Table 9 - Autogenous and drying shrinkage test results
Autogenous Shrinkage Drying Shrinkage

(28days) (26weeks)
Kind of
W/C Percentage of Percentage of
admixture
Strain shrinkage Strain shrinkage
(x 10'6) reduction (x 10-6) reduction
(%) (%)
0.35
SP 215 - 618 -
HSP 165 23.3 571 7.6
0.25
SP 240 - 523 -
HSP 144 40.0 481 8.0
0.20
SP 315 - 521
HSP 248 21.3 478 8.3
0.15
SP 730 - 400 -
HSP 412 43.6 365 8.8
Table 10- Results of freezing and thawing test
Kind of Durability factor

W/C
admixture (300 cycles)
SP 95
0.35
HSP 93
SP 93
0.25
HSP 91
SP 99
0.20
HSP 98
SP 99
0.15
HSP 99
Table 11 -- Results of accelerated carbonation test
Carbonated thickness
Kind of
W/C (26weeks)
admixture
(mm)
SP 0.0
0.35
HSP 0.0
SP 0.0
0.25
HSP 0.0
SP 0.0
0.20
HSP 0.0
SP 0.0
0.15
HSP 0.0
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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g
...
Fig. 1 -- L-flow test meter.
400mrn
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 2 --Autogenous shrinkage strain tester.

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484 Saito et al.
800 . . . . - - - - - - - - - - - , 800
W/C0.35,N W/C 0.20,SFC
700 ~ 700
I 600
~ sool'!!""-~-D--
i 600 ------------------~-
~ 500
~
00
400 J 400
300 "' 300
200 '----'----'----~ 200
30 60 90 0 30 60 90
Elapsed time (min) Elapsed time (min)
-
800 . . . . - - - - - - - - - - - - - - - - - , 800
W/C0.25,L
~ ~e::::::~-----=o:.:~~ 700
i
700
600 I 600
A soo ~ 500
W/C O.IS,SFC
g 400 ~------------
J 400
"' 300
300 ~-------------
200 '----'----'----~ 200
30 60 90 0 30 60 90
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 3 --Change in slump flow versus of time.
14 . . . . - - - - - - - - - - - - - - - - - , -14
W/C0.35,N W/C 0.20,SFC
6 ---------------------
4 '----~-~----~~ 4
30 60 90 0 30 60 90
12 . . . . - - - - - - - - - - - - - , 10
W/C 0.25,L W/C O.IS,SFC
.:s 6
4 ~
~------------- 2
2 0
30 60 90 0 30 60 90
Fig. 4 --Change in L-flow velocity versus time.

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N0.35 UJ.25 SFC0.20 SFCO.l5

Cement-W/C
Fig. 5 -· Dosage of admixture of all mixes.
N0.35 UJ.25 SFC0.20 SFCO.JS

Cement-W/C
Fig. 6 ··Initial setting times of all mixes.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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486 Saito et al.
-200 .-------.,----.----~---,
: W/C0.35,N : : W/C020,SFC
,-----,----- ----T----~----~-----
~
1 I
I : :
I
I
I
200 ritiii~~~~~~~~~~~~
~ ----T----~-----,----- ~ ----T----~----~-----
1 I 1 I
I I I I I I
~ ----T----,----~----- 600 ----T----~----~-----
~ L---~~-----Ll----~:----~
1 I 1
I
~ L--~-~--~-~
7 14 21 28 7 14 21 28
Elapsed time (days) Elapsed time (days)
-200 -200
i W/C025,L
l
I I
I I
: : W/C0.15,SFC
----T----~----~----- ----T----~----~-----
:g I I I :g I I I
! •i
g
~ ·i
0 I I I
200 200 ~--i----i----~-----
I I I
I I
__ i____ j_____ ~ -"~

I
~ ...i
0
400 -~--~----i----- 400 T
~: ----~----~-----
~"
600
~ 600
:
800 ~
14 21 28 14 21 28
Elapsed time (days) Elapsed time (days)
Fig. 7 --Autogenous shrinkage strain versus time.
200 r-----------------------------------,
180
;?160
6140
~120
~100 ~==~~~--1
·~ 80
~60
8 40
20
N0.3S N0.35 L02S L0.25 SFC020 SFC0.20 SFCO.IS SFCO.IS

SP HSP SP HSP SP HSP SP HSP
Cemont (W /C}- admillture
Fig.8 -- Compressive strength development.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
SP-239-32
Effects of an Inorganic Acid Based

Alkali-Free Accelerator on the Setting
and the Compressive Strength
Development of a Hydrating Clinker
Containing Different Setting Regulators
by C. Maltese, C. Pistolesi, A. Bravo, F. Cella, T. Cerulli,

and D. Salvioni
Synopsis: In this paper, the influence of different setting regulators on the

performances of an inorganic acid based alkali-free accelerator was analysed.
Setting time and compressive strength development were determined on clinker
samples added with ~-hemihydrate or anhydrite and admixed with the alkali-
free accelerator. It was found that the lower is the setting regulator instantaneous
dissolution rate, the shorter is the final set and the higher the compressive strength
development (therefore the more efficient is the accelerator). In order to understand
this phenomenon, physical (hydration temperature profile), chemical (TG and XRD),
morphological (ESEM-FEG and specific surface area measurements) analyses were
carried out on paste samples added with the accelerator.
Keywords: alkali-free accelerators; compressive strength; setting

regulator; setting time

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488 Maltese et al.
Cristiano Maltese graduated in physical chemistry at the University of Pavia. In 1995 he
got a master degree in material science at the University of Kent at Canterbury (UK).
Since 1997 he has been working in the building materials department of Mapei Research
and Development Centre in Milan and he is author of some papers in the cement and
concrete field.
Carlo Pistolesi graduated in Civil Engineering at the University of Ancona. Since 1992 he
has been working in Mapei, Research and Development Centre in Milan, Italy as chief in
charge of the building materials department of the and now he is working in the
development of repair concrete mortars and admixtures. He is author of some papers in
the concrete field.
Anna Bravo graduated in bioorganic chemistry at the University of Milan. In 1997 she
got a P.h.D. in industrial chemistry at the Politecnico of Milan with a internship at the
N.R.C. in Ottawa (Canada). Since 2000 she has been working in the Central Analytical
Department ofMapei Research and Development Centre in Milan and she author of some
papers in the cementitious field.
Fiorenza Cella graduated in geology at the University of Milan. In 2000 she got a P.h.D.
in applied mineralogy at the University of Milan with a internship at the CTG Italcementi
Group in Guerville (France). Since 2000 she has been working in the Central Analytical
Department ofMapei Research and Development Centre in Milan and she author of some
papers in the cementitious field.
Tiziano Cerulli graduated in organic chemistry at the University of Milan. Since 1989 he
has been working as chief in charge of the Central Analytical Department of Mapei
Research and Development Centre in Milan. He is author of several papers, most of them
in the cementitious field.
Davide Salvioni is microscopy specialist co-operating with the Analytical Department of

Mapei Research Laboratory, Milan, Italy. He is author of several papers on various
aspects of material sciences.
INTRODUCTION
Alkali-free accelerators are relatively new liquid concrete admixtures used in the
area of underground construction (1, 2, 3, 4, 5). For safety reasons in the European
market they are replacing the classical alkali-rich accelerators, like sodium aluminate or
sodium silicate. Furthermore, the concrete sprayed with these new alkali-free accelerators
can reach higher long term compressive strengths (6). The accelerating admixtures cause
a fast concrete setting allowing to project the cementitious material onto the tunnel wall.
The concrete coat acts as a consolidating shield useful to prevent the tunnel convergence
(7). Several alkali-free accelerators are available on the market. They can be divided into
two main categories both containing aluminium sulphate complexes stabilized either by
inorganic or by organic acids (8). The capability of concrete to stick on the substrate is
related to the efficacy of the reaction between accelerator and hydrating cement. This
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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reaction is commonly evaluated by measuring the final set time or the compressive
strength development of accelerated cement pastes (9,10). It could be influenced by
several parameters such as: accelerator type and its solid content, class and chemical
composition of cement, setting regulator, environmental conditions, concrete
temperature. In this paper the effects of the setting regulators on the interaction between
accelerator and hydrating cement were studied. Different hydraulic binders were prepared
by mixing a clinker with two calcium sulphate phases characterised by different
instantaneous dissolution rates (11): ~-hemihydrate (38 g/1 min) and anhydrite (1 g/1
min). Setting time and compressive strength development of the above mentioned
samples admixed with water and an inorganic acid based alkali-free accelerator were
determined. The sample hydration was followed by thermo-chemical hydration profile,
ESEM-FEG (Environmental Scanning Electron Microscopy- Field Emission Gun), XRD
(X Ray Powder Diffraction), TG (Thermo-Gravimetry) and specific surface area
measurements (by BET method).
EXPERIMENTAL DETAILS
Raw materials
Cement pastes (Tab.l) were prepared by mixing a clinker (from Cementerie Barbetti,
Gubbio, Italy - Tabs.2,3), ~-hemihydrate (from Lages, Italy, J.t: 11 J.tm) or anhydrite
(from Yesos Ibericos, Spain, J.t: 8 J.tm), water (water/solid= 0.45). An inorganic acid
based alkali-free accelerator was used (Tab.4).
Mechanical test
The samples were prepared by mixing by a spatula clinker, calcium sulphate (~
hemihydrate or anhydrite) and water for 1 minute. Afterwards the accelerator was added
and mixed for 10 seconds. Final set time (each result is an average of two measurements)
was carried out according to ENV 196/3 (Vicat needle method- Fig.l,2). The procedure
is explained elsewhere (9). Compressive strength development (each result is an average
of four values - Tab.5) was also determined on 25x25mm (diameter x height) cylindrical
specimens cured at 23°C and 50% R.H .. During the first hours of hydration, as the
samples were too soft (mechanical strength lower than 1 MPa), a digital force gauge
(Imada model DPS 100 equipped with a needle -3 mm section) was used to determine the
compressive strength. At later curing time, when the samples became harder
(compressive strength higher than 1 MPa), a machine type Controls L 1400 was utilised.
Morphological and chemical-physical analyses
Paste samples, mixed and cured as described for the mechanical tests, were
studied as follows.
Hydration temperature profile during the first 12 hours of hydration was measured (Fig.3)
by a digital thermometer (Testo model 781) inserted in a 50 g sample. The cell containing
the specimen was kept in a temperature controlled box (20°C).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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490 Maltese et al.
X Ray powder diffraction (XRD) pattern was analysed (Fig. 4 to 6- Philips model PW
1830 diffractometer with Cu(Ka) radiation) after 5 minutes and 6 hours. These samples
were treated with acetone in order to stop cement hydration.
Water loss between 80° and 300°C (mainly coming from C-S-H and hydrated
sulphoaluminates (12)) and calcium hydroxide (300°C-500°C (13)) after 5 minutes and 6
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
hours of curing were determined by Thermo-Gravimetry (Tab.6 - Netzsch model

STA409- each value is an average of two measurements).
Specific surface area was also detected (Tab.7- each result is an average of three values).
The analyses were carried out by B.E. T. method using Nitrogen as carrier (Coulter model
SA31 00) after 5 minutes and 6 hours of curing.
At the same hydration times, an ESEM FEG (Environmental Scanning Electron
Microscopy- Field Emission Gun - Philips model XL30) study was performed (vapour
pressure of 6.0 Torr and 5°C by means of a Peltier stage- Figs. 7-15).
RESULTS
Mechanical test
The results summarized in Fig.l point out that calcium sulphate form influences
the final set of non accelerated paste sample (R,1k<Ranhct<Rheta). The accelerator addition
causes a significant setting time reduction on both the samples without calcium sulphate
(ACc1k- Fig.2- in comparison with Rc 1k- Fig.l) or containing anhydrite (ACanhd- Fig.2-
compared to Ranhd- Fig.l). On the contrary, a strong retardation was observed when~
hemihydrate was used as setting regulator (ACheta - Fig.2 - compared to Rheta- Fig.l ). The
compressive strength results (Tab.5) follow a similar trend (R, 1k>Ranhct>Rheta and
ACc~k>ACanhd>ACanhd) even if, after 4 hours, the strength of the references (Rc1k. Ranhd and
Rheta) becomes higher than the accelerated samples.
Chemical-physical analyses
The hydration temperature profile is related to the rate of heat release ( 14). The
exothermic peak observed during the first two hours of curing (Fig.3 - standard
deviation: +/- 0.5°C) is due to early cement hydration and hydrated sulphoaluminate
formation. Figure 3 shows an increase of the peak height on the samples admixed with
the alkali-free accelerator (ACclk, ACbeta and ACanhd in comparison with R, 1k. Rheta and
Ranhct). This effect arises from aluminium and sulphate ions coming from the accelerator
which promote a massive ettringite formation (15). ACanhct shows the highest peak
intensity.
The XRD patterns (Figs.4-6) point out signals of ettringite crystals in all the
samples. The use of the flash setting accelerator seems to cause an increase of the
ettringite peak intensity. ACanhd is the sample with the highest ettringite peak intensity.
The inorganic acid based alkali-free accelerator could retard cement hydration as the
portlandite content after 6 hours of hydration is significantly lower than the reference
(Figs. 4-6). Nevertheless, after 6 hours, also Rheta has a lower portlandite amount
compared to Rc1k and Ranhct, suggesting that this setting regulator could slow down alite
hydration. Both Ranhd and ACanhd show anhidrite signals also after 6 hours of curing. This

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result confirms that the instantaneous dissolution rate of this calcium sulphate type is
lower than ~-hemihydrate, suggesting that a lower initial concentration of sulphate ions
could be expected in Ranhd and ACanhd in comparison with ~eta and ACbeta·
TG analyses emphasise a reduction of the calcium hydroxide content in the
samples added with the alkali-free accelerator (Tab.6) thus confirming the XRD patterns.
The accelerator increases the water loss between 80°-300°C in particular on the samples
after 5 minutes of hydration. This effect could be related to the massive formation of
hydrated sulphoaluminates promoted by the accelerator.
Morphological analyses
The results in Tab.7 underline that ACcik has the largest surface area (after 5 minutes of
curing). Furthermore the specific surface area of ACanhd is larger than ACbeta· Therefore
some morphological differences among the accelerated samples should be evident.
The ESEM micrographs of the reference pastes Rc1k. Rheta and Ranhd show significant
differences: the sample without calcium sulphate points out well shaped plates of likely
AFm phase and few crystals of ettringite (Fig. 7); on the contrary the sample containing ~
hemihydrate is characterised by small and rounded masses (Fig.8) on a gel like material
which covers cement grains; whereas few small but well shaped prismatic needles
appears in Ranhd (Fig.9). From the literature (16) it is known that calcium sulphate based
setting regulators promote the formation of an amorphous layer of AFt phase on
hydrating cement grains which slows down further hydration (dormant period). This
protective coat cannot be formed in Rc1k (as it does not contain the setting regulator) and
the low amount of available soluble sulphate ions (for example coming from the fast
dissolution of alkaline sulphate) could give origin to well shaped crystals of ettringite
(Fig.7). Moreover, Fig. 8 supports the hypothesis that a fast nucleation rate occurs in Rheta
(for the higher instantaneous dissolution rate of ~-hemihydrate) and a larger amount of
gel like material could be formed. In Ranhd, for the lower instantaneous dissolution rate of
anhydrite, more ordered and larger ettringite crystals could be obtained. As time
proceeds, the morphology of the samples becomes more similar.
In Figs. 10 and 11 (ESEM micrographs of ACc1k and ACanhd after the first minutes of
hydration) thin and long rods of AFt phase are visible. On the contrary, the
microstructure of ACbeta is deeply different (Fig.l2): short and disordered masses (whose
chemical nature is not clear) are present everywhere. These differences support the
hypothesis about the existence of many nucleation germs in ACbeta, which could hinder a
proper growth of well formed ettringite crystals.
After 6 hours, Figures 13 and 14 (ACc1k and ACanhd) show a significant growth of
ettringite crystals (which appear slightly longer and thinner in ACc~k). At the same curing
time, short prismatic needles of likely ettringite and plates of AFm phase are evident in
ACbeta (Fig.15).
DISCUSSION
According to the literature (17, 18, 19), alkali-free accelerator reacts with
hydrating cement promoting the formation of hydrated sulphoaluminates (particularly
AFt phase) thus determining a rapid viscosity increase of cement pastes which results in a
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492 Maltese et al.
short setting. The growth of these phases contributes to the mechanical strength
development. The accelerating performances are commonly evaluated by determining the
final set and the compressive strength development of cement pastes admixed with the
accelerator (9): the shorter is the final setting time and the higher is the strength
development the more efficient is the accelerator.
The results in Figs.l, 2 and Tab.5 indicate that the lower is the initial sulphate
concentration (ACc~k<ACanhct<ACheta and Rc!k<Ranhct<Rheta), the shorter is the final set, the
higher is the compressive strength development both for non accelerated and for
accelerated samples.
Schwiete already observed that setting of non-accelerated hydrating cement is
influenced by the setting regulator (20) which could be anhydrous or hydrated calcium
sulphate in different crystallographic forms (21 ). During the first hydration stage, calcium
and sulphate ions, supplied by the setting regulator, react with aluminium (normally
present in cement phases like C3A and C4AF) and water to form an amorphous layer of
sulphoaluminates with AFt phase at the edge (16), which slows down further hydration
(dormant period). The morphology of such AFt phase depends on the setting regulator
(16) as confirmed by the ESEM micrographs in Fig.8 (~eta), Fig.9 (Ranhct) and Fig.7
(Rc1k). If only a low amount of calcium sulphate (or none at all) is present a quicker set
can be observed (Fig. 1) due to a rapid early reaction of aluminate phases with the
formation of plates of AFm phase (22) on a thin layer of hydrated sulphoaluminates. The
lower mechanical strength development of Rheta respect to Rc1k and Ranhd (Tab.5) may be
explained considering that a less permeable coat layer of hydrated sulphoaluminate could
be formed in the sample containing ~-hemihydrate thus hindering a proper cement
hydration (as supported by the lower amount ofportlandite detected after 6 hours in ~eta
- XRD patterns and TG analyses).
The accelerator is usually added during the dormant period, when the amorphous
layer of hydrated sulphoaluminates is already formed. In order to understand the effects
of the setting regulators on the accelerator performance, the different morphology of non
accelerated samples Rc1k (without calcium sulphate - Fig.7), Rheta (containing calcium
sulphate with the highest dissolution rate - Fig. 8) and Ranhd (containing the calcium
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
sulphate with the lowest dissolution rate - Fig.9) should be considered. The
microstructure of Rc1k and Ranhct is characterised by thin and slight long prisms of
ettringite or plates of AFm phase; whereas rounded and small masses of a
sulphoaluminate gel like material are present in Rheta· These differences could affect the
kinetics of ettringite formation arising from the accelerator addition. In fact, the
morphology during the first hydration minutes of ACc1k (Fig.lO) and ACanhd (Fig.ll) is
different respect to ACbeta (Fig.l2). These morphological variations are also confirmed by
the specific surface area (after 5 minutes of hydration, the surface area of ACclk and
ACanhd is significantly larger than ACheta- Tab.7) and the water loss between 80°C and
30ooc (which is higher for ACc1k and ACanhct compared to ACbeta). Therefore the different
initial microstructure of ACclk and ACanhd compared to ACbeta could explain their different
setting behaviour. In the samples without setting regulator or containing anhydrite, a low
nucleation rate could be expected: few nucleation germs are formed, which promote a
proper growth of well shaped and long ettringite crystals favouring a fast setting. On the
contrary, the sample containing ~-hemihydrate could be characterised by a faster
nucleation rate: several nucleation germs are originated inhibiting a proper growth of

