Cement and Concrete Research 78 (2015) 81–99

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Cement and Concrete Research

journal homepage: http://ees.elsevier.com/CEMCON/default.asp

Chemical admixtures — Chemistry, applications and their impact on

concrete microstructure and durability
J. Plank a,⁎, E. Sakai b, C.W. Miao c,d,e, C. Yu d,e, J.X. Hong d,e
a
Department of Chemistry, Technische Universität München, TUM Center for Advanced PCE Studies, 85747 Garching, Germany
b
Department of Ceramics Science, Tokyo Institute of Technology, Tokyo 152-8552, Japan
c
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China
d
State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Research Institute of Building Science, Nanjing 210008, China
e
Jiangsu Sobute New Materials Co. Ltd., Nanjing 211103, China

a r t i c l e i n f o a b s t r a c t

Article history: An overview of current PCE compositions and synthesis methods is provided, followed by novel applications for
Received 18 March 2015 PCEs including C–S–H-PCE nano-composites and a description of still unresolved challenges for PCE technology.
Accepted 12 May 2015 In addition, the functionality of chemical admixtures in specific applications for low-carbon cements and
Available online 17 June 2015
concrete systems is discussed. The action mechanisms of retarders and the recycling system of sludge water by
using retarder are introduced. Furthermore, the influence of fluoride ion and the effectiveness of PCE polymers
Keywords:
Admixture (D)
in blended cements and the effect of non-adsorbed polymer are presented. And the impact of special interface
Concrete (E) modifying materials, of a refined pore structure and of chemical admixtures, particularly shrinkage-reducing
Microcracks (B) agents, is described. The article concludes that more accurate quantitative micro-analytical methods and
Polycarboxylate modeling tools will be needed to obtain a holistic understanding of factors affecting the microstructure of
Shrinkage reducing agent (C) concrete, with the final goal of achieving a more durable concrete.
© 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2. PCE superplasticizers — present and future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.1. Chemistry of PCE superplasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.1.1. MPEG-type PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.1.2. APEG-type PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.1.3. VPEG-type PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1.4. HPEG-type PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1.5. IPEG-type PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1.6. PAAM-type PCEs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1.7. Organo-silane modified PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2.1.8. Crosslinked PCE molecules (XPEG-type PCEs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1.9. Phosphated PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.2. Novel applications for PCEs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.3. Challenges for current PCE technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2.3.1. Enhanced tolerance to different cement compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2.3.2. Enhanced clay tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
2.3.3. Use of sacrificial agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.3.4. Introduction of novel PCE structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.4. Future perspectives of PCE technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.4.1. PCE as cement additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.4.2. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

⁎ Corresponding author at: Technische Universität München, Lichtenbergstr, 4, 85747 Garching, Germany. Tel.: +49 89 289 13151; fax: +49 89 289 13152.
E-mail address: sekretariat@bauchemie.ch.tum.de (J. Plank).

http://dx.doi.org/10.1016/j.cemconres.2015.05.016
0008-8846/© 2015 Elsevier Ltd. All rights reserved.
82 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99

3. Chemical admixtures in low-carbon cement and concrete systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

3.1. Impact of the action of PCE superplasticizer on blended cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.1.1. Effect of C3A content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.1.2. Influence of impurity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.1.3. Molecular structure of PCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.1.4. Interaction between PCE and high-volume slag cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2. PCE superplasticizers for high durability concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2.1. PCE for ultra-high strength cement with silica fume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2.2. Effect of non-adsorbed PCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.3. Fresh concrete sludge recycling system using retarders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4. Chemical admixtures for durability improvement and their application in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.1. Air entraining agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.2. Shrinkage reducing agents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3. Expansive agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.3.1. CaO- and ettringite-based expansive agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.3.2. MgO- based expansive agent (MEA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4. Curing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.4.1. Superabsorbent polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.4.2. Water evaporation retardant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

1. Introduction (SCC) which no longer requires compaction. Moreover, specific PCE

Various types of chemical admixtures are used to improve the
construction properties of concrete such as workability, pumpability,
setting properties, the mechanical performance, the durability such as
freeze thaw resistance and the shrinkage properties. Also, chemical ad-
mixtures enable the manufacture and construction of special concretes
such as high fluidity concrete, high strength concrete, underwater con-
crete, and sprayed concrete. This three-part article reviews recent de-
velopments in admixture chemistry and applications, with a focus on
polycarboxylate (PCE) superplasticizers and retarders. Furthermore,
new insights into optimized concrete microstructures and the role of
shrinkage-reducing agents for improved concrete durability are
presented.
This contribution attempts to provide an overview of recent devel-
opments in the field of PCE technology and of its perspectives in the fu-
ture in Section 2 of this paper. The invention of polycarboxylate comb
polymers in 1981 as a novel class of concrete superplasticizers clearly
presents a milestone in concrete technology [1]. With the help of
these admixtures, it now became possible to formulate highly advanced
concretes such as ultra-high strength concrete (UHPC) which can attain
compressive strength values N 150 MPa, or self-compacting concrete
molecules were designed which can provide long slump life (N 2 h) for
ready-mix concrete without sacrificing early strength [2]. These few ex-
amples illustrate the extraordinary contribution of PCE superplasticizers
to modern concrete technology. In Section 2 of this paper, an overview
of current PCE technology including some recent trends will be present-
ed. This is followed by a review of new applications. In the third part of
this section, the shortcomings and deficiencies of PCEs as evidenced in
daily operations, and potential solutions for them will be discussed.
Finally, an outlook will be given on what still can be expected from
PCE technology in the future.
In Section 3 of this paper, chemical admixtures such as PCE and
retarders for low carbon cement and concrete systems and their mech-
anisms of action are introduced and summarized. The RC Specifications
of the Japan Society of Civil Engineers suggest a unit water content of
175 kg/m3 from the point of view of ensuring the durability of concrete
[3]. Both the water reduction and slump retention are required, PCE-
superplasticizers are widely used. In addition to higher performance of
concrete, reduction of CO2 is becoming an important issue in the cement
and concrete field. The development of superplasticizers for such low
carbon cement and concrete is also important. For example, there is
optimization of superplasticizer in the use of blended cement or low

Fig. 1. Esterification (grafting) process for the synthesis of MPEG-type PCEs producing a highly uniform, random (statistical) copolymer, as evidenced by GPC.
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99 83

Fig. 2. Free radical copolymerization route for the synthesis of MPEG-type PCEs producing a gradient polymer with non-homogeneous distribution of side chains.

carbon type cement using flux and mineralizer. Also, low carbon cement
and concrete can be achieved by extending the service life using ultra
high strength cementitious materials, namely ultra-high durability ce-
mentitious materials. In these cases also the development of new
superplasticizers is necessary.
Retarders are added as auxiliary agents to retardant type of AE
water reducing agents and AE high range water reducing agents [4]
for use in concreting during hot weather. Also, retarders are used
in the joints of mass concrete and for integrating old and new con-
crete, in the slip-forming method, for processing the pile heads of
in-situ piles, for scrubbed finish concrete, and for green cuts of dam
concrete. In addition, retarders are also used in ready-mixed
concrete as a stabilizer for effectively utilizing adhering mortar [5].
Also, retarders play an important role in methods of using ready
mixed concrete factory cleaning water, adhering mortar and
returned concrete as sludge water, and in technology for using
sludge as sludge water arising at factories producing centrifugally
cast products such as Hume pipes [6,7]. Retarders are helping to
achieve low-carbon cement and concrete through the reuse of ce-
ment that would otherwise be waste.
In Section 4 of this paper, the effect of microstructure on the proper-
ties of concrete especially the durability is reviewed from the following
three aspects, interfacial transition zone, pore structure and micro-
cracks respectively. Concrete structure exhibits durability problems
which are caused by concrete corrosion under the severe inland and
marine environments. Concrete deteriorates when exposed to wet and
subfreezing conditions, natural or polluted water rich in salts, and ex-
tremely dry and windy conditions. Moreover, cracks generated from
shrinkage may accelerate the transportation of aqueous solutions and
other mediums, leading to a reduced durability of concrete.