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long ettringite crystals (so fine grained crystals cannot produce a rigid structure). The
ESEM micrographs prove that the growth of ettringite crystals in ACbeta (Fig.15) is
significantly slower compared to ACc1k and ACanhct (Figs.l3,14). Furthermore, also C3 S
hydration in ACbeta seems to be hindered (as confirmed by the lower calcium hydroxide
concentration detected by XRD and TG after 6 hours of hydration). Therefore, the
retarded setting and the lower compressive strength development of ACbeta could arise
from the disordered layer of ettringite formed during the first minutes of the reaction
between hydrating cement and alkali-free accelerator which slow down ettringite growth
and c3s hydration.
CONCLUSION
This study points out that the initial sulphate ions content could influence the
efficiency of an inorganic acid based alkali-free accelerator. It was found that the lower is
the calcium sulphate instantaneous dissolution rate the more efficient is the accelerator.
This behaviour could be related to the different morphology of the ettringite formed
during the first instant of the reaction between hydrating cement and alkali-free
accelerator. Such a morphology depends on the different nucleation/growth ratio of the
ettringite crystals: anhydrite favours crystal growth whereas J3-hemihydrate promote the
nucleation. For shotcrete applications, it is recommendable to use cement containing
anhydrite as setting regulator or, at least, to avoid cement with ~-hemihydrate.
REFERENCES
1) Myrdal, R., 1999 September, "Modem chemical admixtures for shotcrete",

Proceedings of the 3rd International Symp. On Sprayed Concrete, Go!, Norway,
1999, ed. N. Barton et al., pp. 375-382;
2) Leikauf, B., Oppliger, M. "Alkali-free accelerators for sprayed concrete" Chimia 52
1998 pp. 222-224;
3) Dal Negro, E., Maltese, C., Pistolesi, C., 2003, "Use of advanced alkali-free
accelerators for high performance concrete" Gallerie e Grandi Opere Sotteranee,
No. 70, pp. 51-58;
4) Paglia, C., Wombacher, F., Bohni, H., 2001, "The influence of alkali free and
alkaline shotcrete accelerators within cement systems" Cern. Con. Res., No. 31, pp.
913-918;
5) Sharrocks, D., 1998, "Investing in new accelerators", Concrete Engineering
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
International, No.2, pp. 14-15;

6) Zampini, D, Walliser, A., Oppliger, M., Melbye, T., Maltese, C., Pistolesi, C.,
Tansini, G., Portigliatti, E., Dal Negro, E., 2004, "Liquid based set accelerating
admixtures for sprayed concrete: a comparison between alkali-free and alkali-rich
accelerators" Gallerie e Grandi Opere Sotteranee, No. 72, pp. 30-40;
7) Hoek, E., 2000, Practical Rock Engineering, A.A. Balkema Publishers, Rotterdam;
8) Maltese, C., Pistolesi, C., Bravo, A., Cerulli, T., Salvioni, D., Squinzi, M., 2005
November 13-16, "Formation of nanocrystals of AFt phase during the reaction
between alkali-free accelerators and hydrating cement: a key factor for setting and

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494 Maltese et al.
hardening of sprayed concretes", Proceedings of 2nd International Symposium on
Nanotechnology in Construction, Bilbao, Spain;
9) Cerulli, T., Dal Negro, E., Hansen, R., Maltese, C., Pistolesi, C.,Wilberg, J., 2002
September 22-26, "Physical mechanical analysis of concrete sprayed with two
different accelerators: morphological and chemical implications", ih International
Symposium on Sprayed Concrete, Davos, Switzerland, 2002, ed. K.Berg et al., pp.
58-72;
10) De Belie, N., Grosse, C. U., Kurz, J., Reinhardt, H. W., 2005, "Ultrasound
monitoring of the influence of different accelerating admixtures and cement types
for shotcrete on setting and hardening behaviour", Cern. Con. Res., No. 35 pp. 2087-
2094;
11) Doskov, K., Bier, T.A., Wohrmeyer, C., 1999April 13-15, "Formulating dry-mix
mortars with calcium aluminates cement", La Farge Calcium Aluminates, presented
at the workshop on dry-mortars- St. Petersburg, Technical paper TP-GB-CH-LAF-
03/99;
12) Ghosh, S.N., 1999, Cement and concrete science and technology, Vol. 1, Part 2, ed.
S.N. Ghosh, pp.l73-252;
13) Ramachandran, V.S., 1979, "Differential thermal method of estimating calcium
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
hydroxide in calcium silicate and cement pastes", Cern. Con. Res., No. 9, pp. 677-
684·
14) Taylor, H. F. W., 1998, Cement Chemistry, 2"ct edition, p.212 (Publisher: Thomas
Telford);
15) Bravo, A., Cerulli, T., Maltese, C., Pistolesi, C., Salvioni, D., 2003, "Effects of
increasing dosages of an alkali-free accelerator on the physical chemical properties
of a hydrating cement paste", Proceedings of th CANMET/ACI, Berlin, Germany,
2003, ed. V.M. Malhotra, pp. 211-225;
16) Scrivener, K.L., Pratt, P.L., 1984, "Microstructural studies of the hydration of C3A
and C4AF independently and in cement paste", Br. Ceram. Proc., No. 35, pp. 207-
219;
17) Paglia, C., Wombacher, F., Bohni, H., Sommer, M., 2002, "An evaluation of the
sulphate resistance of cementitious material accelerated with alkali-free and alkaline
admixtures: laboratory vs field", Cern. Con. Res., No. 32, pp. 665-671;
18) Burge, T.A., 2001, "Mode of action of alkali-free sprayed shotcrete accelerators"
Shotcrete: Engineering Developments, ed. Bernard, pp. 79-85;
19) Cerulli, T., Pistolesi, C., Maltese, C., Salvioni, D., 2002, "Alkali rich and alkali free
accelerators for shotcrete: physical, chemical and mechanical effects on cement
hydration", Proceedings of ICMA 2002, San Diego, California, pp. 1-17,
www.cemmicro.org;
20) Schwiete, H.E., Ludwig, U., Jager, P., 1966, "Investigation in the system 3CaO-
CaS04-CaO-H20", Proceedings of Highway Research Board, Symposium on
Structure ofPortland Cement Paste and Concrete, Washington, 1966, pp. 353-367;
21) Odler, I., 2000, Special inorganic cements, ed. E&F.N. Spon, p. 205;
22) Locher, F.W., 1981, "Hydration of pure Portland cement" The proceedings of th
!CCC, Paris, 1981, Vol.4, pp. 49-54- (provided by: www.iccc2007.org).

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Table I - Mixture compositions (expressed as g)
Sample R.n. ACclk ~ .. ACbeta R.Dhd ACaabd
Clinker 100 100 95 95 95 95
Jl-hemihydrate 5.0 5.0
Anhydrite 4.7 4.7
Accelerator 6 6 6
Water 45 45 45 45 45 45
Table 2 - Clinker chemical and physical characteristics (analyses perfonned according to

ENV 196/2)
Blaine
Na20
Density specific
CaO(%) Si02 (%) Ah03 (%)Fe203 (%) MgO (%) S03(%) Cl(%) Equivalent (kg/mJ)
surface
(%) 2
area (m /g}
66.45 19.74 6.23 2.52 1.36 1.04 0.1 0.5 3150 331
Table 3 - Clinker phase composition detennined by Rietveld analysis (expressed as % -

standard deviation is indicated between brackets)
c~ CaO Ca(OH)2
69.2 8.7 17.1 2.2 0.5 0.2 1.5
(+/- 0.2) (+/- 0.7) (+/- 0.2) (+/- 0.1) (+/- 0.05) (+/- 0.05) (+/- 0.1)
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 4 - Accelerator chemical-physical characteristics
pH (ISO 4316) 2.5
Density (glee - ISO 758) 1.36
Dry Content (% - EN 480/8) 44.0

11 Ah03;
Chemical composition(%)
16.2 so3

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.1:::-
\0
0\
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
3:
S»
~
(D
"'
Table 5 -Compressive strength development (MPa)
Hydration Time R.n. R.,.,. R.nbd AC,u. AC,_ Ac...d

-
(D
(D
S»
:-
l hour <0.01 <0.01 <0.01 0.076 (+/-0.01) <0.01 0,03 (+/-0.01)
2 hours 0.02 (+/-0.005) <0.01 <0.01 0.092 (+/-0.01) <0.01 0.04 (+/-0.0 I)
3 hours 0.06 (+/-O.oJ) <0.01 <0.01 0.11 (+/-0,02) <0.01 0.04 (+/-0.01)
4 hours 0.08 (+/-O.oJ) <0.01 0.01 (+/-0.005) 0.12 (+/-0.02) <0.01 0.04 ( +/-0.0 I)
6 hours 0.2 (+/-0.02) 0.08 (+/-0.01) 0.14 (+/-0.02) 0.14 (+/-0.02) 0.01 (+/-0.005) 0.05 (+/-0.01)
8 hours 0.4 (+/-0.05) 0.13 (+/-0.02) 0.37 (+/-0.05) 0.16 (+/-0.02) O.Ql (+/-0.005) 0.14 (+/-0.02)
24 hours 6.3 (+/-1.0) 7.8 (+/-1.0) 7.1 (+/-1.0) 6.4 (+/-1.0) 8.8 (+/-1.0) 6.1 (+/-1.0)
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(/)
c
"'C
(D
-"'
'"'I
"'C
-
cu
;::;·
No
(D
'"'I
"'::s
cu
Table 6 - Thennogravimetric analyses
c.
n
::r
R.tk ~ R..bd AC,Ik AC- ACanhd (D
1.5 3
5 min 1.0 0.3 0.9 0.7 0.8
;::;·
Calcium Hydroxide(%)
6 hours
5 min
4.9
1.8
2.2
2.2
2.8
1.3
1.6
7.2
1.0
5.1
1.7
8.8
-
cu
)>
c.
Water Loss(%; 80°- 300°C) 3
~
6 hours 4.1 3.3 5.4 9.0 7.7 9.3
c
ta
"'::s-·
n
0
::s
~
-
n
ta
(D
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\0
.......
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498 Maltese et at.
Table 7 - Specific surface area
R.u. Rbeta R.nbd ACeu. ACbeta ACanbd

Smin 2.2 2.2 2.4 6.6 3.0 5.3
Specific surface
area (m2/g) 6 hours 14.9 6.9 14.1 12.8 6.0 9.4
500 +---------
400 +---------
300 +---------
200
100
Rclk Rbeta Ranhd

Sample
Fig.1- Final setting time of reference samples.
40~-------
35+--------
30+---------
25+--------
t
ii
20+---------
15+---------
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
10
ACclk ACbeta ACanhd

Sample
Fig.2- Final setting time of accelerated samples.

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31 .:_-
29 ------- -
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
27
25
23
19 -~---~---r--~--
0 a o 12 0 12
time (hours)
Fig.3- Hydration temperature profile.
Countsls
60
40
20
5 mino
100
50
400
portlandite
m
200
100
6 hrs o
100
50
10 15 20 25
Position["2Theta[
Fig. 4- XRD patterns of Rcik and ACc1k·

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soo Maltese et at.
Cauntsls
100
ettringite
.. ------------ i
I
"'
150
100
"'
100
100
10 15 20 25
Position ['2Theta)
Fig. 5- XRD patterns of Rbeta and ACbeta·
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Countsls
ettrin~ite ,, anhydrite
! ------------,
100 ' ',
' -,
: '
100
100
10
Position["2Theta[
Fig. 6 - XRD patterns of Ranhd and ACanhd'

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 7- ESEM micrograph of Rcik after 5 min of hydration (unit length: t1Jm).

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502 Maltese et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 8- ESEM micrograph of Rbeta after 5 min of hydration (unit length: t!Jm).
Fig. 9- ESEM micrograph of Ranhd after 5 min of hydration (unit length: t!Jm).

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,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 10- ESEM micrograph of ACctk after 5 minutes of hydration (unit length: 21Jm).
Fig. 11- ESEM micrograph of ACanhd after 5 minutes of hydration (unit length: 21Jm).

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504 Maltese et al.
Fig. 12- ESEM micrograph of ACbeta after 5 minutes of hydration (unit length: 211m).
Fig. 13- ESEM micrograph of ACcik after 6 hours of hydration (unit length: 211m).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Superplasticizers and Chemical Admixtures in Concrete sos
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Fig. 14- ESEM micrograph of ACanhd after 6 hours of hydration (unit length: 211m).
Fig. 15- ESEM micrograph of ACbeta after 6 hours of hydration (unit length: 211m).

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so6 Maltese et at.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-33
Effect of Functional Groups on the

Performance of Lignosulfonates in
Cement-Water Systems
byJ.Zhor
Synopsis: The relationship between the number of individual functional
groups present in lignosulfonate molecular structures and the performance of
lignosulfonates in fresh cement pastes was investigated. Lignosulfonate fractions
from three different pulping processes (sulfite, sulfate and organosolv) were included
in this study. The dispersing, set-retarding and air-entraining effects of these
fractions in ordinary Portland cement pastes were studied. Elemental composition,
methoxyl and sulfonate group contents were determined analytically. An algorithm
was developed to generate model molecular structures representing individual
lignosulfonate fractions. Each model structure was based on the results of the
chemical analysis, the model structural segment typical of each particular lignin and
additional literature data. The numbers of sulfonate, carboxyl, phenolic hydroxyl,
aliphatic hydroxyl and methoxyl groups in each proposed molecular structure were
determined. The numbers of C·C and C-0-C inter-unit bonds in each molecule were
calculated as well.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Correlations between selected functional group counts and the dispersing,

set-retarding and air-entraining effects of lignosulfonates were determined. For
the dispersing effect, methoxyl was the most positively correlated and carboxyl
was the most negatively correlated group. Sulfonate had a very low correlation
with the dispersing effect. For the set-retarding effect, the C-C inter-unit bond was
the most positively correlated and sulfonate was the most negatively correlated.
For the air-entraining effect, carboxyl was the most positively correlated and
aliphatic hydroxyl was the most negatively correlated group. A low correlation was
found between sulfonate and the air-entraining effect. The results are interpreted
from the perspective of cement hydration processes and the implications on
the understanding of lignosulfonate interactions with cement-water systems are
discussed.
Keywords: air entrainment; cement paste; chemical analysis;

dispersant; hydration; lignin and derivatives; molecular structure;
plasticity; retardation; setting time; water-reducing admixture

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508 Zhor
ACI member Jiri Zhor earned his PhD in Materials at the University of New Brunswick,
Canada. After several years of industrial experience with various concrete applications,
he has been engaged in research on concrete admixtures for more than fifteen years. His
current research interests include molecular properties of functional polymers used as
admixtures in cement-based materials and mechanisms of cement-polymer interactions at
the initial stages ofhydration.
INTRODUCTION
In the current era of new formulations of synthetic polymers constantly

emerging, it is easy to forget that lignosulfonates have been used as water-reducing and
retarding admixtures for cement and concrete [ 1] for over sixty years. They were
introduced in the nineteen-thirties [2,3] and have been studied extensively ever since [4-
10]. Throughout the years the focus of researchers has been repeatedly shifted towards
emerging families of new synthetically prepared superplasticizers such as
polycondensates of sulfonated naphthalene and melamine with formaldehyde [11,12],
and more recently polycarboxylates [13]. The interest in lignosulfonates has been
somewhat rejuvenated during the last decade [14-16], which is not surprising considering
the fact that lignosulfonates continue to be extensively used in the production of concrete
admixtures for both technological and economic reasons.
Lignosulfonates or sulfonated lignins are typically obtained as by-products from

the production of pulp (cellulose fiber) during sulfite pulping of softwood.
Lignosulfonates can also be prepared by deliberate sulfonation of unsulfonated lignins
acquired from other pulping processes such as kraft or organosolv pulping. Although
modifications to industrial lignins and lignosulfonates are necessary for obtaining the
required properties, the overall production costs of lignosulfonate-based admixtures are
still relatively low compared to their synthetically prepared counterparts. Nevertheless, in
order to remain competitive, lignosulfonate performance has to be elevated to the level of
high-range water reducing admixtures or superplasticizers. Several researchers have
reported such enhanced performance [7,8,17,18]. Generally, optimization of molecular
weight has been used to increase the dispersing effect of lignosulfonates [19], however,
intrinsic reasons for the increased efficiency are not fully understood. To facilitate further
performance improvement, a detailed knowledge of the impact of molecular structure
variation on lignosulfonate effectiveness as a concrete admixture is desirable. While the
effect of the degree of sulfonation on lignosulfonate performance has been discussed
previously [7,8], no attempt has been made to correlate the broader range of molecular
properties of lignosulfonates with their application effects in cement-water systems until
recently [20].
From the chemical point of view, lignosulfonates are polydisperse natural

polymers. According to the present understanding, lignin and lignosulfonate
macromolecules are composed of phenylpropane (C6C3) building units also known as C9
units. Each lignosulfonate sample is a mixture of macromolecules of different molecular
weights ranging from about 0.5 to about 1,000 kDa, depending on the number of C9 units.
In each molecule, the C 9 units are linked together by various C-C and C-0-C inter-unit
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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linkages. Moreover, the individual Cy units in the molecule are not identical. They differ
in types and numbers of functional groups attached to the carbon-based backbone.
Besides the inter-unit linkages, the functional groups in lignosulfonate molecules include
methoxyl, secondary and primary hydroxyl, phenolic hydroxyl, aromatic and aliphatic
carboxyl and sulfonate. Additional carbonyl containing groups such as aldehydes,
ketones and esters, as well as various double bonds are also present. The functional
groups and inter-unit linkages typically present in lignosulfonate molecules are
summarized in Table 1. The basic C9 phenylpropane unit of lignin with common notation
for carbon atoms is shown in Figure 1. Correlations between selected functional groups
counts and the dispersing, set-retarding and air-entraining effects of lignosulfonates in
fresh cement pastes were investigated and the findings are reported in this paper.
MATERIALS
Three samples of sodium lignosulfonates derived from sulfite, kraft and

organosolv pulping processes designated SL, KL and OL were included in this study.
Normal portland cement- CAN/CSA-A5 Type 10 (ASTM C 150, Type I) and potable
water were used for the preparation of cement pastes. The properties of these materials
are reported elsewhere [20].
METHODS
Sample Preparation and Chemical Analyses
Each lignosulfonate sample was divided into molecular weight fractions by

ultrafiltration using Amicon TCF10 laboratory unit and Diaflo® disk membranes with 1,
3, 10, 30 and 100 kDa nominal molecular weight cut-off (MWCO). Three series of four
lignosulfonate fractions (1-3, 3-10, 10-30 and 30-100 kDa MWCO) designated SLl to
SL4, KL1 to KL4 and OLl to OL4 were used for further investigation, while the
fractions below 1kDa and above 100 kDa MWCO were excluded. The weight-average
molecular weight (Mw) of each lignosulfonate fraction was determined by aqueous high-
performance size-exclusion chromatography (HPSEC). Sulfate analysis was performed
by suppressed high-performance ion chromatography (HPIC). Quantitative chemical
analysis for total carbon, hydrogen, oxygen, sodium, calcium, sulfur and the total
methoxyl group content was carried out at the E+R Microanalytical Laboratory, Inc.,
Parsippany, NJ, USA. Total sulfur content was also determined by atomic emission
spectrometry (AES-ICAP) at the Research and Productivity Council, Fredericton, NB,
Canada. All organic sulfur was considered to be present in the form of sulfonate (SL) or
methylsulfonate (KL, OL). A detailed description of the experimental procedures is
available elsewhere [20].
Molecular Structure and Functional Groups Determination
Even though the quantitative analyses of functional groups and structural

linkages in unsulfonated lignins can be successfully carried out by NMR methods, such
as 1H NMR, 13 C NMR or 31 P NMR [21], these methods have not been used to analyze
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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510 Zhor
sulfonated lignins to date. This is partly because of the difficulties presented by
heterogeneity, polydispersity, solubility, and other issues related to lignosulfonate
samples. As resources for the development of applicable NMR or other analytical
methodologies necessary for precise structure elucidation were unavailable in this
project, the focus was shifted to the generation of model molecular structures
representing individual lignosulfonate fractions. These model lignosulfonate structures
were derived from the 16 C9 unit structure proposed by Adler [22] and from all accessible
experimental and literature data. Even though the accuracy of such model structures is
limited, the proposed molecular structures were considered to be a reasonable
approximation of true lignin structures for the purpose of this research. All model
structures were designed in the form of lignosulfonic acid using a two-step procedure. In
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
the first step, a typical model 16 C9 unit segment was designed for each type of
lignosulfonate (SL, KL and OL). It complied with the data on elemental composition,
functional groups content, inter-unit linkages and other molecular characteristics
collected from the literature. In the second step, model molecular structures representing
the individual lignosulfonate fractions analyzed in this study were designed. These were
based on the results of experimental analysis acquired in this work, the model 16 C9 unit
segments from step one and additional experimental data obtained from the literature. As
a result, a complete molecular structure including all functional groups and linkages was
proposed for each lignosulfonate fraction. The detailed procedures and algorithms for
designing model molecular structures are available elsewhere [20].
Testing in Fresh Cement Pastes
The performance of sulfonated lignin samples in fresh cement pastes was

measured by two test methods developed specifically for the purpose of admixture
evaluation. These methods were the modified mini-slump test (MS-test) and the torque
test (T -test). The dispersing effect, considered as the main effect, was determined
independently by both methods. The side effects were measured as follows: the set-
retarding effect was determined by the T-test and the air-entraining effect was determined
by MS-test. A detailed description of these methods can be found elsewhere [20].
Correlation Analysis
The relatively small number of samples included in this study (3 sets of 4

lignosulfonate fractions) did not permit a comprehensive statistical analysis. As an
alternative, a new correlation methodology was developed. It was based primarily on
comparisons between the trends observed for functional group counts (FG) and
application effects of lignosulfonates in cement-water systems. Essentially, two distinct
correlation methods, similarity by distance and linear regression were combined. The
graph similarity method was based on the observation that, when plotted against the
molecular weight, both applications effects and FG follow more or less similar trends.
The Euclidean distance of data points in a metric space [23] was used as a basis for the
quantification of graph similarity. In addition, classical linear regression analysis was
performed. As a result, two compatible correlation coefficient values were obtained for
each FG-effect relationship: the correlation coefficient for similarity by distance R 0 , and