Fig. 3. Chemical compositions of typical APEG-, VPEG- and HPEG-type PCE polymers.
84 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Since their accelerated development in the last four decades,
chemical admixtures have been commonly used in concrete produc-
tion to enhance the workability, mechanical properties and durabil-
ity. It is generally accepted that the introduction of high-range water
reducer, so called superplasticizer, allows a highly improved work-
ability for concrete at a relatively low water to cement ratio, which
leads to improvement of strength and permeability. Besides, other
chemical admixtures are also applied to gain benefits in various du-
rability issues. These materials can entrain air to impart resistance
of freezing and thawing, reduce water evaporation to mitigate
shrinkage, and generate expansion to compensate shrinkage and
prevent cracking. In this paper, the mechanism and recent research
progress of air entraining agent, shrinkage reducing agent, expansive
agent and curing agent are reviewed. And their application recently
in construction projects of China are also demonstrated as case
study, which shows a promising future in promoting research
achievements into field application.
2. PCE superplasticizers — present and future
2.1. Chemistry of PCE superplasticizers
As of today, a great diversity of chemically very different PCE
products is applied which includes:
Fig. 4. Chemical structures of typical IPEG-, XPEG- and PAAM-type PCE polymers.
2.1.1. MPEG-type PCEs
They constitute the first type of PCE which was introduced into the
Japanese market by Nippon Shokubai under the name ‘FC 600’ [7].
MPEG-PCEs can be synthesized following two different routes:
(a) Esterification of poly(methacrylic acid) with methoxy poly
(ethylene glycol) utilizing an acid catalyst (e.g. p-toluol sulfonic
acid) and an azeotropic solvent or vacuum to remove the water
[8]. This process produces a highly uniform comb polymer with
regular (statistical) distribution of the MPEG graft chains along
the polyanionic trunk chain (random copolymer, see Fig. 1).
Disadvantages of this method are long reaction times and de-
pending on the quality of the acid catalyst relatively low esterifi-
cation degrees. Note that residual MPEG has been shown to
entrain a considerable amount of air into concrete [9]. A practical
solution to these problems is offered by trans-esterification of
poly(methacrylate methyl ester) with MPEG under similar con-
ditions as above. The advantage of this method is a higher degree
of esterification because methanol presents a better ‘exit group’
than water. Disadvantages are the higher cost for the PMA meth-
yl ester and the necessity to hydrolyze the remaining methyl
ester groups after grafting.
(b) Aqueous free radical copolymerization of ω-methoxy poly(ethyl-
ene glycol) methacrylate ester macromonomer with methacrylic
acid presents the second and quite common route to prepare
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
MPEG-PCEs [10] (Fig. 2). This reaction is easy to carry out, com-
position and performance characteristics of the polymer can be
controlled by the molar ratios of the monomers, and the trunk
chain length is adjusted by utilizing chain transfer agents such
as mercaptans, methallyl sulfonic acid or hypophosphite. Here,
it has to be considered that the relative reactivities of both mono-
mers may vary, depending on the pH. Notably, the macromo-
nomer can exhibit a higher reactivity than methacrylic acid. As
a consequence, in many polymerizations not uniform, but gradi-
ent polymers are attained which at the beginning of the polymer-
ization exhibit a higher side chain density than towards the end
of the reaction. Recently, such gradient polymers possessing spe-
cific compositions have been synthesized on purpose by applying
RAFT polymerization technique [11]. It was found that these
polymers adsorb more strongly on cement as a result of their
large anionic blocks in the trunk chain. Additionally, they exhibit
higher sulfate tolerance and thus perform more robust with dif-
ferent cements, as they are less desorbed by SO2− anions than
4
comparable PCE molecules possessing a random distribution of
the lateral chains. Hence, these gradient PCE polymers are con-
sidered to be advantageous.
In both processes (a) and (b), attention must be given to the diol
content. Commercial MPEG may contain variable amounts of PEG
which presents a diol. When PEG (diol) is present in the esterification
reaction, then crosslinking between two poly(methacrylic acid) back-
bones will occur. However, such crosslinked PCE molecules are known
to provide very poor – if any – dispersing performance [12]. Similarly,
when some PEG impurity is present in the synthesis of the
Fig. 5. Synthesis route for an organo-silane modified PCE polymer.
85
macromonomer MPEG-methacrylate ester, then a diester is formed
which in the subsequent copolymerization reaction again produces a
crosslinked PCE, with potentially negative consequences. It has been
found that the diol content present in MPEG ideally should be b 1.0%,
while a content of 4% already shows significant reduction in PCE perfor-
mance [12].
2.1.2. APEG-type PCEs
This kind is prepared from α-allyl-ω-methoxy or ω-hydroxy poly(-
ethylene glycol) ether and maleic anhydride or acrylic acid as key
monomers via free radical copolymerization, either in bulk or in aque-
ous solution (Fig. 3) [13]. APEG-PCEs always possess a strictly alternat-
ing monomer sequence (ABAB), because the allyl ether macromonomer
does not homopolymerize as a consequence of mesomeric stabilization.
This stabilization makes allyl ethers to react rather slowly and can lead
to low conversion of the monomers. Polymerization in bulk works well
for side chain lengths of up to 34 EO units and produces a viscous PCE
copolymer with 100% solid content which thus requires dilution with
water to obtain a pourable liquid of ~60 wt.% solid content. Polymeriza-
tion in water typically yields copolymers possessing very short trunk
chains (‘star polymers’) made of ~10 repeating units only which were
found to exhibit superior dispersing performance. The disadvantages
of aqueous copolymerization are longer reaction times, lower conver-
sion rates and lower concentration of the finished PCE solution.
At first APEG-PCEs suffered from a reputation of causing delayed
plastification (i.e. the slump of concrete increased over ~ 30 min to
reach a maximum, then dropped afterwards). Such behavior is highly
unwanted as it often results in overdosing of PCE and subsequent bleed-
ing of concrete.
86 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 6. Chemical structure of a PCE superplasticizer containing a phosphate anchor group.
Meanwhile, this problem has been solved, for example by incorpora-
tion of specific comonomers as spacer molecules such as styrene which
can modulate the conformational flexibility of the trunk chain. This
method provides PCE molecules with pronounced stiffness, as evi-
denced by higher values for the hydrodynamic radius [14]. Time depen-
dent adsorption measurements revealed that such modified APEG-PCEs
can adsorb faster and thus avoid the effect of delayed plastification.
2.1.3. VPEG-type PCEs
Such PCEs are obtained by aqueous free radical copolymerization of
e.g. 4-hydroxy butyl-poly(ethylene glycol) vinyl ether and maleic anhy-
dride or acrylic acid (Fig. 3) [15]. Their polymerization must be conduct-
ed at temperatures b30 °C to avoid monomer degradation. As a result, a
specific low temperature initiator is required. The advantage of vinyl
over allyl ether technology is the much higher reactivity of vinyl ethers.
2.1.4. HPEG-type PCEs
Here, α-methallyl-ω-methoxy or ω-hydroxy poly(ethylene glycol)
is used as macromonomer in copolymerization with e.g. acrylic acid
(Fig. 3) [16]. This kind of PCE which is easy to polymerize emerged a
Fig. 7. TEM image of C–S–H-PCE nanocomposite foils (left) and their effectiveness as strength enhancing seed material for CEM I 52.5 R (right).
few years ago especially in China. There, even a process where copoly-
merization is performed at room temperature has been developed and
is applied in many factories [17].
2.1.5. IPEG-type PCEs
This type of PCE (sometimes also referred to as TPEG-PCE) is synthe-
sized from isoprenyl oxy poly(ethylene glycol) ether as macromonomer
by copolymerization with e.g. acrylic acid (Fig. 4) [18].
In recent years, this PCE has become popular, especially in China, be-
cause of its excellent performance which often exceeds that of any other
type of PCE, and its simple preparation utilizing free radical copolymer-
ization. A disadvantage of IPEG-PCEs is their potential to decompose
into isoprene, water and glycol [19]. To prevent this undesired process,
the IPEG macromonomer and the IPEG PCE should not be handled in
bulk, but always kept in aqueous solution.
2.1.6. PAAM-type PCEs
These zwitterionic PCEs possess mixed side chains composed of
polyamidoamine (PAAM) and PEO segments (Fig. 4). This structural fea-
ture distinguishes them fundamentally from all other PCEs which exclu-
sively contain PEO/PPO side chains. The PAAM-type PCE is said to
fluidify cement at w/c ratios as low as 0.12 [20]. Its disadvantage is the
high cost of the PAAM side chain.
In spite of the great diversity of current products, industrial and
academic researchers still develop and introduce new PCE polymers
with additional structural features. Those include:
2.1.7. Organo-silane modified PCEs
Recently, two groups independent from each other presented novel
silylated PCE polymers. The first group incorporated 3-trimethoxysilyl
propyl methacrylate (MAPTMS) as a new comonomer into a conven-
tional MPEG-type PCE while the second group utilized N-maleic γ-
amidopropyl triethoxy silane (MAPS) as an organo-silane modified
monomer (Fig. 5) [21,22]. The consideration behind the introduction
of a silane functionality into the PCE molecule was to obtain a chemical