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the correlation coefficient for linear regression RLR· Provided both R0 and RLR possessed
the same sign (indicating positive or negative correlation), the mean value of the two
coefficients RAvG was determined for each FG-effect relationship. This value, denoted
according to the effect involved (RPL, RFL, RRET and RArR), was used as a measure of the
degree of correlation between FG and the respective application effect. The mean value
of coefficients RPL and RFL, denoted Rms, was used to quantify the correlation between
FG and the overall dispersing effect. Furthermore, only the FG having RAvG2:0.3 were
considered correlated with the respective application effects, all others were excluded.
The selection of outliers, and other details on the correlation methodology used in this
work are described elsewhere [20].
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
RESULTS
Performance in Fresh Cement Pastes
Three series of lignosulfonate fractions: SLl to SL4, KLl to KL4 and OLl to
OL4 were tested in fresh cement pastes. The results for dispersing (both plasticizing and
fluidifying), set-retarding and air-entraining effects plotted against the weight-average
molecular weight Mw are depicted in Figure 2.
Molecular Structure and Functional Groups Determination
The lignosulfonate fractions were analyzed for molecular weight and chemical
composition. The results are summarized in Table 2. Model molecular structures
representing individual lignosulfonate fractions were designed. Their molecular
parameters matched the analytical data presented in Table 2 as well as the literature data
on functional groups and structural linkages with an accuracy of ±5%. An example of a
proposed model molecular structure for a lignosulfonate fraction (SL series) composed of
fifty-two C9 units is shown in Figure 1. The relationships between selected functional
group counts per 100 C9 units and molecular weight of lignosulfonates (SL, KL and OL)
are depicted in Figure 3 and Figure 4. The complete sets of proposed molecular structures
representing the lignosulfonate fractions and the molecular properties of these structures
are available elsewhere [20].
Correlation Analysis
Correlation coefficients RrL and RFL describing the relationship between

individual functional group counts and plasticizing and fluidifying effects, are
summarized in Table 3 and Table 4, respectively. Correlation coefficients for the
relationship between the functional group counts and the overall dispersing effect R 01s
calculated as the mean of RrL and RFL values are presented in Table 5. Correlation
coefficients RsET describing the relationship between functional group counts and the set-
retarding effect are presented in Table 6. Correlation coefficients RArR describing the
relationship between functional group counts and the air-entraining effect are presented
in Table 7. For each effect, the functional groups are divided into positively and

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512 Zhor
negatively correlated values and sorted according to their correlation coefficient absolute
values in descending order.
DISCUSSION
Dispersing Effect
In the MS-test, the initial lignosulfonate-cement interactions take place in the

pre-induction period of cement hydration. The lignosulfonate molecules approach the
cement particles at the same time when they are being solvated upon first contact with
water. Initially, some lignosulfonate molecules may hydrogen bond to the yet non-
ionized surfaces of unhydrated cement particles. Later on, they may adsorb via calcium
bridges at the electrical double-layer formed on the negatively charged ionized surfaces
of cement grains. The dispersion mechanism is most likely electrosteric, with the need for
an optimum molecular weight and a delicate balance between the hydrophobic and
hydrophilic portions of the lignosulfonate molecules. The correlation results are
summarized in Table 3. The high positive correlation to polar aliphatic hydroxyls, which
are only partially ionized in the cement pore solution (pH ;:::; 13), suggests that a certain
degree of hydrophilicity is needed for a good plasticizing effect. The positive correlation
to inter-unit linkages, both C-C and C-0-C, indicates the importance of molecular weight
for the plasticizing effect. On the other hand, the negative correlation to all groups with
pKa<l2, fully ionized in cement-water systems, confirms that the hydrophilicity of the
dispersant molecules needs to be controlled.
A different scenario than in the MS-test is in place during the T-test. At the time
of lignosulfonate addition, 20 minutes after the initial contact of cement with water,
cement hydration is well under way [20]. As a result, lignosulfonate molecules can
adsorb both on the amorphous C-S-H gel coating covering the cement grains and on
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
ettringite, located both at the surface of cement grains and in the pore solution. These
interactions can not only inhibit and/or alter the ettringite crystal growth, but they also
can affect the dispersability of the whole system. The results are shown in Table 4. The
high positive correlation to methoxyls and C-C bonds indicates that the hydrophobicity of
lignosulfonates molecules is beneficial to the fluidifying effect. In other words, the
"repulsion" between hydrophobic lignosulfonate surfaces and the hydrophilic cement
grains seems, not surprisingly, to be a contributing factor to the dispersion stability.
Similar to the plasticizing effect, the negative correlation to the hydrophilic group counts
indicates that extreme hydrophilicity can be detrimental.
Presumably, the correlation between functional group counts and the overall
dispersing effect presented in Table 5 may provide an improved less test-dependent
insight into their relationship. Here, the methoxyl content is the most positively
correlated, probably due to its contribution to the hydrophobic and steric properties of the
molecule. The high correlation of inter-unit linkages (C-C and C-0-C) indicates the
positive contribution of molecular weight to the overall dispersing effect reported
previously [8,9]. The aliphatic carboxyl content is highly negatively correlated, which is
consistent with its contribution to an excessive negative charge on lignosulfonate

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polyanions. No truly significant correlation between the sulfonate group content and the
dispersing effect can be found, which is in accordance with a previous report [8].
Set-Retarding Effect
As set retardation is generally considered an unwanted side effect, a negative

correlation between functional group counts and the set-retarding effect is desirable. The
most negatively correlated functional group count to the set-retarding effect listed in
Table 6 is sulfonate. This is consistent with the previous report that for a given molecular
weight an increased degree of sulfonation reduces the initial set retardation [8).
Undoubtedly, Ca2+ is the hydration rate-determining ion as it is crucial for the

formation of all hydration products. This led to the conclusion that set retardation is
affected by the chelating capacity of the retarding admixtures such as lignosulfonates or
carbohydrates [24]. Moreover, it was pointed out that organic retarders such as salicylates
form amorphous complexes with aluminum but not with calcium [25]. Even though the
lignosulfonate complexation with aluminum and/or calcium is probably a contributing
factor, it does not necessarily have the predominant effect under all circumstances.
Particularly in the case of delayed admixture addition, as it happens in the T-test, by the
time the admixture is entered into the system, the hydration have already reached the
dormant stage and the rate of hydration reactions is minimal. Therefore it is not so
surprising that mechanisms other than chelation may play an important role.
As can be seen in Table 6, an increase in retardation is strongly correlated to an

--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
increase in carbon-carbon inter-unit bond and the methoxyl group count. This indicates
that retardation may be influenced by the formation of a hydrophobic membrane around
the hydrating cement particles, which slows down the dissolution of cement minerals and
the transfer of hydrated ions in the pore solution. A similar hydrophobic layer on the
surface of cement particles caused by the adsorption of surfactants may reportedly
increase the air stability in cement-water systems [26]. In agreement with the above
concept, polar lignosulfonate functionalities (pKa<12) are instrumental in reducing the set
retardation as they are negatively correlated to the retardation effect.
Air-Entraining Effect
Similar to the set-retarding effect, a negative correlation between functional

group counts and air-entraining effect is desired. As shown in Table 7, the primary
hydroxyl group count and the total aliphatic hydroxyl group count are the most
negatively correlated functional groups to the air-entraining effect. This is consistent with
the previously observed positive effect of methylolation on the reduction of air-
entrainment of cement mortars [9]. The opposite is true for the aliphatic carboxyl group
count which is highly positively correlated to the air-entraining effect. This can be
justified by the fact that both high solubility and good electrophoretic mobility contribute
to the ability of surfactants to stabilize the air bubbles. Perhaps surprisingly, the
correlation of sulfonate group count to the air-entraining effect is rather low, which was
also reported previously [8]. According to the above concept, smaller molecules should
be capable of maintaining greater foam stability. Indeed, this was confirmed by the

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514 Zhor
relatively high negative correlation of molecular weight-related inter-unit linkage counts
(C-0-C and C-C) to the air entraining effect. An increase in the air-entraining effect with
a decrease in molecular weight of lignosulfonate was also previously reported [27].
CONCLUDING REMARKS
The correlation analysis based on a combination of the graph similarity method

and linear regression resulted in the identification of positively and negatively correlated
functional group counts with respect to the three application effects of lignosulfonates in
cement-water systems. This analysis gave valuable information about the influence of
individual functional group counts on dispersing, set-retarding and air-entraining effects
of lignosulfonates. The results presented here show good agreement with the data
published by other researchers. This attests to the reliability of the methodology used in
this study.
The implications of this research on the understanding of lignosulfonate
interactions with cement-water systems were considered and the connection between the
most correlated functional group counts and individual application effects was discussed.
The presented research provides a new insight into the mechanisms of lignosulfonate
interactions with cement hydration products at the early stages of hydration, however,
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
further research is needed in order to explore these interactions in a greater detail.
ACKNOWLEDGEMENTS
This research was funded in part from various resources of the University of
New Brunswick, Canada. Financial support during laboratory experiments granted by Dr.
Bremner is particularly acknowledged. The author also wishes to thank Dr. van
Heiningen, Dr. Ni, Dr. Deslongchamps and Dr. Turner for providing an access to the
analytical equipment and molecular modeling software, and for valuable discussions.
REFERENCES
1. ASTM C 494: Specification for Chemical Admixtures for Concrete, Annual Book of
ASTM Standards, Vol. 04.02: Concrete and Aggregates, ASTM, Philadelphia, PA,
2000.
2. Mark, J. G., Concrete and Hydraulic Cement, US Patent No. 2,141,570, 1938.
3. Scripture, E. W., Cement Mix, US Patent No. 2,169,980, 1939.
4. Ernsberger, F. M. and France, W. G., Portland Cement Dispersion by Adsorption of

Calcium Lignosulfonate, Industrial and Engineering Chemistry, Vol. 37, No. 6, pp.
598-600, 1945.
5. Young, J. F., Hydration of Tricalcium Aluminate with Lignosulfonate Additives,

Magazine of Concrete Research, Vol. 14, No. 42, pp. 137-142, 1962.

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,`---
6. Collepardi, M. , Marcialis, A. and Solinas, V., The influence of Calcium
Lignosulfonate on the Hydration of Cements, II Cemento, Vol. 70, pp. 3-14, 1973.
7. Ramachandran, V. S., Effect of Sugar-Free Lignosulfonates on Cement Hydration,

Zement, Kalk und Gips, Vol. 31, No.6, pp. 144-146. 1978.
8. Rixom, M. R. and Waddicor, J., Role of Lignosulphonates as Superplasticizers, In

Developments in the Use of Superplasticizers, Proceedings, 2nd International
Conference on Superplasticizers in Concrete, Ottawa, ON, Canada, Edited by V. M.
Malhotra, ACI SP-68, ACI, Detroit, MI, pp.359-379, 1981.
9. Bialski, A. M. and Nayak, K. V., Superplasticizers from Lignosulfonates, In

Proceedings, 4th International Symposium on Wood and Pulping Chemistry, Paris,
France, Vol.l, pp.83-90, 1987.
10. Zhor, J., Bremner, T. W. and Lora, J. H., Effect of Chemical Characteristics of
Alcell® Lignin-Based Methyl-Sulfonates on Their Performance as Water-Reducing
Admixtures, In Proceedings, 4th International Conference on Superplasticizers and
Other Chemical Admixtures in Concrete, Montreal, Canada, Edited by V. M.
Malhotra, ACI SP-148, ACI, Detroit, MI, pp. 333-351, 1994.
11. Ferrari, G., Basile, F., Dal Bo, A. and Mantoni, A., The Influence of the Molecular
Weight of Beta-Naphthalene Sulfonate Based Polymers on the Rheological
Properties of Cement Mixes, Il Cemento, Vol. 83, No.4, pp. 445-454, 1986.
12. Cunningham, J. C., Dury, B. L. and Gregory, T., Adsorption Characteristics of

Sulphonate Melamine Formaldehyde Condensates by High Performance Size
Exclusion Chromatography, Cement and Concrete Research, Vol. 19, No.6, pp. 919-
926, 1989.
13. Yamada, K., Takahashi, T., Hanehara, S. and Matsuhisa, M., Effects of the Chemical
Structure on the Properties of Polycarboxylate-Type Superplasticizer, Cement and
Concrete Research, Vol. 30, No.2, pp. 197-207,2000.
14. Zhor, J. and Bremner, T. W., Role of Lignosulfonates in High Performance

Concrete, In Proceedings, International Symposium on the Role of Admixtures in
High Performance Concrete, Monterrey, Mexico, Edited by J. G. Cabrera and R.
Rivera-Villareal, RILEM Publications, pp. 143-165, 1999.
15. Gustafsson, J. and Reknes, K., Adsorption and Dispersing Properties of

Lignosulfonates in Model Suspensions and Cement Paste, In Proceedings, 6th
Concrete, Nice, France, Edited by V. M. Malhotra, ACI SP-195, pp. 181-193,2000.
16. Perche, F., Houst, Y. F., Bowen, P. and Hofmann, H., Adsorption ofLignosulfonates
and Polycarboxylates - Depletion and Electroacoustic Methods, In Proceedings, 7th

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Concrete, Berlin, Germany, Supplementary Papers, pp. 1-15,2003.
17. Zhor, J. and Bremner, T. W., Influence ofNew Environmentally Beneficial Lignin-
Based Superplasticizer on Concrete Performance, In Radical Concrete Technology,
Edited by R. K. Dhir and P. C. Hewlett, E&FN Spon, London, UK, pp.301-311,
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1996.
18. Kauppi, A., Banfill, P. F. G., Bowen, P., Galmiche, L., Houst, Y. F., Lafuma, F.,
Mader, U., Perche, F., Petersen, B.G., Reknes, K., Schober, 1., Siebold, A. and Swift,
D., Improved Superplasticizers for High Performance Concrete, In Proceedings, 11th
International Congress on the Chemistry of Cement, Durban, South Africa, Edited by
G. Grieve and G. Owens, pp. 528-537, 2003.
19. Zhor, J. and Bremner, T. W., Influence of Lignosulphonate Molecular Weight

Fractions on the Properties of Fresh Cement Paste, In Proceedings, 5th International
Conference on Superplasticizers and Other Chemical Admixtures in Concrete,
Rome, Italy, Edited by V. M. Malhotra, ACI SP-173, pp. 781-805, 1997.
20. Zhor, J., Molecular Structure and Performance of Lignosulfonates in Cement-Water

Systems, PhD dissertation, University ofNew Brunswick, Canada, 2005.
21. Argyropoulos, D. S., Quantitative Phosphorus-31 NMR Analysis of Lignins, a New

Tool for the Lignin Chemist, Journal of Wood Chemistry and Technology, Vol. 14,
No. 1, pp. 45-63, 1994.
22. Adler, E., Lignin Chemistry - Past, Present and Future, Wood Science and
Technology, Vol. 11,No. 2,pp.169-218, 1977.
23. Dshalalow, J. H., Real Analysis: An Intoduction to the Theory of Real Functions and
Integration, Chapman&Hall/CRC, Boca Raton, FL, 2001.
24. Young, J. F., Reaction Mechanisms of Organic Admixtures with Hydrating Cement
Compounds, In Concrete Admixtures, Transportation Research Record 564, pp. 1-9,
1976.
25. Chandra, S., Flodin, P., Interactions of Polymers and Organic Admixtures on
Portland Cement Hydration, Cement and Concrete Research, Vol. 17, No.6, pp. 875-
890, 1987.
26. Ramachandran, V. S., Admixture and Addition Interactions in the Cement-Water

System, Il Cementa, Vol. 83, No. 1, pp. 13-38, 1986.
27. Kobayashi, A., Tadaaki, H., Yamakawa, 1., Sato, K., On the Dispersing and Air
Entraining Effect of Lignosulfonate, Mokuzai Gakkaishi, Vol. 13, No. 3, pp. 118-
122, 1967.

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Table 1 -- Typical functional groups and inter-unit bonds in lignosulfonate molecules
investigated in this work.
Group Molecular Lewis pK. Group Count

Name Formula Structure Main Range Range per c900
0
II
Sulfonate R-S03H R-S-OH -4.5 - -2.0 10-70
II
0
Aliphatic
R-COOH R-C
1P 1.5 - 5.0 0-50
Carboxyl
'OH
Aromatic
Ar-COOH 2.5 - 4.5 0-50
Carboxyl o-t:H
Phenolic
Ar-OH Q-oH 8.0 - 12.0 10-80
Hydroxyl
H
Primary I
R-CH20H R-C-OH 12.0 - 16.0 20-70
Hydroxyl I
H
R'
Secondary I
R2CHOH R-C-OH 12.0 - 16.0 10-40
Hydroxyl I
H
H
Methoxyl Ar-OCH3 Q-o-b-H >20 60- 110
I
H
e.g.
Ar-0-R R
Inter-Unit
R-0-R' >20 10-80
Ether Bond o-o-t-H
Ar-0-Ar' I
R'
e.g.
Ar-R R
Inter-Unit
R-R' o-b-H N/A 10-80
C-CBond
Ar-Ar' I
R'
Notes: 1. C900 stands for 100 C9 umts. 2. Other carbonyl-contammg functionalities
.. ..
such as ketones, aldehydes and esters, as well as ethylenic structures are also
present in lignosulfonate molecules.