bond between the C–S–H surfaces and the superplasticizer, made possi-
ble through condensation of silanol (–Si–OH) groups present in both
compounds. If formed, such a bond would anchor the PCE molecule
irreversibly on the surface of cement hydrates and thus provide a mol-
ecule which cannot be desorbed e.g. by sulfate ions or anionic retarder
molecules as a result of competitive adsorption. Indeed, both groups
found that such silylated PCE polymers exhibit superior sulfate toler-
ance. Additionally, the MAPS modified PCE was shown to disperse ce-
ment at substantially lower dosages than the same non-modified PCE
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 8. Dispersion performance of a conventional PCE superplasticizer in 13 different
cements, illustrating the problem of poor cement tolerance and cement incompatibility.
[22]. For this copolymer, 29Si-MAS-NMR spectroscopy provided clear
analytical evidence for the formation of a chemical bond between the
novel PCE and the mineral surface.
2.1.8. Crosslinked PCE molecules (XPEG-type PCEs)
According to an early theory, the ability of an individual PCE mole-
cule to cover as much surface area on cement as possible directly corre-
lates to its dosage [23]. Hence, polymers which stretch out on the
surface are believed to present more effective PCEs. Following this con-
cept, slightly crosslinked PCE molecules utilizing diesters (e.g. from PEG
and methacrylic acid or maleic anhydride) (Fig. 4) were synthesized
and shown to provide enhanced dispersion [24]. Moreover, hyper-
branched and dendrimeric PCE polymers were suggested using
polycarboxylated polyglycerols [25]. Surprisingly, they do not much
enhance cement dispersion when compared to conventional PCE prod-
ucts. Still, they present an interesting approach which perhaps requires
further fine-tuning in the synthesis.
Fig. 9. Synthesis route for a novel PCE copolymer exhibiting improved cement compatibility.
87
2.1.9. Phosphated PCEs
Superplasticizers generally achieve their dispersing power through
adsorption on the surface of cement, especially that of ettringite [26].
Such adsorption is facilitated through anionic anchoring groups which
typically include carboxylate or dicarboxylate groups. Already some
years ago, it has been shown that phosphonate presents a more power-
ful anchoring group than carboxylate [27]. Very recently, novel
superplasticizers have been presented which incorporate phosphate
as an anchoring group [28,29]. Phosphatation can be accomplished by
esterification of e.g. hydroxyethyl methacrylate with phosphoric acid,
leading to a PCE copolymer as shown in Fig. 6. The phosphated PCEs
are said to adsorb on cement almost instantaneously which presents a
major advantage in specific concrete and dry-mix mortar applications.
Furthermore, they appear to be more sulfate-tolerant, compared to con-
ventional PCE superplasticizers.
2.2. Novel applications for PCEs
The exceptional performance of current commercial PCE products
enabled us to build spectacular concrete structures. A prominent exam-
ple is the construction of Burj Khalifa in Dubai, with 820 m currently the
tallest skyscraper in the world. Up to 650 m its structure consists of high
strength concrete incorporating VPEG-type PCEs and a retarder. This
combination provided a formulation which was pumpable up to a re-
cord height of 650 m, and showed slump retention over 3 h at temper-
atures as high as 50 °C. Such formulations were unthinkable before the
advent of PCE polymers.
Another significant application of PCE is in sprayed concrete (also re-
ferred to as shotcrete) which is applied in tunneling e.g. for high speed
railway tracks, metro lines, and mining operations [30]. There, PCE poly-
mers are admixed to concrete which is then combined with alkali-free
accelerators such as Al(OH)SO4 or amorphous Al(OH)3 at the nozzle of
the spraying gun. In shotcrete, PCEs can reduce the water-to-cement
88 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 10. Fundamental types of interaction between PCE and montmorillonite clay (left) and chemical sorption (intercalation) of a poly(ethylene glycol) side chain in between alumosilicate
layers (right).
ratio to lower values than those attainable from polycondensates which
results in higher strength of concrete. This effect is highly desirable, be-
cause it allows thinner concrete liners to support the tunnel.
Apart from concrete, PCE superplasticizers now are also used in large
quantities in the manufacture of gypsum wallboards [31]. There, the PCE
products allow to substantially reduce the amount of mixing water re-
quired for the gypsum slurry. As a result, the wet gypsum body contains
more air as the boards' density is kept constant, and can be dried with
much lower energy demand which reduces cost. Thus, the primary mo-
tivation for PCE use here is reduction of energy cost, while the associat-
ed gain in strength is second. Specific PCE products which are
characterized by extremely fast adsorption (within few seconds) have
been designed for this application. This technology has become popular
in the U.S., the largest market for gypsum wallboards, and in Europe as
well.
A very recent invention includes the application of C–S–H-PCE nano-
composites as seed crystals for the hydration of the silicate phases C3S
and C2S [32,33]. The nanocomposites can be prepared by combining
aqueous solutions of e.g. sodium silicate and calcium formate with a
PCE solution. The resulting instantaneous precipitate contains nanofoils
of C–S–H with surface adsorbed and possibly intercalated PCE (Fig. 7).
The nanofoils greatly accelerate the silicate hydration by reducing the
free activation energy ΔG of crystallization to zero. In cement this barri-
er needs to be overcome to initiate C–S–H nucleation. The result is a
much enhanced early strength development, especially after 6–12 h of
hydration, without sacrifice on the final strength (Fig. 7).
2.3. Challenges for current PCE technology
In spite of these many advances, still some areas exist where
improvements in PCE technology are required. Those include:
2.3.1. Enhanced tolerance to different cement compositions
Already in the early days of PCE use, applicators noticed that most
PCE products exhibit a marked sensitivity for different cement qualities.
As an example, Fig. 8 displays the performance of a typical conventional
PCE product with 13 different cements. While before it was known that
increased C3A contents in a cement require elevated dosages of super-
plasticizer to cover the more abundant surfaces of ettringite sufficiently
[26,34,35], it was now found that additional factors influence PCE dos-
age. Free dissolved sulfate (e.g. from alkali sulfates) was identified as
one reason for decreased cement compatibility of PCEs [36–38]. While
initially it was believed that the reason behind the decrease in PCE per-
formance caused by sulfate was coiling (shrinkage) of the PCE molecule
[38], it is now established that competitive adsorption between PCE and
sulfate presents the main effect, whereby sulfate desorbs PCE from the
surface of cement and thus prevents it from developing its dispersion
power [39]. In accordance with this model, ready-mix type PCEs
which are characterized by a high grafting density (and correspondingly
low anionic character) are stronger affected by sulfate than the more
anionic PCEs used in precast concrete applications. The industry has
solved the problem of sulfate sensitivity by introducing blocks of highly
anionic charge into the trunk chain (e.g. in gradient polymers) or by in-
corporating a few, but highly surface-affine anchor groups into the PCE
molecule such as e.g. dicarboxylates, phosphates or phosphonates [40].
Still, researchers are aware that PCE performance can be affected by ce-
ment constituents other than sulfate. Intensive investigations are ongo-
ing to identify them.
Recently, a novel PCE structure has been patented which is claimed
to exhibit much improved cement tolerance, independent of variations
in sulfate contents and other cement constituents [41]. The main feature
of this novel polymer is a cyclic structural unit built into the polymer's
trunk chain (Fig. 9). Still, the reason behind the improved cement com-
patibility of this polymer remains unexplained. However, recent find-
ings suggest that most PCE copolymers act as morphological catalyst
for ettringite, i.e. they can modify the size and aspect ratio of this cement
hydrate, thus sometimes leading to abundant amounts of exceptionally
small, nano-sized ettringite which constitute an enormous surface area
which needs to be coated with PCE in order to achieve sufficient dis-
persion [42].
2.3.2. Enhanced clay tolerance
Over the last years, applicators have observed that PCE
superplasticizers – unlike polycondensates – exhibit a pronounced sen-
sitivity to clay and silt contaminants [43–45]. As a result, their perfor-
mances are greatly reduced or the PCEs become entirely ineffective.
Montmorillonite, a 2:1 smectite clay, has been found to be more harmful
than other clay minerals such as kaolinites or muscovites [46,47]. Gen-
erally, the capacity of clays to sorb water, hydrate and swell leads to
more viscous cement pastes. This effect results in a loss in workability
or a higher water demand independent of whether a superplasticizer
is present or not.
Previous research has established that in cement pore solution, the
surfaces of bentonite clay particles become positively charged as a result
of Ca2+ adsorption onto the negative alumosilicate layers. Onto these
surfaces, polyanionic superplasticizers such as polycondensates or
polycarboxylates adsorb, thus resulting in a partial depletion of
superplasticizer available for cement dispersion. This way, clay com-
petes with cement for superplasticizer. Moreover, PCE polymers can
Table 1
Properties of PCE samples synthesized.
Samples M-9 M-23
Side chain length (mol) 9 23
Molecular weight 53400 41200
MAA ratio (mol) 69% 40%
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99 89