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518 Zhor
Table 2 -- Molecular weight and chemical composition of lignosulfonate (SL, KL
and OL) fractions.
Sample
Code
Mw{kDa) c ("lo) H(%) Na(%) Ca(%) 8(%) 0(%) OCH3(%)
SLl 0.82 42.05 3.57 8.14 0.28 7.70 38.26 7.95

SL2 1.79 49.32 4.17 5.77 0.72 7.41 32.63 11.20
SL3 4.69 52.67 4.47 4.95 0.44 6.23 31.24 l1.45
SL4 11.19 53.48 4.57 3.70 0.61 5.70 31.93 11.23
KL1 0.77 42.04 3.85 l1.41 -- 8.73 33.97 7.85
KL2 1.48 48.38 3.99 7.89 --- 6.58 33.15 8.78
KL3 3.11 53.80 4.59 6.27 ·- 5.37 29.97 10.49
KL4 5,07 53.00 4.53 5.88 -- 4.86 31.74 10.53
OL1 0.76 47.44 4.01 9.70 --- 3.82 35.04 10.21
OL2 1.35 55.26 4.15 6.46 ·-- 3.51 30.62 l1.32
OL3 1.98 56.98 4.18 5.88 --
2.60 30.35 11.49
OL4 3.41 57.40 4.49 4.63 --- 1.93 31.54 12.36
Notes: 1. Results are reported m mass (w/w) percentages.
2. Data are corrected for moisture and impurities.
Table 3 -- Correlation between functional groups of model molecular structures of

lignosulfonate fractions and their plasticizing effect in cement-water
systems.
Correlation Rank Functional Group I Bond Count Correlation Coeff. RpL
I Oet Inter-Unit Bond 0.7I9

2 OHpnn Group 0.679
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
3 OCH3Group 0.581
Positive 4 OHa~.totGroup 0.576
5 C-C Inter-Unit Bond 0.441
6 OHsecGroup 0.317
I All pKa<12 Group -0.697
2 COOHa~Group -0.619
3 OHphGroup -0.569
Negative 4 COOH101 Group -0.546
5 All pKa<5 Group -0.528
6 S0 3HGroup -0.367

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lignosulfonate fractions and their fluidifying effect in cement-water
systems.
Correlation Rank Functional Group I Bond Count Correlation Coeff. RFL
1 OCH3Group 0.533
Positive 2 C-C Inter-Unit Bond 0.467
3 Oet Inter-Unit Bond 0.320
1 All p.K,<5 Group -0.650
2 All p.K,<12 Group -0.451
Negative 3 COOHtotGroup -0.409
4 COOHa1Group -0.369
5 S03HGroup -0.292

lignosulfonate fractions and their overall dispersing effect in cement-water
systems.
Correlation Coefficient
Correlation Rank Functional Group I Bond Count
RpL ~ Ro1s
1 OCH3Group 0.581 0.533 0.557
2 0., Inter-Unit Bond 0.719 0.320 0.520
Positive 3 C-C Inter-Unit Bond 0.441 0.467 0.454
4 OHpnnGroup 0.679 0.154 0.416
5 OHaJ.totGroup 0.576 0.068 0.322
1 All pK0 <5 Group -0.528 -0.650 -0.589
2 All p.K,<ll Group -0.697 - 0.451 -0.574
3 COOHa1Group -0.619 -0.369 -0.494
Negative
4 COOHtot Group -0.546 -0.409 -0.478
5 S03HGroup -0.367 -0.292 -0.329
6 OHphGroup -0.569 -0.068 - 0.318

lignosulfonate fractions and their set-retarding effect in cement-water
systems.
Correlation Rank Functional Group I Bond Count Correlation Coeff. RsEr
1 C-C Inter-Unit Bond 0.729

Positive 2 OCH3 Group 0.531
1 S03HGroup -0.593
Negative 2 All p.K,<S Group -0.513
3 All p.K,<I2 Group -0.318
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520 Zhor
lignosulfonate fractions and their air-entraining effect in cement-water
systems.
Correlation Rank Functional Group I Bond Count Correlation Coeff. ~
I All pK,<l2 Group 0.774

2 COOHa~Group 0.7ll
3 All pK,<5 Group 0.652
Positive
4 OHphGroup 0.530
5 COOH""Group 0.518
6 S~HGroup 0.405
I OHprm Group -0.732
2 ORa~."" Group -0.731
3 Oct Inter-Unit Bond -0.720
Negative
4 OCH3 Group -0.686
5 OR..., Group -0.565
6 C-C Inter-Unit Bond -0.361
6
5
¢ 4
,......o
f3
2
3
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 1--Basic C9 phenylpropane lignin unit with common notation for carbon atoms
and an example of lignosulfonate model molecular structure (fraction SL4).

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160 0.37
E -
... 133 :;i:0.34
. E
~106 (o.31
rs
<
:52
.!o.28
g
~0.25
1'-
0.22
2.2 4.4 6.6 6.6 11.0 0.0 2.2 4.4 6.6 6.8 11.0
Mw,kDa Mw,kDa
15.0 25
I!!
j!12.6 - 20
.0:: ~
g-10.2 - ~ 15
ii
1 7.8 i
0 10
& ~
i 5.4 -
3.0
0.0 2.2 4.4 6.6 8.6 11.0 0.0 2.2 4.4 6.6 6.6 11.0
Mw. kDa Mw. kDa
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Figure 2 --Relationship between plasticizing, fluidifying, set-retarding and

air-entraining effects in fresh cement pastes and molecular weight of lignosulfonate
samples (SL, KL and OL).

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522 Zhor
100 ,--------,===;--.---r------r==:;-]
S03H OSL : 0SL
J 80 J 80
I :
-6---~----:-----:-----: 6KL , ---~ "KL
i 60 DOL !. 60 -o---~----:-----:-----: DOL

1: §
8 40 ----, - -~,---=--=-"'-'""'-'7,-~-~-~-"'1 8 40
e""
Cl
20 ~- -:---- -!-----!----- e"""' 20
Cl
' ' '
0.0 2.2 4.4 6.6 8.8 11.0 0.0 2.2 4.4 6.6 8.8 11.0
Mw,kDa Mw, kDa
100 ,-----;rc==;-r--;-------,== 150

0 COOH,., : : 0SL
J 80 - - - - r - - - -,- - - - -,- - - -
1
-~
IIKL J125
~ '
---,I
'
"" 60 DQL !100

1: I
8 40 § 75
e"" 20
~
e"'"" so
" o'--~-'-~--'-~~~-.L-~_j "
0.0 2.2 4.4 6.6 8.8 11.0 2.2 4.4 6.6 8.8 11.0
Mw. kDa Mw.kOa
100 .--~=o---r---r----r==
§ 80
u
z. 60
§
8 40
i
I
I I
20 - - - - r - - - -,- - - - -,- - - - -,-
" 1 ' '
0.0 2.2 4.4 6.8 8.8 11.0 0.0 2.2 4.4 6.6 8.8 11.0
Mw. kDa Mw. kDa
Figure 3 --Relationship between various fully ionizable (pK0 <12) functional group
counts per 100 C9 units and molecular weight of lignosulfonate samples
(SL, KL and OL).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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,--_=
~=:---1:---,:--,:----,
100
J~ ----r----r----r----~-----
" 40 -{}-
~60 !30
0 0
8 40 8 20
"e"" 20
0
e""
0
10
0.0 2.2 4.4 6.6 8.8 11.0 0.0 2.2 4.4 6.6 8.8 11.0
Mw, kDa M.., kDa
120 r---:r==-,----,----,------,
~~ I I I I
" 90
K8o
§
- - - -:- - -: ~- - 8
~
70
I 1 ~Kl
r 1 - - - -~- - - - -~ 2 60
0
20 L_~~-~~~-L-~~:=o=o~L~
0.0 2.2 4.4 6.6 8.8 11.0 0.0 2.2 4.4 8.8 8.8 11.0
M.., kDa M,,kDa
100 ,---:r:=:--,------,,.------,------,
o.... 100 r-------:~§J=,.:--T,----.,---r:,j=O=SL=I
j
!
~
80
60 f: ~::t : ::::
t=-~~
40
0
e"" 20 (:t Q I : : I
0.0 2.2 4.4 6.6 8.8 11.0 0.0 4.4 6.6 8.8 11.0
Mw. kDa M..,kDa
Figure 4 --Relationship between various partially ionizable (pK}12) functional group

and inter-unit bond counts penoo C9 units and molecular weight of lignosulfonate
samples (SL, KL and OL).
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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524 Zhor
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-34
Influence of D-Sorbitol on the

Properties of Binders to Immobilize
Acid Nuclear Wastes
by M. Collepardi, G. Grossi, M. Pellizon Birelli,

and G. Ventura
Synopsis: A combination of ground granulated blast furnace slag, fly ash and
calcium hydroxide has been used to immobilize acid nuclear wastes in the form of a
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
hardened system in the absence of any aggregate. An aqueous solution of NaOH (19
M) was used for two purposes: first, to neutralize the acid waste and to transform it in
a very basic system (pH>13); second, to activate the hardening ofthe binder.
Due to the liquid-solid ratio lower than 0.70, the fresh mixture is relatively stiff.
Superplasticizers based on sulfonated naphthalene and melamine or acrylic
polycarboxylate do not work to fluidify this system. D-Sorbitol as well as other alditols
are very effective in terms of higher workability and lower workability loss of this
cementitious system. Surprisingly this chemical admixture increases the compressive
strength of this cementitious grout at both early and longer ages at a given water-
binder ratio.
The properties of this cementitious system in the absence and in the presence of
D-sorbitol as chemical admixture (0.2-o.s% by weight of binder) have been studied
in the form of workability of the fresh mixture, early and later compressive strength,
leachability by water and X-ray diffraction analysis of the hydrated products of the
hardened system.
Keywords: blast furnace slag; fly ash; nuclear wastes; solidification/

stabilization; sorbitol

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Mario Collepardi is author or co-author of numerous papers on concrete technology and
cement chemistry. He is also the recipient of several awards for his contributions to the
fundamental knowledge of superplasticizers and their use in concrete.
Giuseppe Grossi, Doctor in Chemistry is a technical consulting of SOGIN. His

experience is mainly based on the chemical treatment of nuclear wastes: he has published
several papers in this area.
Marta Pellizon Birelli is Doctor in Industrial Chemistry. She works in Enco in the area of
R&D for the special cementitious system for immobilization of nuclear wastes.
Giancarlo Ventura is a Geologist expert in nuclear treatments and geological placements
of nuclear wastes in SOGIN. He has published some papers in this area
INTRODUCTION
Solidification/stabilization through the use of specially formulated mortars or grouts

is one of the most commonly used methods to immobilize many nuclear and toxic wastes.
According to Glasser [1], the binding formulations are usually based on Portland cement
and its blends with fly ash (FA) and ground granulated blast furnace slag (GGBFS). The
replacement of Portland cement with these minerals additions is accompanied by many
technological advantages [2].
One of the most important properties needed for such a process is the long-term
durability for many centuries or at least a millennium. Examples of cementitious systems
manufactured more than a millennium ago and still keeping their original properties are
available in the form of pozzolanic materials combined with lime without metallic
reinforcements as the Pantheon in Rome. Such a system was considered in the present
work to be a good candidate as binder to immobilize a special radioactive liquid waste
currently stored at the EUREX pilot reprocessing facility (Saluggia, Italy). This liquid
waste - accumulated since 1970' from the reprocessing of irradiated fuel used in the
Italian Material Testing Reactors- is highly radioactive and contains mainly short-lived
radionuclides (Cs-137 and Sr-90), and only traces of long-lived alpha emitting
radioisotops. Since the liquid waste is acidic (pH<1) and contains a considerable amount
of dissolved aluminum ions (Ae+), the solidification/stabilization process requires a
preliminary treatment of the solution for the conversion of Ae+ into dissolved sodium
aluminate, Na+Al(OH)4". This treatment is carried out through alkalinization of the acidic
solution by using sodium hydroxide NaOH up to a final pH2:13. After alkalinization, the
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
waste should be mixed with a Portland cement-free formulation based on a blend of blast
furnace slag, fly ash and hydrated lime as calcium hydroxide.
The role ofNaOH, used to neutralize the acidic waste, was also that of an activator of
the binding system in order to accelerate the hardening process. On the other hand, the
absence of aggregates in the cementitious system can exclude any form of alkali-
aggregate reaction due to the presence ofNaOH.
The present work is specially devoted to study the influence of D-sorbitol adopted as
chemical admixture to improve the workability of the fresh mixtures. This property,
which is absolutely needed because the liquid waste and the binding system are mixed

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into a stainless steel container without any compaction effort, is probably based on the
sequestring capability of polyols with respect to aluminum products [3].
In order to work safely in a traditional cement-concrete laboratory, an aqueous

solution (Table 1) was designed to simulate one particular tank of intermediate level
waste currently stored at the EUREX plant. It is an acidic aqueous solution containing
dissolved salts (nitrates) of aluminum and iron. Prior to the solidification process the
solution was alkalinized by adding a 19M NaOH so that the pH became higher than 13.
The "reverse strike" procedure (i.e. the acidic solution was added to the necessary
amount of 19M NaOH, and not vice versa) was employed in order to transform Ae+ ions
directly in the water soluble sodium aluminate, Na+Al(OH) 4·, and to avoid the formation
of aluminum hydroxide gel, Al(OH) 3 •
The stoichiometric excess ofNaOH was adjusted in order to activate the blast furnace
slag used in the binding formulation. It should be noted that the small amount of iron
hydroxide precipitated in the alkalinized solution did not interfer during the solidification
process. The final composition of the alkalinized solution is shown in Table 2.
The binder used for the solidification process is a blend of blast furnace slag, fly ash
and lime in the proportion of 65:25:10 (Table 3). The chemical composition of each
component is listed in Table 4. This composition was the result of preliminary tests based
on many cementitious systems including portland cement- not presented in this paper -
indicating the best mixture in term of workability and compressive strength.
Analytical grade of an aqueous solution ofD-sorbitol (70 wt.%) was used.
The grouts were prepared by mixing the alkalinized solution with the binding system.
D-Sorbitol was added to the solution prior to mixing with the binder. The workability
was evaluated according to UNI EN 1015-3 by the flow table test procedure for fresh
mortars by measuring the increase of the grout diameter [4]. Compressive strength at 1, 3,
7 and 28 days was measured on prismatic (40x40xl60 mm) specimens cured at 20°C and
RH>95%.
Long-term stability of the wasteform is estimated by determining the leachability of
Na+ and Ca2+ into a specified amount of demineralized water over specified time periods
for a total of90 days according to ANS/ANSI-16.1. [5]
For the X-ray diffraction analysis the samples were ground in an agate mill to a fine
powder (<90 11m).
Table 5 shows the workability of the fresh grouts as a function of the waste-binder
ratio. In the absence of any drop table, the workability should be as high as possible (at
least 100%). On the other hand, the amount of liquid should be relatively low in order to
reduce the radiological load of the final waste form. The compromise was to choose the
waste-binder ratio of 0.60 (corresponding to a water-binder ratio of 0.39) and to improve
its workability by using a fluidifying chemical admixture. The use of usual
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528 Collepardi et at.
superplasticizers (sulfonated naphthalene or melamine and polycarboxylates) was
unsuccessful. Then, alternative chemical admixtures were tried. Among them, polyols
worked very well. In particular D-sorbitol resulted to be the best.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Table 6 shows the workability of the fresh grouts with addition of D-sorbitol and its
loss during the first hour after mixing. According to the nuclear expertise, the fresh
mixtures should be workable (flow>100%) without any compaction effort at least during
1 h. The results indicate that 0.4-0.5% of a 70% D-sorbitol aqueous solution with respect
to the binder system is good enough for the workability requirements.
Figure I shows the compressive strength of the hardened grouts as a function of the
curing time. Surprisingly the addition of D-sorbitol is not associated with any retarding
effect both at early and at later ages.
Table 7 shows the Leachability Index (LI) values calculated according to the long-
term test procedure (90 days). All the binder systems satisfy the condition that ensures a
good containment of soluble salts (LI>7 for sodium and LI>8 for calcium). Moreover, the
presence of D-sorbitol and the waste-binder ratio do not substantially affect this property
required for wasteform durability.
Results obtained by XRD analysis (Figure 2) show that the binding formulation is
mainly constituted of the amorphous phase (broad hump centred at 28=30°) and some
crystalline phases (quartz, mullite, portlandite). After 28 days of curing new phases are
detected in the hardened grouts; these were recognized as calcite CaC03, hydrotalcite
Mg 6Ah(C0 3)(0H) 16 ·4H20 and calcium silicate hydrate C-S-H.
CONCLUSIONS
In the absence of any mechanical compaction the workability of the fresh grouts
represented the most important parameter to be considered. Due to the presence of a
considerable amount of aluminum in the nuclear waste the workability of the waste-
binder system was very low. Only in the presence of D-sorbitol the fluidity reached an
optimum value, even at water-binder ratio as low as 0.39. Moreover, in the presence of a
70% D-sorbitol aqueous solution (0.4-0.5% by binder weight) the compressive strength
of the hardened system was increased indicating a better durability of the wastefonn.
The results of the research are summarized as follows:
a) The workability increases at very low dosages of a 70% D-sorbitol aqueous solution
(0.2-0.5%)
b) The workability loss satisfy the requirement of a flow> 100 after one hour from the
initial mixing
c) The compressive strength is substantially unchanged at early ages and increases at
later ages
d) The Leachability Index values ofNa+ and ci+ are not affected by the presence ofD-
sorbitol
e) The compounds that form during hydration of grout specimens are not known having
any detrimental effect on wasteform durability.

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REFERENCES
[1] F.P. Glasser, Fundamental aspects of cement solidification and stabilisation, Journal
ofHazardous Materials 52 (1997) 151-170.
[2] M. Collepardi, "Use of fly ash, silica fume, slag and natural pozzolans in Europe:
future directions", International Workshop on the Use of Fly Ash, Silica Fume and
other Siliceous Materials", Sydney, 4-6 July (1988).
[3] P.G. Smith, H.R. Watling, P. Crew, The effects of model organic compounds on
gibbsite crystallization from alkaline aluminate solutions: polyols, Colloids
Surfaces A: Physicochem. Eng. Aspects, 111 (1996) 119-130.
[4] UNI EN 1015-3:2000 Determination of consistency of fresh mortars (by flow table).
[5] ANSI/ANS-16.1-2003 Measurements of the leachability of solidified low-level
radioactive wastes by short-term test procedure.
Table 1 - Composition of the simulated solution
Compound mol/L
H"No3 0.79
~hS04 0.02
k-\I(N03 )]"9H20 1.13
Fe(N03)J"9H20 O.Ql
Table 2 - Composition of the simulated solution after alkalinisation

Compound mol/L
~odium 5.71
!Nitrate 3.00
Sulfate 0.01
!Aluminate 0.81
!Precipitate ofFe(OH)3 (g/L) 0.8
INaOH molar excess(%) 34
~ater (wt.%) 65
bH 14
Table 3 - Binder composition.

Amount Density PROPERTY
Material
(wt.%) f!/cm3
JGBFS 65 2.86 Blaine of 4400 cm2/g
A 25 2.30 ASTMClassF
ime 10 2.19 Ventilated hydrated lime
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530 Collepardi et at.
Table 4 - Composition of the mineral additions (wt.% ).
)xi de GGBFS FA Lime
i02 20.8 38.78 0.90
h03 4.3 28.72 0.10
e203 4.4 15.82 0.07
~ao 64.6 3.50 68.9
~gO 1.0 - 3.6
~a20 0.1 0.51 -
IK2o 0.5 0.24 -
so3 2.7 O.Ql 0.11
ro2 - - 2.1
rhO - - 21.7
01 1.3 6.7 -
)(RJ) Totally amorphous q,m, I* p, c, o*
* q=quartz, m=mulhte, l=hme CaO, p= portland1te Ca(OH)2,
c=calcite and o=periclase.
Table 5- Workability (flow table test) of grouts without chemical

admixtures.
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Waste-binder Water-binder
Admixture Workability(%)
ratio ratio
0.50 0.32 30
no 0.60 0.39 90
0.70 0.46 120
Table 6- Workability as a function ofD-sorbitol aqueous solution (70%)

at a waste-binder ratio=0.60.
D-sorbitol Initial workability Workability(%) at a time of:
wt.% of binder) Omin 30min lb
- 90 0 0
0.2 165 0 0
0.3 180 75 0
0.4 190 150 90
0.5 190 170 120
Table 7- Leachability Index calculated according to ANSI/ANS-16.1.

Leachability
Leachability
D-sorbitol Waste-binder Index
Index
wt.% of binder) ratio (calcium
(sodium Na)
Ca 2)
0.7 8.4 9.8
0.6 8.2 9.5
0.5 0.6 8.1 9.6

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40.0
.. 35.0
a.
:::;;
;; 30.0
"'c:~ 25.0
ti5
.~ 20.0
~c. 15.0
E
8 10.0
5.0
0.0
7 26
Time of curing (days)
Fig. 1- Compressive strength of hardened grouts as a function of D-sorbitol

aqueous solution.
""" l PC A 0
p p p
q
FA m q m,.ol m m m I m I
~s
p
-
sllgglasa
p
di)'WndlllgW.IHI
m P m p p
m p
c.s...
-
21da)os"llydmfdlllend
h rnA
10 15 20 2!1 30 35 40 45 50 55 60
"28
Fig. 2- XRD pattern of binding formulation. Where p= portlandite Ca(OH) 2 , c=calcite,

o=periclase, m=mullite, q=quartz, l=lime CaO, h=hydrotalcite and
C-5-H=calcium silicate hydrate.
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--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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SP-239-35
Effectiveness of Superplasticizers
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Incorporating Shrinkage-Reducing
Admixture in Recycled-Aggregate
Concrete
by V. Corinaldesi and G. Moriconi
Synopsis: Recycled-aggregate concrete is known for its higher tendency to shrink

with respect to concrete prepared with ordinary aggregate, at least when both
coarse and fine recycled aggregate are used. In this work, an attempt was made to
manufacture recycled-aggregate concrete that is less sensitive to shrinkage. Seven
different concrete mixtures were prepared with the same water-to-cement ratio of
0-45 by various kinds of coarse aggregate: ordinary natural gravel, recycled-concrete
aggregate from a suitable treatment of precast-concrete scraps, or a recycled-rubble
aggregate from a crushing plant in which rubble from building demolition is treated.
Different kinds of water-reducing admixtures were also tested: the first one was
based on polycarboxylate polymer, the other two were also based on polycarboxylate
polymer incorporating a shrinkage reducing group. The latter two are characterized
by a different formulation to assure either a set-accelerating or a retarding effect.
The pure superplasticizing admixture was added at a dosage of o.8%, by mass of
cement, while the multifunction admixtures were added at a dosage of 1.6% and
2.0%, by mass of cement, for the accelerating and the retarding types, respectively.
Compressive strength tests were carried out at different curing times, and free-drying
shrinkage was measured up to 70 days of age. The results were positive, particularly
in terms of very low shrinkage of recycled-aggregate concrete containing the
shrinkage reducing admixture.
Keywords: recycled-aggregate concrete; recycled concrete; shrinkage-

reducing admixtures

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534 Corinaldesi and Moriconi
Valeria Corinaldesi is a Civil Engineer and has a Ph.D. in Materials Engineering; she
holds a permanent position as researcher at the Department of Materials and Environment
Engineering and Physics of the Technical University ofMarche, Ancona, Italy.
Giacomo Moriconi is Professor of Materials Science and Technology at the Technical

University of Marche, Ancona, Italy and is the Head of the Department of Materials and
Environment Engineering and Physics. He is the author and co-author of numerous
papers in the field of cement and concrete technology, building materials performance,
and durability.
INTRODUCTION
Previous results obtained by the authors (Corinaldesi and Moriconi 2001; Corinaldesi et
a!. 2001; Corinaldesi and Moriconi 2002; Corinaldesi and Moriconi 2003a; Corinaldesi
and Moriconi 2003b) as well as those reported in the literature (Hansen 1992; Kasai
1998; Dhir et a!. 1998) showed how the use of aggregates coming from recycling process
allows the production of structural concrete, at least concerning their mechanical
performance. One ofthe critical points concerning the employment of recycled aggregate
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is its higher tendency to shrink compared to ordinary aggregate concrete. This is
especially the case when both coarse and fine recycled aggregate are used (Corinaldesi et
a!. 2001; Hansen and B0egh 1985). This behavior could increase cracking vulnerability
of recycled-aggregate concrete even though tensile stresses induced by shrinkage strain
are lower, given the lower elastic modulus of the concrete (Corinaldesi et a!. 2001;
Hansen and B0egh 1985).
In this work an attempt was made to manufacture recycled-aggregate concrete that is less
sensitive to shrinkage which uses only coarse recycled aggregate, water-soaking the
recycled aggregate before its introduction in concrete, thus creating an internal water
reserve, and also introducing water-reducing admixture.
Shrinkage-reducing admixtures (SRAs) are chemical admixtures based on neopentil

glycol, (CH 2) 2-C-(CH20H) 2, or other similar products, such as polypropylenglycol ether
(Palacios and Puertas 2005; Maltese et al. 2005), that reduce drying and/or autogeneous
shrinkage (Collepardi et a!. 2005; Berke eta!. 2003; Nakanishi et a!. 2003). They can be
used either in addition to traditional superplasticizing admixtures or incorporated in them
by attaching a shrinkage reducing group to the polycarboxylate polymers, thus producing
a new multifunction admixture (Collepardi 2005a; Collepardi 2005b).
The mechanism through which shrinkage-reducing admixtures are able to reduce plastic,
autogeneous and especially drying shrinkage of concrete seems to be the lowering of
surface tension of the water in capillary pores (Rongbing and Jian 2005; Folliard and
Berke 1997; Bentz 2001). In fact, as water-filled pore begin to loose moisture, curved
menisci are formed, and the surface tension of water pulls the walls of the pores. With the
reduced surface tension of water, the force pulling the walls of the pores is probably
decreased, and the resultant shrinkage strain is reduced in tum.

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MATERIALS
A commercial portland-limestone (20% maximum limestone content) blended cement

type CEM IIIA-L 42.5R according to the European Standards EN-19711 was used. The
Blaine fineness of cement was 410m2/kg, and its specific gravity was 3.05 kg/m 3•
Natural sand (with a maximum size of 5 mm) was used in each concrete mixture. Its main
physical properties are reported in Table 1, and its grain-size distribution is plotted in Fig.
1.
The kind of coarse aggregate was changed: either an ordinary natural gravel or a
recycled-concrete aggregate from a suitable treatment of precast-concrete scraps or a
recycled aggregate from a crushing plant in which rubble from building demolition is
suitably selected, ground, cleaned and sieved. Their main physical properties of the
aggregates are reported in Table I, and their grain-size distributions are plotted in Fig. I.
In particular, the recycled-concrete aggregate (indicated below as 'Recycled concrete')

comes from concretes scraps characterized by 50 MPa cubic strength class supplied by a
precasting plant in Piacenza (Italy), while the recycled-rubble aggregate (indicated below
as 'Recycled rubble') comes from an industrial crushing plant in Villa Musone (Italy), its
average composition is 70% concrete, 27% masonry and 3% miscellaneous (bitumen,
glass, wood ... ).
As shown in Fig. I, the maximum-particle size of the coarse aggregates was 20 mm; in
particular, it can be noticed that the grain-size distribution curves of 'Natural gravel' and
'Recycled rubble' are quite the same. While the 'Recycled concrete' appears slightly
finer.
In terms of water absorption, strong differences can be detected (Table I). It should be
underlined that both recycled-aggregate fractions were added to the mixture after water-
soaking, in a condition very close to that defined as saturated surface-dried. This was
done to create an internal water supply able to reduce drying-shrinkage as well as to
avoid water absorption of aggregate during mixing and, consequently, to maintain
concrete workability for enough time to be cast.
A common water-reducing admixture based on polycarboxylate polymers (30 % aqueous

solution) was used and is referred to here as 'Superplasticizing admixture' or simply
'SP'.
Two patented multifunction admixtures were used, both based on polycarboxylate

polymers (responsible for the water-reducing action) that also incorporate a shrinkage-
reducing group. Their difference consists on a different formulation for assuring either a
set-accelerating or retarding effect.
The type showing an accelerating effect is indicated below as 'Superplasticizer with PC-
type SRA', where 'PC' means precast concrete; in fact, this chemical admixture can be
properly used in precast-concrete production since it allows early forrnwork removal.
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On the other hand, the type showing a retarding effect is indicated below as
'Superplasticizer with RM-type SRA', where 'RM' means ready-mix concrete. In fact,
this chemical admixture was suitably studied for ready-mix concrete production to ensure
enough time for transport and placement of concrete without much loss in workability.
PROPORTIONING OF CONCRETE MIXTURES
Seven different concrete mixtures were prepared with the same water-to-cement ratio of
0.45 and the same slump of 170 mm, to guarantee sufficient workability, by varying the
kinds of coarse aggregate and chemical admixture.
In Table 2, the mixtures proportions of the three concretes prepared using natural
aggregate are reported. The first mixture, indicated as 'Nat+SP', was prepared with the
pure water-reducing admixture added at a dosage of 0.8%, in terms of total mass of
admixture by mass of cement, which guaranteed a water reduction of 25%. The same
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water reduction was achieved using superplasticizer with PC-type SRA dosed at 1.6%, by
mass of cement. A slightly lower water reduction of 20% was obtained by the
superplasticizer with RM-type SRA dosed at 2.0%, by mass of cement. Natural sand and
gravel were combined at a percentage of 40% and 60% by volume respectively in order
to achieve optimum grain size distribution of the whole inert fraction according to the
Bolomey particle size distribution curve (Collepardi 1991).
In Table 3, the mixture proportioning of the four evaluated concrete mixtures prepared
using recycled aggregate are reported. The mixtures indicated as 'RecCon+SP' and
'RecRub+SP' were prepared with the pure water-reducing admixture at the same dosage
of 0.8%, by mass of cement.
The 'RecCon+SP' concrete was prepared using the recycled-concrete aggregate coming
from precasting plant as coarse aggregate; this aggregate fraction was combined at a
volume portion of 70% with 30% natural sand to enhance grain-size distribution
according to the Bolomey particle-size distribution curve. The same kind of mixture was
prepared with superplasticizer and the PC-type SRA at a dosage of 1.6%, by mass of
cement: in this case the concrete mixture is indicated as 'RecCon+PC-SRA'.
The 'RecRub+SP' concrete was prepared by using the recycled-rubble aggregate coming
from rubble recycling plant as coarse aggregate besides to natural gravel. Natural sand,
natural gravel, and recycled-rubble fractions were combined at 40%, 30%, and 30%,
respectively, by volume, for optimizing the grain-size distribution of the whole inert
fraction according to the Bolomey particle-size distribution curve. The same kind of
mixture was prepared using superplasticizer with RM-type SRA at a dosage of 2.0%, by
mass of cement: in this case the concrete mixture is indicated as 'RecRub+RM-SRA'.
SAMPLE PREPARATION AND CURING
Twelve cubic specimens (100-mm side) were cast for each concrete mixture, then wet-
cured at 10°C (natural ambient conditions) in order to evaluate compressive strength

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development after 1, 3, 7, and 28 days. For the four concrete mixtures where shrinkage-
reducing admixtures were employed, three other specimens were cast and cured at 1ooc
and relative humidity of 80%.
Three other prismatic specimens (1 00 x 100 x 500 mm) were cast for each concrete
mixture, wet cured for 2 days at l5°C (natural ambient conditions), then cured at the
same temperature and relative humidity of 65% (natural ambient conditions) up to 70
days in order to evaluate concrete drying shrinkage. In spite of the different laboratory
temperature and relative humidity, shrinkage testing was carried out according to the
procedure described in the Italian Standard UNI 6555-73 "Hydraulic Shrinkage
Determination".
EXPERIMENTAL RESULTS AND DISCUSSION
The results obtained for compressive strength tests carried out on wet-cured specimens
after 1, 3, 7, and 28 days are reported in Fig. 2. By comparing the 28-day compressive
strength of the three concretes prepared with the pure superplasticizer 'SP' it can be
noticed that the kind of aggregate used does not influence concrete strength. When the
other two chemical admixtures were used, slightly higher compressive strengths were
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
obtained for the PC type and slightly lower values for the RM type, although the
maximum difference detected was within 7 MPa.
The effect of curing condition, wet (100% R.H.) or humid air (80% R.H.), on
compressive strength of concrete containing SRA can be evaluated on the basis of results
reported in Table 4.
Drying-shrinkage
Free drying-shrinkage tests were carried out up to 70 days of curing at l5°C and relative
humidity of 65%. Results obtained are reported in Fig. 3. By comparing drying-shrinkage
of natural-aggregate concretes the effectiveness of the two superplasticizers incorporating
a shrinkage-reducing group can be evaluated: after 70 days concrete shrinkage was
decreased by 24% and 62% in presence ofRM-type SRA and PC-type SRA, respectively.
At the same curing time, Rongbing et al. (Rongbing and Jian 2005) found a 30%-40%
drying shrinkage reduction by means of SRA dosed at 2%, by mass of cement.
Concerning concrete prepared using either the recycled-concrete aggregate fraction or the
recycled-rubble fraction, the drying shrinkage was very low, less than 180 1-1rnlm after 70
days of testing. Actually, for the two concrete mixtures prepared with recycled aggregate
and SRA (i.e. 'RecCon+PC-SRA' and 'RecRub+RM-SRA'), values of drying shrinkage
less than 50 !lmlm were detected: after 70 days concrete shrinkage was decreased by 79%
and 73% in the presence of RM-type SRA and PC-type SRA, respectively, when
compared to the same concrete prepared with pure superplasticizer. The reason probably
lies on the positive effect of the preliminary water-soaking of recycled aggregate in

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reducing concrete shrinkage. This results in the formation of an internal water supply,
which is shown to be particularly effective in the presence of SRA.
CONCLUSIONS
In terms of compressive strength, the kinds of aggregate and superplasticizer (with or

without shrinkage reducing group) does not seem to influence compressive strength. It
should be reminded that recycled-concrete aggregate was added at a dosage of 70% of the
total amount of the inert fraction, while recycled-rubble aggregate at a dosage of 30% of
the total inert fraction.
The kind of curing, too, does not seem to influence compressive strength of concretes
prepared by using SRA, at least in the range 80%-100% ofre1ative humidity.
Concerning drying shrinkage, the two superplasticizers incorporating a shrinkage

reducing group were effective in reducing shrinkage, particularly the PC-type SRA which
allows more than 60% drying shrinkage reduction after 70 days of testing.
For the recycled-aggregate concretes the measured values of drying shrinkage were
always very low, less than 180 f,lmlm after 70 days of testing: the reason probably lies on
the positive effect of the preliminary water-soaking of the recycled aggregate fraction.
Values of drying shrinkage less than 50 f.tmlm were detected for the concrete prepared
with both recycled aggregate and SRA.
ACKNOWLEDGMENTS
The writers acknowledge the General Admixtures Spa ofPonzano Veneto, Treviso (Italy)
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for supplying chemical admixtures.
REFERENCES
Bentz, D.P., Geiker, M.R., and Hansen, K.K., 2001, "Shrinkage-reducing admixtures and
early-age desiccation in cement pastes and mortars", Cement & Concrete Research, V.
31, pp. 1075-1085.
Berke, N.S., Li, L., Hicks, M.C., and Bal, J., 2003, "Improving concrete performance
with shrinkage-reducing admixtures", Superplasticizers and Other Chemical Admixtures
in Concrete: Proceedings of the Seventh CANMETIACI International Conference, Berlin,
Germany, 2003 (SP-217), ed. V.M. Malhotra, American Concrete Institute, pp. 37-50.
Collepardi, M., 1991, Concrete Science and Technology (in Italian), Third Edition,
Hoepli, Milano, Italy, p. 301.
Collepardi, M., 2005a, "Admixtures: Enhancing Concrete Performance", Admixtures-

Enhancing Concrete Performances: Proceedings of the 61h International Congress on

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Global Construction: Ultimate Concrete Opportunities, Dundee, Scotland, 2005, ed. R.K.
Dhir, T.A. Harrison, and M.D. Newlands, Thomas Telford, London, U.K., pp. 217-230.
Collepardi, M., 2005b, "Chemical Admixtures Today", Concrete Technology for

Sustainable Development with Emphasis on Infrastructure: Proceedings of the Second
International Symposium, Hyderabad, India, 2005, ed. N. Bhanumathidas, and N.
Kalidas, pp. 527-541.
Collepardi, M., Borsoi, A., Collepardi, S., Ogoumah Olagot, J.J., and Troli, R., 2005,
"Effect of shrinkage reducing admixture in shrinkage compensating concrete under non-
wet curing conditions", Cement & Concrete Composites, V. 27, pp. 704-708.
Corinaldesi, V., and Moriconi, G., 2001, "Role of Chemical and Mineral Admixtures on
Performance and Economics of Recycled-Aggregate Concrete", Fly Ash, Silica Fume,
Slag and Natural Pozzolans in Concrete: Proceedings of the Seventh CANMETIAC1
International Conference, Madras, India, 2001 (SP-199), ed. V.M. Malhotra, American
Concrete Institute, pp. 869-884.
Corinaldesi, V., and Moriconi, G., 2002, "Rubble Processing to Manufacture Structural
Recycled-Aggregate Concrete", Cement and Concrete: Proceedings of the 5th
International Symposium, Shanghai, China, 2002, ed. Wang Pei-ming, Tongji University
Press, Volume 2, pp. 796-802.
Corinaldesi, V., and Moriconi, G., 2003a, "The Use of Recycled Aggregates from
Building Demolition in Self-Compacting Concrete", Self-Compacting Concrete:
Proceedings of the 3rd International RILEM Symposium, Reykjavik, Iceland, 2003 (PRO
33), ed. 0. Wallevik, and I. Nielsson, RILEM Publications S.A.R.L., France, pp. 251-
260.
Corinaldesi, V., and Moriconi, G., 2003b, "Recycled Aggregate Concrete under Cyclic
Loading", Role of Concrete in Sustainable Development: Proceedings of the
International Symposium dedicated to Professor Surendra Shah, Dundee, Scotland, UK.,
2003, ed. R.K. Dhir, M.D. Newlands, and K.A. Paine, Thomas Telford, London, U.K.,
pp. 509-518.
Corinaldesi, V., Tittarelli, F., Coppola, L., and Moriconi, G., 2001, "Feasibility and
Performance of Recycled-Aggregate Concrete Containing Fly Ash for Sustainable
Building Development", Sustainable Development of Cement and Concrete: Proceedings
of the Three-Day CANMETIACI International Symposium, San Francisco, US.A., 2001
(SP-202), ed. V. M. Malhotra, American Concrete Institute, pp. 161-180.
Dhir, R.K., Henderson, N.A., and Limbachiya, M.C., 1998, Use of Recycled Concrete
Aggregate, Thomas Telford Publishing, London, U.K., 525 pp.
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Folliard, K.J., and Berke, N.S., 1997, "Properties of High-Performance Concrete
Containing Shrinkage-Reducing Admixture", Cement & Concrete Research, V. 27, pp.
1357-1364.
Hansen, T.C., 1992, Recycling of Demolished Concrete and Masonry, Report of

Technical Committee 37-DRC on Demolition and Reuse of Concrete, RILEM Report 6,
E & FN Spon, London, U.K., 316 pp.
Hansen, T.C., and B0egh, E., "Elasticity and Drying Shrinkage of Recycled-Aggregate
Concrete", Technical Paper, ACI Journal, Sept-Oct 1985, pp. 648-652.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Kasai, Y., 1998, Reuse of Demolition Waste, Volume Two, Chapman and Hall, London,
U.K., pp. 500-774.
Maltese, C., Pistolesi, C., Lolli, A., Bravo, A., Cerulli, T., and Salvioni, D., 2005,
"Combined effect of espansive and shrinkage reducing admixtures to obtain stable and
durable mortars", Cement & Concrete Research, V. 35, pp. 2244-2251.
Nakanishi, H., Tamaki, S., Yaguchi, M., Yamada, K., Kinoshita, M., Ishimori, M., and
Okazawa, S., 2003, "Performance of a Multifunctional and Multipurpose Superplasticizer
for Concrete", Superplasticizers and Other Chemical Admixtures in Concrete:
Proceedings of the Seventh CANMETIACJJnternational Conference, Berlin, Germany,
2003 (SP-217), ed. V.M. Malhotra, American Concrete Institute, pp. 327-342.
Palacios, M., and Puertas, F., 2005, "Effect of superplasticizer and shrinkage-reducing
admixtures on alkali-activated slag pastes and mortars", Cement & Concrete Research,
v. 35, pp. 1358-1367.
Rongbing, B., and Jian, S., 2005, "Synthesis and evaluation of shrinkage-reducing
admixture for cementitious materials", Cement & Concrete Research, V. 35, pp. 445-448.
Table 1 - Physical properties of aggregate fractions

Water Specific gravity in SSD\"> Passing75 m
Fraction
absorption(%) condition (kglm1 sieve(%)
Natural sand 2.5 2640 0.9
Natural gravel 1.8 2660 0.0
Recycled concrete 6.3 2480 0.0
Recycled rubble 7.5 2340 0.0

SSD - saturated surface-dried

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,,,,```,-`-`,,`,,`,`,,`---
Table 2- Mixture proportioning of concrete made with natural-aggregate
Mixtures Nat+SP Nat+PC-SRA Nat+RM-SRA
Water/Cement 0.45 0.45 0.45
Water (kg/m3) 165 165 175
Cement (kg/m3) 365 365 390
Natural sand (kg/m3) 735 730 710
Natural gravel (kg/m3) 1100 1095 1060
Superplasticizin~ admixture
(kg/m)
3 - -
Superplasticizer with PC-type
SRA(kg/m3) - 6 -
Superplasticizer with RM-type
SRA(kg/m3) - - 8

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V'l
~
t.)
Q
~
::::1
Q)
_
... ...... _ -
Mixtures
~
.. -~ ·~ ~···~
RecCon+SP
a ~- -~••-• - - -
--- ···-· ·--
RecCon+PC-SRA
-·- - - --
RecRub+SP RecRub+RM-SRA
s::
tD
!!!.
Water/Cement 0.45 0.45 0.45 0.45 Q)
::::s
Q.
Water (kglm3) 165 165 165 175
3:
Cement (kglm3) 365 365 365 390
..,
0
Natural sand (kglm3) 550 545 735 710 -·n
0
::::s
Natural gravel (kglm3) - - 550 530 -·
Recycled concrete (kg/m3) 1195 1190 - -
Recycled rubble (kglm3) - - 485 465
-
Superplasticizing admixture (kglm3) 3 - 3
Superplasticizer with PC-type SRA (kglm 3

) - 6 - -
Superplasticizer with RM-type SRA (kglm3) - - - 8
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Table 4- Effect of curin~ on 28-day compressive strength of concretes prepared with SRA
Wet curing Humid air curing
Relative Humidity(%) 100 80
Temperature (°C) 10 10
Mixtures 28-day compressive strength (MPa)
Nat+PC-SRA 44.9 44.6
Nat+RM-SRA 42.0 42.3
RecCon+PC-SRA 48.5 49.8
RecRub+RM-SRA 42.1 44.9
100
[:r-c.- ~... ,..,. .~l!' ~I[ __~!]_,__
1*1:-nr. . . . ;
i
Natural sand
j
-+ R~cled ru~rv_j
---~ :
l .I,,
· I
I /i !,
1(:.: 1 ·+·····'·····
'} i
:
0 .btf
0.1
I I
il Jic
• '
1
Sieve opening (mm)
! !i
10
! I
100
Fig. 1- Grain-size distribution of various aggregates.
10 15 20 25 30
Curing time (days)
Fig. 2- Compressive strength versus curing time.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
300,-----------------------------------,
R,:iii8i+Si>-~
-o-
-D- Nat+RM-SRA
Nat+PC-SRA
I
_...RecCon+SP
..... RecCon+PC-SRA
_..,RecRub+SP
~,~·,~~ui!!-~M§.~I
400~----~------~------~----------~
0 20 40 60 80 100
Curing time at 1s•c and 65% R.H. (days)
Fig. 3- Free drying-shrinkage versus curing time.

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SP-239-36
Performance of Self-Consolidating
Concrete made with Diutan Gum
by K.H. Khayat, A. Mechaymech, and B. Skaggs

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Synopsis: Dynamic and static stability of self-consolidating concrete (SCC) affect the
production, transport, and overall performance of the concrete. Viscosity-modifying
admixtures (VMAs) are often incorporated to enhance the stability of SCC, especially in
the case of cast-in place concrete. The influence of a new type of polysaccharide, diutan
gum, on key characteristics of sec targeted for the construction and repair of concrete
infrastructure is examined. The investigation compares the performance of SCC made
with diutan gum and different types of high-range water reducing admixtures
(HRWRAs), including polynaphtalene sulphonate (PNS)-based and two polycarboxylate
polymer (PCP)-based HRWRAs. The effect of admixture combination on workability,
rheology, stability, and setting time was investigated. The robustness of optimized VMA-
HRWRA system and key durability parameters of the concrete were also determined.
Test results indicate that the use of diutan gum increases the plastic viscosity and yield
stress of SCC. Regardless of the VMA and HRWRA combination, the use of diutan gum
can significantly decrease segregation and bleeding, and lead to greater homogeneity of
the concrete during the dormant period of cement hydration. The performance of SCC
made with diutan gum depends on the type of PCP in use. Out of two PCP-based
HRWRA, one system resulted in lower HRWRA demand, increase in viscosity with the
increase in VMA content, and greater stability. The use of PCP and diutan gum is shown
to lead to adequate robustness where the sec can tolerate small changes in sand moisture
content without significant effect on sec properties. sec made with medium dosage of
diutan gum and PCP is shown to develop adequate air-void system and excellent frost
durability and resistance to de-icing salt scaling.
Keywords: admixture compatibility; frost durability; rheology; self-

consolidating concrete; stability; superplasticizer; viscosity-modifying
admixture

Provided by IHS under license with ACI 545 Licensee=UNI OF NEW SOUTH WALES/9996758001
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546 Khayat et at.
Kamal H. Khayat, F ACI, is Professor of Civil Engineering at the Universite de
Sherbrooke. He is a member of ACI committees 234, Silica Fume in Concrete; 236,
Material Science of Concrete; 237, Self-Consolidating Concrete; and 552, Geotechnical
Cement Grouting. His research interests include self-consolidating concrete, rheology,
and concrete repair.
A. Mechaymech is a Ph.D. candidate at the Universite de Sherbrooke, Quebec, Canada.

His research interests include use of specialty admixtures in self-consolidating concrete.
B. Skaggs is Principal Scientist at CP Kelco in San Diego, California. He is a member of

ACI and ASCE. His research interests include rheology, viscosity-modifying admixtures
for various construction based materials and industrial applications.
INTRODUCTION
Polysaccharides are high molecular weight, water-soluble organic polymers that can be
used to enhance the resistance to washout, bleeding, and segregation of cement-based
materials. Such viscosity-modifying admixtures (VMAs) play a key role in the
production of self-consolidating concrete (SCC), especially in the case of ready-mixed
concrete. Incorporating small dosage rates of VMA in SCC can enhance cohesiveness
and stability of the plastic concrete, as well as the robustness of the material. Greater
robustness refers to the ability of freshly mixed concrete to tolerate small changes in
material characteristics without adverse effect on workability. This includes changes in
concrete temperature, sand humidity and fineness modulus, and dosage rate of HRWRA.
Greater robustness can lead to more consistent and reliable daily production of the
concrete.
The increased yield stress of the concrete associated with the incorporation of VMA
necessitates an increase in high-range water-reducing admixture (HRWRA) demand.
Polysaccharides supplied as dry powdered materials are usually converted into liquid-
based suspensions to facilitate dispensing and ensure homogeneous dispersion of the
VMA during concrete mixing. Superplasticizers provide suitable suspension mediums for
polysaccharides. Such slurry medium should prevent the polysaccharide from hydrating
and must be selected to ensure adequate compatibility with the admixtures in use.
The mode of action of VMA depends on the type and concentration of the polymer, and
its performance depends on the type of the HRWRA used in the mixture. In this study,
the performance of a new type of polysaccharide, diutan gum, in enhancing the plastic
properties of SCC is investigated. Diutan gum is produced using a carefully controlled
aerobic microbial fermentation process utilizing a suitable carbon source. The backbone
is comprised of D-glucose, D-glucuronic acid, D-glucose, and L-rhamnose. The diutan
repeat unit contains two L-rhamnose units substituted on C3 of every 1-4-linked glucose
residue. The side chains shield the carboxylate group in the double-helix more completely
by hydrogen-bonding to the oxygen in the carboxylate group (1 ). This renders the
molecule unsusceptible to cation-mediated bridging (2). Van der Waals interactions of
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the side chain and backbone reduce the conformational freedom of the diutan molecules
(3). This stiffens the biopolymer molecular structure rendering it relatively insensitive to
temperature and pH, thus making the diutan gum suitable in high temperature
applications, systems with high pH, and high calcium ion concentrations, including
gypsum systems, cement grouts, mortars, and concrete.
Diutan rheological properties are defined by the conformation (chain shape) and
molecular weight (chain length), and tendency for the gum molecules to associate. The
chain conformation and molecular weight define the hydrodynamic volume swept out by
the molecule. One could relate conformation to the chain shape assumed in solution and
molecular weight to the chain length. The hydrodynamic volume and the tendency of the
molecule to associate with itself and neighboring molecules define the rheological
performance.
The influence of using diutan gum in SCC at various concentrations along with
polynaphtalene sulphonate (PNS)-based and polycarboxylate polymer (PCP)-based
HRWRAs is investigated in this study. The effect of admixture combination on HRWRA
demand, fluidity loss, stability of air volume, self-consolidating properties, and setting
time is evaluated. Similarly, the robustness of diutan gum used with a compatible
HRWRA is determined, and frost durability and de-icing salt scaling resistance of the
concrete are evaluated.
The testing program involved the evaluation of the effect of various VMA-HRWRA
combinations on fresh characteristics of SCC. Diutan gum was combined with different
types of superplasticizers: polynaphtalene sulphonate (PNS) and two polycarboxylate
polymers (PCP), referred to here as PCPl and PCP2. The SCC mixtures were
proportioned with 0.42 w/cm and 475 kg/m3 of blended cement. The diutan gum was
added at three concentrations of0.04%, 0.08%, 0.12%, by mass of water, and the dosage
rate of the HRWRA was adjusted to maintain a fixed slump flow consistency (665±15
mm). Given a w/cm of 0.42, these diutan gum concentrations correspond to 0.017%,
0.034%, 0.05%, by mass of binder. Such values can be considered as very low to medium
concentrations of the polysaccharide for use in sec.
The SCC mixtures were air-entrained to ensure initial air volume of 5% to 8% and were
tested to determine the retention of slump flow, air volume stability, rheological
properties, dynamic and static stability, and setting time. The robustness of SCC made
with diutan gum and PCPl was evaluated for ±10°C changes in concrete temperature and
±1% variations in sand humidity. The mixtures were tested to determine admixture
demand, workability, and compressive strength. The resistance to freezing and thawing
and to de-icing salt scaling ofSCC made with diutan gum and PCPl was also evaluated.
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548 Khayat et al.
MATERIALS
Blended cement containing Type 10 (GU) cement and substitutions of cement with 22%
Class F fly ash and 6% silica fume, by mass, was employed. The chemical and physical
properties of the binder components are given in Table 1. Continuously graded crushed
limestone aggregate with nominal size of 10 mm was used to facilitate the filling of
densely reinforced elements. The coarse aggregate has a specific gravity of 2.74 and
0.3% absorption. Well-graded siliceous sand was used. The sand has a specific gravity of
2.69, 1.22% absorption, and fineness modulus of2.40.
A polynaphtalene suphonate-based superplasticizer with 42% solid content and 1.21

specific gravity was used for the HRWRA. Two types ofpolycarboxylate-based polymers
were also used. The first, PCP I, is a polymer with a molecular mass of 20,000 to 30,000
and solid content of 32.4%. The second polycarboxylate-based polymer, PCP2, has 27%
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solid content and specific gravity of 1.08. Diutan gum was used in a dispersed solution of
8% concentration with each of the investigated HRWRA in order to facilitate dispending
and ensure better dispersion of the gum in concrete.
CONCRETE MIXING AND TEST METHODS
The concrete was mixed in an open pan mixer of 100-L capacity. The mixing sequence
consisted of homogenizing the sand and coarse aggregate for one minute in the mixer
before introducing one third of the mixing water. The cement was then added, along with
the HRWRA and the remaining water. After three minutes of mixing, the VMA diluted in
HRWRA was introduced, and the concrete was mixed for two additional minutes. The
temperature of the concrete during sampling was maintained at 20 ± 2°C, unless
otherwise specified. Following concrete mixing, the initial slump flow, concrete
temperature, unit weight, and air volume were determined. This was followed by
evaluating the passing ability, stability, and rheological parameters of the concrete. The
slump flow was determined immediately after mixing, which corresponded to
approximately 5 min of age. The remaining measurements were done between 5 and 15
min following the initial contact of cement with water. The characteristics of the fresh
concrete were again determined at the age of 70 minutes. The fresh concrete remained in
the mixer and was agitated for one minute at 10-min intervals.
The passing ability was evaluated using the J-Ring and L-box test methods. In both cases,
the gaps between the reinforcing bars were set to 35 mm. The filling capacity of the SCC
was evaluated using the caisson filling capacity test (4). The caisson test consists of an
acrylic box with dimensions of 300 x 500 x 300 mm with several closely spaced smooth
horizontal bars with clear spacing of 34 mm. The static stability of the concrete was
evaluated using the surface settlement and electrical conductivity tests. In the former test,
concrete is cast in a PVC column measuring 200 mm in diameter and 600 mm in height.
Settlement is monitored using an LVDT fixed on top of a thin acrylic plate anchored to
the upper surface of the concrete (5). The settlement is monitored until a steady state
condition is reached.

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The electrical conductivity approach was used to evaluate in-situ bleeding and
segregation of the concrete. The method is based on monitoring changes in electrical
conductivity occurring as a result of composition variations in the plastic material along a
given height of concrete sample (6). During the dormant period, the distribution of
electrical conductivity over the height of the test sample reflects the homogeneity of the
plastic concrete. In a qualitative way, this homogeneity can be related to bleeding and
segregation. Segregation may be defined as the precipitation and sedimentation of solids,
accompanied by the migration of liquids through percolation. An increase in the
concentration of electrolytes within the interstitial solution promotes an increase in
conductivity. This concentration exists between the four pairs of electrodes in this test
(top, 2nd pair, 3rd pair, bottom). A reduction in conductivity of the bottom electrode is an
indication of segregation. Further description of the test method and interpretation of
electrical conductivity values are described in references 6 and 7.
The rheological parameters were determined using a modified Tattersall two-point

workability rheometer, MK III version. An H-shaped impeller rotating in a planetary
motion is used. The testing protocol consists of gradually increasing the mixing speed to
a maximum velocity. Subsequently, the testing speed is reduced in predetermined steps
varying from 0.6 to 0.1 rev/sec, and the required torque to shear the material at each
speed is recorded. The data are used to derive the rheological parameters assuming a
Bingham fluid model.
TEST RESULTS AND DISCUSSION
Tables 2 to 4 show the mixture proportioning and properties of the investigated SCC. The
mixtures had w!cm of 0.42, binder content of 475 kg/m3 , and fixed sand/(sand +
aggregate) ratio of 0.50, by volume. The dosage rates of the HRWRA and air-entraining
admixture (AEA) were adjusted to secure initial slump flow and air volume of 665 ± 15
mm and 6.5 ± 1.5%, respectively.
HRWRA demand
The influence of diutan gum on HRWRA demand is illustrated in Fig. 1. SCC made with
PNS necessitated greater HRWRA demand than similar concrete made with PCP,
regardless of the VMA content. The two reference mixtures made without any VMA had
the lowest HRWRA demand; the reference mixtures prepared with PNS and PCP2 had
HRWRA demands of 6.9 and 2.1 L/m3 , respectively (Tables 2 to 4). The combination of
PCP and diutan gum led to considerably lower HRWRA demand than similar concrete
made with PNS and diutan gum. For example, the PNS and PCPI and PCP2 mixtures
made with 0.08% diutan gum had HRWRA demand of 9.5, 4.0, and 5.4 Llm3,
respectively.
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550 Khayat et al.
The increase of the concentration of diutan gum from 0.04% to 0.08%, by mass of water,
necessitated greater HRWRA demand, regardless of the HRWRA type. Further increase
in VMA dosage to 0.12% did not increase the PCP2 demand. This was not the case for
the PCP! HRWRA, despite the lower level of slump flow consistency. The HRWRA
demand of the mixtures made with PCP I and different VMA concentrations were 0.3 to
1.3 L/m3 lower than similar mixtures made with PCP2. Compared to PCP-based
HRWRA, the use of PNS-based HRWRA resulted in lower loss in slump flow
consistency. SCC made with PNS-based HRWRA and diutan gum had better fluidity
retention compared to concrete made with PCP-based HRWRA and diutan gum. In the
case of SCC without diutan gum, the concrete made with PCP2 had the highest level of
slump retention.
Rheological parameters
Table 5 summarizes the rheological parameters of the investigated mixtures. The torque-
angular velocity data are plotted to fit the Bingham model. The correlation coefficients of
the derived linear relationships were greater than 0.99. Despite similar slump flow values
of 665 ± 15 mm, some variations were obtained for the apparent yield stress values (g) of
the various mixtures. The initial values of g varied from 0.3 to 1.0 N.m for all mixtures,
regardless of the VMA-HRWRA combination. The torque plastic viscosity (h) values at
10 min ranged between 3.3 and 12.6 N.m.s. The highest viscosity was obtained in the
case of the SCC made with 0.04% diutan gum. For the mixture made with PNS and
0.04% of diutan gum, the h value was high. The lowest viscosity values were obtained
with the sec proportioned with the mid concentration of diutan gum of 0.08% in
mixtures made with PCP2- and PNS-based HRWRA.
Figure 2 shows the effect of increasing VMA dosage on h of SCC made with different
HRWRA types determined at 10 and 70 minutes. It is important to note that the dosage of
the HRWRA was adjusted to maintain constant slump flow of 665 ± 15 mrn. The
reference non-VMA concrete made with PCP 1 also exhibited slightly greater torque
plastic viscosity than that made with PNS or PCP2. Regardless of the HRWRA type, the
increase in diutan gum from 0 to 0.04% led to higher plastic viscosity compared to non-
VMA mixtures. At low gum concentration of 0.04%, the highest viscosity was obtained
for concrete made with PNS, both at 10 and 70 minutes of age. With the increase in VMA
content to 0.08% and 0.12%, a further increase in viscosity was obtained for the sec
made with PCPl-based HRWRA. The increase ofVMA content to 0.08% and 0.12% in
the case of concrete made with PNS or PCP2 resulted in reduction in viscosity, both at 10
and 70 minutes. This can be due to the high concentration of HRWRA required in the
mixtures compared to the SCC made with PCP!. In other words, the effect of HRWRA
was more dominant compared to that of the diutan gum used at 0.08% and 0.012%
dosage rates. Furthermore, mixtures made with 0.08% and 0.12% diutan gum had for the
most part 1.5% to 2% greater air volume than those made with 0.04% diutan gum and
PNS or PCP2; the increase in air volume contributes to the reduction in viscosity.
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Passing ability and filling capacity
The results of the L-box, J-Ring, and caisson filling capacity tests are presented in Tables
2 to 4. The increase in L-box blocking ratio (h2/hl), J-Ring spread diameter, and filling
capacity reflect an increase in passing ability and resistance to blockage of concrete flow
among closely spaced obstacles. The reference non-VMA mixtures had h2/hl values of
0.74 to 0.90. The incorporation ofVMA at low and medium concentrations led to a slight
increase in passing ability; however, further increase in VMA content to 0.12% led to
some reduction in blocking ratio, especially in the case of the PCPl HRWRA that
exhibited the highest viscosity level.
The spread between slump flow and J-Ring flow values are given in Tables 2 to 4 and
varied from 0 to 80 and 0 to 60 mm after 10 and 70 minutes, respectively. In general,
spread between non-restricted slump flow and restricted J-Ring flow values lower than 50
mm would correspond to adequate passing ability. The increase in VMA concentration
resulted in lower spread between the slump flow and J-Ring flow values at 10 and 70
minutes. The filling capacity ranged between 85% and 99% at 10 min and 61% and 98%
at 70 minutes. In general, filling capacity values greater than 80% would yield adequate
performance for the filling of highly restricted section (5). Compared to reference SCC
made without any VMA, the increase in diutan gum content is shown to enhance the
filling capacity of the SCC, regardless of the HRWRA type, both at the age of 10 and 70
minutes.
Static stability
Surface settlement is affected by consolidation of the plastic concrete. Such stability

depends on the viscosity of the mixture and length of the dormant period. Concrete with
prolonged dormant period could present greater risk of segregation. The effect of VMA
dosage and VMA-HRWRA combination on surface settlement is illustrated in Fig. 3. The
maximum settlement varied between 0.1% and 0.7%. The incorporation ofVMA led to a
reduction in settlement, especially in the case of concrete made with PCPl. Combination
of diutan gum at 0.04% with PCPl or PCP2 yielded the lowest settlement; these mixtures
also had relatively high levels of viscosity. The non-VMA concrete made with PCPl had
greater settlement than similar concrete made with PNS or PCP2. For mixtures containing
diutan gum, SCC made with PNS exhibited greater surface settlement than similar
concrete proportioned with PCP-based HRWRA. This can be due to the higher demand
ofHRWRA in the former concrete, which can prolong the dormant period.
The stability indices determined from electrical conductivity of SCC made with PNS and
PCP2 are given in Table 6. Based on the conductivity data, it is possible to define
stability indices that determine the evolution of bleeding and segregation of the fresh
concrete (7). The bleeding index is taken here as the cumulative area between
conductivity values of the top electrode pair and the second pair. This area is considered
between the initial and peak values, divided by the effective time required to reach the
peak value. The segregation index is defined as the cumulative area between the bottom
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552 Khayat et at.
pair of electrode and mean of conductivity of all electrode pairs, considered between the
initial and peak values, divided by elapsed time required to reach the peak value. Finally,
the homogeneity index is defined as the cumulative area between the mean of top two
pairs and mean of bottom two pairs considered from the initial value to the peak values
divided by the elapsed time required to reach the peak value. A perfectly homogenous
system would yield bleeding, segregation, and homogeneity indices nearing zero.
In general, SCC mixtures made with either PNS or PCP2 exhibited low stability indices,
which reflect the stable nature of the selected SCC. These mixtures had maximum surface
settlement values lower than 0.5%. For SCC made with PNS, the increase in
concentration of the diutan gum led to sharp decrease in bleeding index nearing zero at
0.12% gum content. Similarly, the increase of diutan gum from 0 to 0.08% resulted in
sharp reduction in segregation and homogeneity indices. However, such added stability
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was not observed when the gum concentration increased to 0.12%. This is believed to be
due the high content of PNS-based HRWRA that was 11.3 Llm3 . The bleeding and
segregation indices were similarly affected by the type of the HRWRA. In the case of
SCC prepared with PCP2, the increase in diutan gum concentration from nil to 0.08% led
to some increase in the bleeding, segregation, and homogeneity indices. Again, this could
be related to the greater HRWRA demand that increased from 2.1 to 5.3 L!m3 . The
increase in VMA content to 0.12% did not necessitate any additional HRWRA demand
and resulted in about 50% reduction in stability indices compared to the sec made
without any VMA.
Stability of air
As shown in Table 2, the AEA dosage of concrete made with PNS dosage and VMA was
similar to that of the reference non-VMA concrete. On the other hand, the incorporation
of diutan gum necessitated very large increase in AEA in mixtures made with PCP. For
example, the required AEA dosage increased from 50 to 500 ml/m3 with the addition of
0.04% diutan gum in order to maintain the targeted initial air volume of 5% to 8%. This
is thought to be due to the increase in HRWRA demand, and hence increase in
concentration of de-foamer making it more difficult to air-entrain the sec at
conventional dosage rates of the AEA.
As mentioned earlier, the concrete was subjected to occasional agitation in the mixer for
60 min before the second set of testing. The SCC made with PNS exhibited 0.7% to 3.5%
loss in air volume, with the upper values obtained with mixtures made with the higher
VMA contents. Concrete proportioned with PCPl exhibited stable air content between 10
and 70 min, except in the case of the PCPl + 0.12% Diutan where the air content
increased by 2.4% with the occasional agitation. The reference PCP2 concrete had also
stable air content; however, the incorporation ofVMA resulted in 2.0% to 4.5% increase
in air volume between 10 and 70 minutes. Therefore, care must be taken in selecting the
HRWRA type that would not lead to excessive increase in air volume in SCC made with
diutan gum.

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Setting time
The initial setting time of mixtures made with PNS and PCP2 are shown in Fig. 4. The
initial setting time ranged from approximately 7.5 to 14.5 hours, and the final setting time
varied from approximately 8 and 16 hours. For SCC incorporating PCP2, the increase of
diutan gum from nil to 0.08% or 0.12% resulted in an increase in HRWRA demand from
2.1 to 5.3 Llm3 as well as a delay of 6.5 hours in initial setting time. In the case of SCC
made with PNS-based HRWRA, an increase in diutan gum from 0 to 0.08% resulted in a
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delay of 3.5 hour in initial setting. Further increase in gum content to 0.12% resulted in
further delay of 3.5 hours in initial setting. As discussed earlier, the increase in diutan
gum concentration resulted in an increase in the PNS-based HRWRA demand from
approximately 7 to 11 L!m3 • The higher PNS content can prolong the dormant period.
Robustness of optimized VMA-HRWRA combinations
Based on the above results, liquid-based VMA containing diutan gum and PCP!
HRWRA was prepared for further investigation. The admixture was used at medium
dosage to proportion air-entrained SCC. Five SCC mixtures were prepared with diutan
gum and PCP! to evaluate the robustness to changes in concrete temperature (± l0°C)
and sand moisture content that deviate ± 1% from surface saturated dry condition (SSD).
Achieving robust concrete is quite important since the conditions on the building site vary
frequently, thus affecting water demand, changes of self-consolidating properties,
kinetics of cement hydration, air entrainment, and stability.
Tables 7 and 8 present the mixture proportioning and test results of the SCC evaluated for
robustness investigation. In order to produce concrete of 32°C, the coarse aggregate,
sand, and cement were stored at 38°C for 24 hours before mixing, and the mixing water
was heated to 42°C. For the concrete prepared at l2°C, material constituents were
maintained at 5°C, and small quantities of crushed ice were employed to replace part of
the mixing water. The HRWRA and AEA were diluted with half of the mixing water. The
mixing sequence was the same as that described earlier.
Effect of sand moisture on robustness
The optimized PCP! + 0.08% Diutan mixture proportioned at SSD showed good
workability and homogeneity at 10 and 60 minutes. The slump flow and filling capacity
values were 675 mm and 99% at 10 min, and 700 mm and 95% at 60 minutes. The torque
plastic viscosity (h) values were 6.8 and 5.2 N.m.s at 10 and 60 min, respectively. The
demand of the PCP! HRWRA in the reference SCC was 4.0 L/m3 •
An increase in sand moisture of+ 1% resulted in additional water (w!cm of 0.44) and an
increase in slump flow of 45 mm without much difference in filling capacity and initial
air content. With the higher slump flow, the SCC with the higher water content exhibited
lower apparent yield stress (g) of 0.2 at 10 and 60 minutes. Regardless of the sand

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554 Khayat et at.
humidity(± 1%), the surface settlement of the sec was quite low at 0.16% to 0.20%.
Despite the higher effective wlcm of the SCC made with sand at+ 1% humidity (wlcm of
0.44 vs. 0.42 for the concrete prepared at SSD), approximately 8% greater compressive
strength was obtained after 28 and 56 d of age compared to the reference concrete
prepared at SSD. The difference in compressive strength is believed to be due to the
spread in air content between the two concrete mixtures. At the time of sampling of
cylinders for compressive strength testing, the concrete made with SSD and + 1% sand
humidity had air contents of 9% and 7.5%, respectively. This can account for the spread
in compressive strength results. Beyond the difference in air content, the increase in sand
humidity did not appear to have a negative effect on compressive strength.
A reduction in the quantity of water that is equivalent to -1% of sand moisture (wlcm of
0.40) caused an increase of2.6% in air content (total air content of 10%) at 10 min and of
2% (from 9% to 11 %) at 60 minutes for a fixed dosage of AEA. The slump flow value
was identical to the mixture at SSD. The torque plastic viscosity (h), filling capacity, and
24-hour compressive strength values were nearly identical to those of the reference sec.
Small increase in settlement (0.2%) was noted. The 28-d and 56-d compressive strength
results of the SCC made with -1% sand humidity are omitted due to experimental error.
Overall, SCC made with PCP1 and diutan gum exhibited good robustness to small
changes in sand moisture where variations in sand humidity of ±1% did not seem to have
much effect on the self-consolidating properties of the concrete (filling ability, filling
capacity, and stability). With the decrease in sand humidity, an increase in air content of
approximately 2.5% was obtained. Care must be taken to adjust the dosage of the AEA to
maintain the air volume within the targeted range.
Effect of temperature on robustness
Compared to the reference SCC at 22°C, the decrease in concrete temperature to l2°C,
without changing the HRWRA content, had limited effect on slump flow at 10 and 60
minutes. The colder concrete developed lower settlement of 0.1 0%. On the other hand,
the volume of air of 9% at 10 and 60 min was higher than the reference SCC. The filling
capacity was nearly 100% at both 10 and 60 min and was slightly greater than that
obtained for the reference concrete. The torque plastic viscosity (h) values were 5.6 and
4.2 N.m.s at 10 and 60 min, respectively, which were approximately 1 N.m.s lower than
those of the control sec at 22°C.
For the second mixture prepared with the PCP1 + 0.08% diutan at 32°C, the slump flow
at 10 min was 710 mm and underwent a loss of 20 mm after 60 min, which is not the case
for the remaining mixtures made with this HRWRA-VMA combination. This loss caused
an increase in yield stress; the measured value at 10 min is 0.4 N.m, and this value
increased to 0.7 N.m at 60 minutes. Compared to the two other mixtures (cold and SSD
state), the hotter mixture showed slightly higher settlement (0.23%), which is still
considered as stable SCC. Its 24-hour compressive strength was 3.9 MPa. The air volume
was 8.9%, which was slightly greater than that at 22°C (7.4%). This volume was 9.5% at
60 minutes. The 28-d and 56-d compressive strengths of the concrete made with l2°C
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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`,,,``````,,,,```,-`-`,,`,,`,`,,`---
and 32°C were similar to those made with 22°C. Small variations in compressive strength
are mainly due to differences in air content between the various mixtures.
Frost durability and scaling resistance ofSCC made with diutan-PCP 1 combination
Given the good performance of SCC made with diutan gum and the PCPI HRWRA,
further investigation was carried out to determine the frost durability and de-icing salt
scaling for SCC made with PCPI and 0.08% diutan gum. The air-void system of the
hardened concrete was determined using I 00 x 200 mm cylinder in accordance with
ASTM C 457, Modified Point Count method. The air content of samples taken at 10 min
of age and after 60 min (concrete subjected to occasional agitation) were 7.4% and 9.0%,
respectively, in the fresh state; these values were 7.0% and 7.8%, respectively, in the
hardened state. The spacing factor values of the concrete sampled at lO and 60 min were
225 and 170 J..lm, respectively. Frost durability testing (ASTM C666, Procedure A)
revealed excellent resistance to freezing and thawing with 100% durability coefficient
and elongation of 120 ,. un!m after 300 cycles of freezing and thawing (Table 9). Two
square samples measuring 500 cm2 each were prepared for each concrete mixture to
determine the de-icing salt resistance. The samples were water-cured for 14 days,
followed by 14 days of air-drying, and 7 days of immersion in salt-saturated solution, in
accordance to the Quebec Concrete Standards (BNQ). The freezing and thawing cycles
were started at 35 days of age. The samples were subjected to one freeze-thaw cycle per
day, 16 hours of freezing at -18°C and 8 hours of thawing at 23 °C. In total, 50 cycles of
freezing and thawing were applied to determine the resistance of the concrete to de-icing
salt scaling. The cumulative mass loss of the PCPI + 0.08% diutan concrete was limited
to 250 g/m2 (Table 9), which is quite low considering the highly fluid nature of the
concrete.
CONCLUSIONS
The influence of different combinations of diutan gum and HRWRA on key properties of
SCC designed for construction and repair of concrete infrastructure is examined. The
concrete was air-entrained with 0.42 w/cm and contained 475 kg/m3 of ternary cement.
Based on the above results, the following conclusions are warranted:
I. Good compatibility is observed between diutan and PNS-based HRWRA and the two
PCP-based HRWRAs. The HRWRA demand and workability characteristics of the
SCC is shown to depend on the selected HRWRA and dosage of the VMA.
2. Regardless of the VMA concentration, concrete incorporating PCP-based HRWRA
necessitated lower HRWRA demand than that made with PNS. The HRWRA
demand was the lowest in the case of the PCP-I HRWRA.
3. Increase in diutan gum concentration led to greater HRWRA demand, especially in
the case ofSCC made with PNS-based HRWRA.
4. At a given slump flow consistency, the increase in diutan gum is shown to increase
plastic viscosity without significant change in yield stress; the latter is due to the

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556 Khayat et al.
increase in HRWRA dosage to maintain a given slump flow consistency. The highest
torque viscosity was obtained with concrete made with PCPl and 0.08% diutan gum.
At low gum concentration of 0.04%, the highest viscosity was obtained in the case of
concrete prepared with PNS-based HRWRA.
5. Despite the adequate stability and resistance to blockage of the reference SCC made
without any VMA, SCC made with low concentrations of diutan gum (0.04%, by
mass of water) led to higher levels of passing ability and filling capacity.
6. Regardless of the HRWRA type, the increase in the dosage of diutan gun resulted in
significant increase in static stability. SCC made with diutan and PCPl exhibited the
lowest level of surface settlement.
7. Stability indices determined from electrical conductivity are shown to decrease with
the increase in diutan gum content in SCC made with PNS, which reflects the greater
level of resistance to bleeding and segregation. For SCC made with PCP2, initial
increase in diutan gum content to 0.08% led to some increase in these indices (lower
stability); this is thought to be related to the considerable increase in HRWRA
demand. Further increase in diutan gum to 0.12% led to considerable enhancement in
stability.
8. SCC made with diutan gum and PNS did not exhibit considerable increase in AEA
demand. On the other hand, mixtures made with PCP and diutan gum necessitated a
fivefold increase in AEA demand compared to non-VMA concrete.
9. Occasional agitation of the SCC for 60 min resulted in some air loss for mixtures
made with PNS. Concrete made with PCP-based HRWRA and no VMA exhibited
stable air content. However, with the use of diutan gum, especially at high dosage
rate of the VMA and the HRWRA to maintain constant slump flow consistency,
considerable increase in air volume was observed following agitation.
10. The coupled effect of VMA-HRWRA delays considerably the setting time,
especially at higher VMA contents.
11. SCC made with PCP 1 and diutan gum demonstrated good robustness vis-a-vis small
changes in sand moisture content and temperature.
12. The optimized PCP1 and diutan gum had adequate air-void system and resulted in
excellent frost durability and de-icing salt scaling resistance.
REFERENCES
1. Cesaro, A., Gamini A., and Navarini, L. "Supramolecular Structure of Microbial
Polysaccharides in Solution: from Chain Conformation to Rheological Properties,"
Polymer, Vol. 33, No.l9, 1992, pp. 4001-4008.
2. Rakitsky, W.G., "Suspending Agent Applications in Cementitious Systems,"
ConChem International Exhibition & Conference, Karlsruhe, Germany, 1993.
3. Talashek, T.A., and Brant, D.A. "The Influence of Side Chains on the Calculated
Dimensions of Three Related Bacterial Polysaccharides," Carbohydrate Research,
1987, Vol. 160, pp. 303-316.
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4. Yurugi, M., Sakata, N., Iwai, M., and Sakai, G., "Mix Proportion for Highly
Workable Concrete," Proceedings, Concrete 2000, Dundee.
5. Khayat, K.H., "Workability, Testing and Performance of Self-Consolidating
Concrete," ACI Materials Journal, Vol. 96, No.3, 1999, pp. 346-353.
6. Pavate, T.V., Khayat, K.H., and Jolicoeur, C., "An In-Situ Conductivity Method for
Monitoring Segregation, Bleeding, and Strength Development in Cement-Based
Materials," ACI SP 195, 6th CANMET/ACI Int. Conference on Superplasticizers and
Other Chemical Admixtures in Concrete, Nice, France, October 2000, Ed. Malhotra,
M., pp. 535-559.
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7. Khayat, K.H., Pavate, T., Assaad, J., and Jolicoeur, C., "Analysis of Variations in
Electrical Conductivity to Assess Stability of Cement-Based Materials," ACJ
Materials Journal, Vol. 100, No.4, 2003, pp. 342-350.
Table 1 - Chemieal and physieal properties of eement, fly ash, and sitiea fume used
in this investigation
Type GU cement Silica fume Fly ash
Si02,% 21.0 93.6 41.9
Ah03,% 4.2 0.3 23.43
Fe203,% 3.1 0.5 18.89
CaO,% 62.0 0.3 7.11
MgO,% 2.9 0.5 0.86
Na20eq.,% 0.74 1.4 1.57
S03,% 2.7 - -
C3S,% 52 - -
C2S,% 21.5 - -
C3A,% 5.7 - -
c~,% 9.5 - -
Blaine specific surface, m2/kg 420 - 410
Surface area B.E.T., m2/kg - 20,250 -
Specific gravity 3.17 2.22 2.53
Percent passing 45 11m, % 95 IOO 90
Bulk unit weight, kg/m3 3150 280 -
L.O.I.,% 2.5 2.8 2.97

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558 Khayat et al.
Table 2 - Mixture proportioning and results of SCC made with diu tan gum aud
PNS
~~ t;~
zo tJgga J) ~ .2
S:> ~C!i
0
" ~0~ ~;;;o
Cement kglm' 475 475 475 475

Sand kglm' 774 777 777 777
Coarse aggregate kglm' 802 804 801 801
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Water kglm' 199.5 199.5 199.5 199.5
PNS-based HRWRA Um' 6.9 7.0 10.0 11.3
AEA mllm' 750 600 700 800
Diutangum g/m' 0 80 160 240
Temperature 10min ·c 21 21.8 21.8 21.9
Unit weight lOmin kglm3 2206 2240 2191 2202
Entrained air lOmin % 6.8 6.2 8.5 8.0
content 70min % 6.1 5.5 5.0 6.2
10min mm 650 680 690 660
Slump flow
70min mm 520 680 665 680
10min nun 620 680 680 610
J-Ring
70min nun 500 620 660 680
Slump flow- 10min mm 30 0 10 50
J-Ring 70min mm 20 60 5 0
lOmin sec 0.53 3.10 1.69 2.69
h2/h1 0.90 0.90 0.88 0.74
L-box
70min sec 1.44 4.01 1.31 2.7
h2/h1 0.54 0.81 0.73 0.8
10min % 90.0 98.5 97.2 93.7
Filling capacity
70min % 61.1 98.1 95.5 97.0
Max. settlement % 0.51 0.4 0.3
Initial hr 7:20 - 10:45 14:15
Setting time
Final hr 8:10 - 12:20 15:45

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Table 3 -Mixture proportioning and resnlts of SCC made with diutan gum and
PCP I
0
~.a .:t
<=...:
0:~ "-'00
00 .2
~~ -~
6~ (.)"<t ~0~ u-:O
""475 ""0 ""0
Cement kglm' 475 475 475

Sand kglm' 777 776 773 776
Coarse aggregate kgim' 804 803 800 802
Water kglm' 199.5 199.5 199.5 199.5
PCPIHRWRA Lim' 2.1 3.0 4.0 5.0
AEA mllm' 10 90 1330 1330
Diutangum glm' 0 80 160 240
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
Temperature IOmin oc 19.6 20.7 20.0 20.7
Unit weight 10min kglm' 2277 2063 2002 2206
Entrained air 10min % 5.5 10 10 7.6
content 70min % 4.8 10 10 10.0
lOmin mm 655 675 660 650
Slump flow
70min mm 540 650 580 590
lOmin mm 635 600 640
J-Ring
70min mm 620 540 580
Slump flow- 10min mm 40 60 10
J-Ring 70min mm 30 40 10
lOmin sec 0.93 3.22 6.41 4.53
h2/hl 0.74 0.82 0.82 0.75
L-box
70min sec 1.00 3.68 9.00 5.00
h2/hl 0.74 0.85 0.52 0.6
lOmin % 88.3 94.4 91.6 91.0
Filling capacity
70min % 73.4 92.8 69.8 78.3
Max. settlement % 0.70 0.11 0.16 0.40

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s6o Khayat et al.
Table 4 - Mixture proportioning and results of SCC made with diu tan gum and
PCP2
.=
~'if:.=
0
~~ ~~ s:!ooo
uo
~~do
~·=
~ ~~ Po.
Cement kgfm' 475 475 475 475
Sand kgfm' 790 777 776 776

Coarse aggregate kgfm' 790 803 803 803
Water kgfm' 199.5 !99.5 199.5 199.5
PCP2HRWRA Um' 2.1 3.6 5.3 5.3
AEA mllm' 50 500 700 500
Diutangum gfm' 0 80 160 240
Temperature 10 min •c 22 22.4 23 -
Unit weight 10min kgfm3 2268 2181 2169 2193
Entrained air lOmin % 5.6 7.5 9.0 7.9
content 70min % 5.0 12.0 11.0 10.9
10min mm 650 680 680 680
Slump flow
70min mm 600 625 660 640
10min mm 570 655 670 640
J-Ring
70min mm 540 590 620 620
Slump flow- 10min mm 80 25 10 40
I-Ring 70min mm 60 35 40 20
10min sec 0.78 3.75 1.84 2.18
h2/h1 0.81 0.9 0.93 0.86
L-box
70 min sec 0.81 5.00 2.28 3.31
h2/hl 0.59 0.72 0.89 0.76
10 min % 84.8 96.1 97.2 96.0
Filling capacity
70min % 76.0 86.6 93.2 91.9
Max. settlement % 0.49 0.2 0.27 0.23
Setting time
Initial hr 08:05 - 14:25 14:15
Final hr 09:20 - 15:55 16:00
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Table 5 -Rheological parameters of investigated mixtures
10 min 70min
Mixtures
g(N.m) h (N.m.s) R2 g(N.m) h(N.m.s) R2
PNSnoVMA 0.3 3.3 0.994 0.6 4.2 0.988
PNS+
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
0.62 12.6 0.993 0.76 11.0 0.992

0.04%Diu
PNS+
0.6 6 0.994 0.6 7.2 0.988
0.08%Diu
PNS+
0.7 7.6 0.996 0.7 7.4 0.990
0.12%Diu
PCPlnoVMA 0.3 5.2 0.992 0.6 5.6 0.998

PCP!+
1.0 7.4 0.998 1.2 6.0 0.997
0.04%Diu
PCP I+
0.6 15 0.994 1.3 13.1 0.998
0.08%Diu
PCP!+
0.7 12.3 0.994 1.l 12.5 0.994
0.12%Diu
PCP2noVMA 0.8 4.2 0.993 0.8 4.6 0.992

PCP2+
0.8 8.8 0.996 1.6 6.5 0.995
0.04%Diu
PCP2+
0.6 5.2 0.998 0.8 4.9 0.996
0.08%Diu
PCP2+
0.4 6.6 0.992 0.8 5.6 0.998
0.12%Diu
Table 6 - Stability indices of evaluated mixtures determined from electrical

conductivity tests
Segregation Homogeneity
Mixtures combinations Bleeding index
index index
noVMA 0.17 0.11 0.16
PNS 0.08%Diu 0.08 0.03 0.05
0.12% Diu 0 0.11 0.12
noVMA 0.06 0.13 0.10
PCP2 0.08%Diu 0.15 0.30 0.45
0.12% Diu 0,03 0.06 0.08

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0\
N
="
:r
~
--
tD
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D)
Table 7 -Mixture constituents used for robustness evaluation of SCC made with diutan gum and PCPl HRWRA
r
SSD mixture temp. Sand humidity Effect of temperature
Units 22°C +1% -1% l2°C 32°C
w/cm 0.42 0.438 0.404 0.42 0.42
Water Urn' 200 208 192 200 200
3 475 475 475 475 475
Binder kg/m
Coarse aggregate kg!m' 800 800 800 800 800
Sand kg/m 777 769 785 777 777
PCPlHRWRA Lim' 4.0 4.0 4.0 4.0 4.0
Diutan gum - 0.08% glm' 160 160 160 160 160
Set retarder 0.75 0.75 0.75 0.75 0.75
Llm3
AEA 0.10 0.10 0.10 0.10 0.10
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Copyright American Concrete Institute en
c
"C
tD
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"C
Results
Table 8- Results of robustDess investigation of SCC made witll di111Dn gum and PCI'l HRWRA
SSDmixture Sand humidity Effect of temperature

-
Dr
(It
;::;·
N.
tD
Units
temp. 22°C +1% -1% I2°C 32°C ~
IOmin 21.7 21.6 22.2 13.6 32.1
Temperature oc Q)
60min 21.5 21.1 21.8 16.9 29 ::s
IOmin 675 720 670 680 710 0.
Slump flow mm
60min 700 720 680 720 690 n
Unit weight kg!m'
10min 2163 2149 2086 2115 2134 ::s"
60min 2137 2208 2046 2093 2091 tD
Entrained air IOmin 7.4 7.5 10.0 9.0 8.9 3
content
%
;::;·
-~
60min 9.0 7.2 11.0 9.0 9.5
lOmin 98.8 99.4 97.6 99.6 98.8 Q)
Filling capacity %
60min 95.3 99.6 97.0 99.6 99.8
g,N.m 0.4 0.2 0.6 0.4 0.4
h, N.m.s IOmin 6.8 5.6 6.6 5.6 5.8
Rbeological R' 0.994 0.999 0.998 0.998 0.995 3
parameters g, N.m
h, N.m.s 60min
0.4
5.2
0.2
4.6
0.6
4.9
0.4
4.2
0.7
4.6
8."
c
R' 0.996 0.998 0.998 0.998 0.998 ;
Max. settlement % 0.16 0.18 0.2 0.10 0.23 (It
Compressive
strength
MPa
I day
28days
2.1
36.2
3.3
39.0
2.2
-
2.9
34.7
3.9
38.1
-·
::s
56 days 41.0 44.5 37.8 40.0
~
::s
n
til
;-
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U'l
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564 Khayat et al.
Table 9 - Frost durability and de-icing salt scaling of SCC made with 0.08% diu tan gum and PCPI HRWRJ
Fresh air content (%) !Omin 7.4

60min 9.0
Hardened air content(%) !Omin 7.0
60min 7.8
Spacing factor (J.lm) !Omin 220
60min 170
Freeze-thaw cycles Durability factor
Elongation (&/Lo)
(%)
0 0 100
56 42 95
102 40 98
143 62 100
187 70 100
213 70 100
251 88 100
282 96 100
320 122 100
De-icing salt scaling cycles Visual code Mass loss (glm2)
0 0 0
5 I 78
10 I 92
15 1 110
25 1 140
56 1 252
700 - Slump flow (mm) - - SP demand (L/m3)
690
I 680
~ 670
<+::
j 660
U'l
650
640
630
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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--
-+----PCP1(10min) _._PCP2(10rnin) -.-PNS(10min)
16 -- *-- PCP1 (70 min) --0-- PCP2 (70 min) -- • -- PNS (70 min)
14
)1~- -----------------
12
0+-----~----~------~-----,------.-----~
0 0,02 0.04 0.06 0.08 0.1 0.12

Diutan gwn (%)
Fig. 2- Effect of diutan gum dosage and HRWRA type on initial rheological parameters
0.8 -----PCP2 -.-PNS -.A:---PCP1
0.7
0.6
~ 0.5
i
I 0.4
rll 0.3
0.2 '\
\-----------------------JI(
0.1
0.0
0 0,02 0.04 0.06 0.08 0.1 0.12
Diutan gwn (%)
Fig. 3- Effect of diutan gum on surface settlement

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566 Khayat et al.
1000 0 Initial set • Final set
900
800
i
'-' 700
-~
gp 600
"fi
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
"' 500
400
300
Fig. 4- Setting time of mixtures made with diutan gum

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CONVERSION FACTORS-INCH-POUND TO Sl (METRIC)*
To convert from to multiply by
Length
inch millimeter (mm) 25.4E+
foot meter (m) 0.3048E
yard meter(m) 0.9144E
mile (statute) kilometer (km) 1.609
Area
square inch square centimeter (cm 2) 6.451
square foot square meter (m 2 ) 0.0929
square yard square meter (m 2 ) 0.8361
Volume (capacity)
ounce cubic centimeter (cm 3 ) 29.57
gallon cubic meter (m 3):j: 0.003785
cubic inch cubic centimeter (cm 3 ) 16.4
cubic foot cubic meter (m 3) 0.02832
cubic yard cubic meter (m 3 ):j: 0.7646
Force
kilogram-force newton (N) 9.807
kip-force newton (N) 4448
pound-force newton (N) 4.448
Pressure or stress
(force per area)
kilogram-force/square meter pascal (Pa) 9.807
kip-force/square inch (ksi) megapascal (MPa) 6.895
newton/square meter (N/m 2) pascal (Pa) l.OOOE
pound-force/square foot pascal (Pa) 47.88
pound-force/square inch (psi) kilopascal (kPa) 6.895
Bending moment or torque

inch-pound-force newton-meter (Nm) 0.1130
foot-pound-force newton-meter (Nm) 1.356
meter-kilogram-force newton-meter (Nm) 9.807
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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s6s Conversion Factors-Inch-Pound to 51 (Metric)
To convert from to multiply by
Mass
ounce-rna~~ (avoirdupoi~) gram (g) 28.34
pound-mass (avoirdupois) kilogram (kg) 0.4536
ton (metric) megagram (Mg) I.OOOE
ton (short, 2000 Ibm) megagram (Mg) 0.9072
Mass per volume

pound-mass/cubic foot kilogram/cubic meter (kgim 3) 16.02
pound-mass/cubic yard 3 0.5933
kilogram/cubic meter (kg/m )
pound-mass/gallon kilogram/cubic meter (kg/m 3 ) 119.8
Temperature§
deg Fahrenheit (F) deg Celsius (C) tc = (IF - 32)/1.8
deg Celsius (C) deg Fahrenheit (F) tF = 1.8tc + 32
* This selected list gives practical conversion factors of units found in concrete technology. The reference
source for information on SI units and more exact conversion factors is "Standard for Metric Practice" ASTM E
380. Symbob of metric units are given in parenthe~es.
t E indicates that the factor given is exact.
:j: One liter (cubic decimeter) equals 0.001 m 3 or 1000 cm 3 .
§ These equations convert one temperature reading to another and include the necessary scale corrections. To
convert a difference in temperature from Fahrenheit to Celsius degrees, divide by 1.8 only, i.e., a change from 70
to 88 F represents a change of 18 For 18/1.8 = 10 C.
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---

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Index
13-naphtalensulphonate, 215 cement hydration, 201

cement kiln dust, 231
A cement paste, 409, 507
admixture(s), 93, 321, 345, 471 Cerulli, T., 67, 487
admixture compatibility, 545 chain length, 231
adsorption, 1, 31, 93, 169, 231, 285, 297, chemical analysis, 507
357. 389, 455 Chen, ).W., 309
air entrainment, 507 chloride-induced corrosion, 249
aggregates, 15 Cioffi, R., 117
alkali-free accelerators, 487 clinker, 285
--`,```,,``,,,`,,,``````,,,,```,-`-`,,`,,`,`,,`---
alkali sulphate, 269 coagulation, 321
alkaline cements, 345 Colangelo, F., 117
amphoteric copolymer, 309 Collepardi, M., 1, 525
artificial aggregates, 67 Collepardi, S., 375
artificial "Terrazzo" flooring, 67 Comparet, C., 151
autogenous shrinkage, 471 compressive strength, 51, 117, 487
autogenous shrinkage strain, 51 concrete, 137, 169, 249, 309
aqueous phase, 357 concrete-equivalent mortar, 185
consolidation, 321
B Corazza, G., 375
Banfill, P.F.G., 345 Cord in,)., 409
Bentur, A., 15 Corinaldesi, V., 533
Bettencourt Ribeiro, A., 77 Corradi, M., 231
blast furnace slag, 525 corrosion inhibitors, 249
bleeding, 321 corrosion rate, 249
Bolzoni, F., 249 critical chloride threshold, 249
Bravo, A., 487
D
c D'Aioia Schwartzentruber, L., 409
calcium carbonate, 321 Dai, Z., 201
Caputo, D., 117 density, 231
carbonation, 249 Dikty, S., 105
Carrajola, A., 77 dispersant, 507
Cella,F.,487 drying shrinkage, 297
cement, 31, 137, 231, 269, 285, 309, 321, durability, 345
357.455

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570 Index
E
EO chain, 31 incompatibility, 215
expansive agent, 375 interaction, 357, 409
intercalation, 201
F incompatibility, 357
Fazio, G., 375 Izumi, T., 105
Ferrari, G., 67
Figi, R., 455
Flatt, R.J., 93, 169 Jeknavorian, A., 15
flocculation, 321 Jiang, F.T., 309
flow retention, 169 Jolicoeur, C., 321
fluidity, 269, 309, 389 Justnes, H., 455
fly ash, 525
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fresh concrete, 423 K
frost durability, 545 Khayat, K.H., 185, 545
Khurana, R., 231
G Kinoshita, T., 51, 471
galvanized steel reinforcement, 441 Kojima, T., 137
Georges, 5., 389 Koyanagi, K., 137
Goidanich, 5., 249 Koyata, H., 15
Golaszewski, J., 423 Kucerova, H., 269
Gon~alves, A., 77
Grossi, G., 525 L
Guillot, L., 357 lignin and derivatives, 507
lignosulfonate, 455
H lignosulphonates, 285
Haehnel, C., 357 Liguori, B., 117
Hamada, D., 31 Lolli, A., 67, 249
Hamai, T., 31 Lombois-Burger, H., 357
Harada, K., 51
Hazrati, K., 15 M
high strength concrete, 471 Magarotto, R., 215, 231
high-range water reducing admixture, Maitrasse, P., 151, 389
185 Maltese, C., 487
Hirata, T., 297 Masanaga, M., 297
Hsu, K.C., 309 McGuire, D., 15
Hwang, S.-D., 185 Mechaymech, A., 545
Hwung, 0.5., 309 Mikanovic, N., 321
hybrid, 471 mineral addition, 117
hydration, 151, 507 mix design, 409
hydration products, 285 molecular structure, 507
hydropobic admixture, 441 Monosi, 5., 375
hyper-branched polymer, 31 Moratti, F., 215

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Moriconi, G., 441, 533 R
mortar(s), 169, 423 recycled-aggregate concrete, 533
Myrvold, B.O., 285 recycled concrete, 533
reinforcement corrosion, 441
N Regnaud, L., 389
Nawa, T., 297, 471 repairing mortar, 375
Nonat, A., 151, 389 restrained shrinkage, 185
Novella, G., 67 retardation, 507
nuclear wastes, 525 rheology, 15, 31, 93, 321, 345, 357, 423,
455.545
0 rheological behavior, 409
Okada, K., 471 RoSier, C., 269
Ormellese, M., 249
over-fluidication, 389 s
Salvioni, D., 487
p Saito, K., 471
Page, M., 321 Sandberg, P., 15
sec,
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Palacios, M., 345 169
paste, 321 Schober, 1., 93, 169
paste flow, 169 secondary fuels, 231
PCE superplasticizers, 231 sedimentation, 321
PCP, 185, 389 segregation resistance, 137
Pedeferri, M.P., 249 self-compacting concrete, 105, 117, 409
Pellay, R., 67 self-consolidating concrete, 185, 545
Pellerin, B., 389 setting regulator, 487
Pellizon Birelli, M., 525 setting time, 51, 487, 507
PEO side chains, 357 Shimoda, M., 31
Perez, J.P., 389 Shonaka, M., 31
performance, 231 shrinkage, 1, 77. 345
petrographic analysis of aggregates, 15 shrinkage reducing, 51
Pistolesi, C., 487 shrinkage reducing admixture(s), 77.
Plank,]., 201 297. 375. 533
plastic viscosity, 31 shrinkage reducing agent, 471
plasticity, 507 Skaggs, B., 545
plasticizers, 455 slag, 345
PNS, 185 slump flow, 389
polyacrylate, 455 slump loss, 1
polycarboxylate, 1, 201, 215, 357, 471 slurry rheology modifier, 137
polycarboxylate ether, 169 solidification/stabilization, 525
polyether, 1 sorbitol, 525
polymer structure, 169 stability, 545
polysaccharide derivative, 105 steric hinderance, 1
Pourchet, S., 151, 389 Sugamata, T., 51
Puertas,F.,345 sulfate(s), 215, 357, 385

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572 Index
surface tension, 297 n yield value, 31
surfactants, 137
sulfonated naphthalene formaldehyde z
condensate, 455 Zeminian, N., 215
superplasticizer(s), 1, 31, 51, 67, 93, 151, zeta potential, 1
169,201,215, 269.35h409,423, Zhor, J., 507
545 Zouaoui, N., 201
supplementary cementitious materials,
231
syngenite, 269
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T
Takahashi, H., 31
temperature, 423
thickener, 105
Tittarelli, F., 441
tricalcium aluminate, 151, 201
Troli, R., 375
u
ultra-fine fly ash, 117
ultra-high·strength concrete, 51
v
Valente, M., 1
Valenti, G., 441
Ventura, G., 525
Vikan, H., 455
viscoelasticity, 137
viscosity, 471
viscosity-enhancing admixture, 409
viscosity-modifying admixture, 545
viscosity-modifying agent, 15
Vlad, D., 201
w
water·reducing admixture, 507
water reduction, 1
workability, 31, 117, 185, 309, 423
y
Yaguchi, M., 51
Yamamoto, T., 297
Yamamuro, H., 105, 137
yield stress, 15

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American Concrete Institute•
Advancing concrete knowledge
SP-239
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Aci sp-239-2006

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American Concrete Institute•

Copyright American Concrete Institute

Superplasticizers and Other

<HD American Concrete Institute•

Copyright American Concrete Institute

Copyright American Concrete Institute

DISCUSSION of individual papers in this symposium may be submitted in accordance

AMERICAN CONCRETE INSTITUTE

Printed in the United States of America

Editorial production: Lindsay K. Kennedy

Library of Congress catalog card number: 2006931607

Copyright American Concrete Institute

In 1981, CANMET, again in association with the American Concrete

were published as ACI SP-68.

The purpose of the third international conference in 1989 was to

In October 1994, CANMET, in association with the American

In October 1997, the Committee forthe Organization ofCANMET/ACI

In October 2000, the Committee for the Organization of CANMETI

Copyright American Concrete Institute

In October 2003, the Committee for the Organization ofCANMET/

In October 2006, the Committee for the Organization ofCANMET/

Thanks are extended to the members of the review panel for

Copyright American Concrete Institute

The Italian Advisory Committee chaired by Mario Collepardi

V.M. Malhotra, P.Eng.

Copyright American Concrete Institute

Preface .................................................................................................................... iii

SP-239-1: Recent Developments in Superplasticizers ............................................... 1

SP-239-2: Use of Chemical Admixtures to Modify the Rheological Behavior of

SP-239-3: Development of New Superplasticizer Providing Ultimate Workability .... 31

SP-239-4: Characteristics of Concrete Containing a Shrinkage-Reducing

SP-239-6: Behavior of Mortars with Different Dosages of Shrinkage Reducing

SP-239-7: Studying Admixtures with the 5C Rheometer .......................................... 93

SP-239-8: Properties of New Polysaccharide as a Thickner for Concrete ................ 105

SP-239-9: Influence of High Volumes of Ultra-Fine Additions on Self-Compacting

SP-239-11: Influence ofThree Types of Superplasticizers on Tricalciumaluminate

SP-239-12: Optimizing Polycaboxylate Polymers .................................................. 169

Copyright American Concrete Institute

SP-239-14: Intercalation of Polycarboxylate Superplasticizers into C3A Hydrate

SP-239-15: Influence of Sulfates Content in Cement on the Performances of

SP-239-16: Tailor-Made Superplasticizers for Modern Concrete ............................. 231

SP-239-17: Effectiveness of Commercial Corrosion Inhibitors for Reinforced

SP-239-18: Cement-Superplasticizers Interaction: The Influence of

SP-239-19: Adsorption of Lignosulphonates on Cement and the Hydration

SP-239-20: A New High Performance Drying Shrinkage-Reducing Admixture ........ 297

SP-239-21: An Amphoteric Copolymer as a Concrete Admixture ........................... 309

SP-239-22: Influence of Surfactant Chemical Admixtures on the Stability and

SP-239-23: Effect of Organic Admixtures on the Activation Process, Rheological

SP-239-24: Interaction between Cements and Superplasticizers .......................... 357

Copyright American Concrete Institute viii

SP-239-27: Rheological Behavior of Fresh Cement Pastes: Interaction between

SP-239-28: Effect ofTemperature on Rheological Properties of Superplasticized

SP-239-29: Hydrophobic Admixtures to Control Corrosion of Galvanized Steel

SP-239-30: Influence of Cement and Plasticizer Type on the Rheology and

SP-239-32: Effects of an Inorganic Acid Based Alkali-Free Accelerator on the

SP-239-33: Effect of Functional Groups on the Performance of Lignosulfonates in

SP-239-34: Influence of D-Sorbitol on the Properties of Binders to Immobilize

SP-239-35: Effectiveness of Superplasticizers Incorporating Shrinkage-

Copyright American Concrete Institute

Copyright American Concrete Institute X

by M. Collepardi and M. Valente

Synopsis: Superplasticizers are considered to be the most important chemical