1
2500
ECM6000
ECM4000 ECM6000
0.8 2000
M23
OPC OPC
0.6 1500 M9
BFS4000 ECM4000
0.4 1000

0.2 BFS6000 500

0 0
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
Dosage of superplasticizer / mass% Dosage of superplasticizer / mass%

Fig. 11. Adsorption of PCE sample M23 and the fluidity of pastes with M23.

intercalate chemically into the interlayer space between the individual
alumosilicate layers, resulting in an organo-mineral phase whereby
their poly(ethylene glycol) side chains occupy the interlayer space, as
is shown in Fig. 10. This reaction with clay is specific for PCEs and is a
consequence of their PEO side chains, as was evidenced by XRD mea-
surements [48]. Consequently, PCEs can be used up by clay by both sur-
face adsorption and chemical sorption whereas polycondensates such
as BNS only are consumed by surface interaction [44,48]. This explains
why PCEs are significantly more affected by clay than polycondensates.
Currently, the industry is probing several strategies to mitigate the
negative effects of clay on PCEs. Those concepts include:
2.3.4. Introduction of novel PCE structures
Obviously, the best solution to the incompatibility problem of PCE and
clay would be a novel PCE structure which does not contain PEO side
chains. Recently, such polymers have been synthesized using either hy-
droxy alkyl esters of methacrylic acid or vinyl ethers as side chain bearing
macromonomers [52,53]. Utilizing XRD analysis, it was found that indeed
these novel polycarboxylates do not undergo side chain intercalation
with clay and adsorb in small quantity only (~25 mg polymer/g clay).
Consequently, they exhibit robust performance even in the presence of
clay contaminants. This behavior perfectly confirms the concept of non-
PEO side chains as a remedy for the intercalation problem of conventional
PCEs.

2.3.3. Use of sacrificial agents

Analysis of sorbed amounts of individual PCE constituents (back-
bone, represented by poly(methacrylic acid) and side chain, represent-
ed by poly(ethylene glycol)) revealed that the side chain sorbs in large
amounts on clay (~ 400 mg MPEG/g clay) while the polymer trunk is
consumed much less (~30 mg PMA/g clay) [49]. This not only signifies
that the PEO side chain present in PCE provides the main interaction
with clay; it also offers a remedy for the problem whereby pure PEG
or MPEG are utilized as sacrificial agents to occupy the interlayer spaces
while the PCE molecule which exhibits a lower tendency to intercalate
as a result of its anionic charge is preserved and can thus interact with
the cement to achieve dispersion [50]. The downside of this concept is
strongly increased foaming, as PEG or MPEG contributes significantly
to the air-entraining problem of PCEs [9]. As another remedy, addition
of cationic polymers which inhibit the swelling of clay entirely has
been proposed [51]. This method offers the advantages of zero water
consumption because the clay will not hydrate at all. Additionally, the
interlayer spacing will not be accessible for the PCEs.
2.4. Future perspectives of PCE technology
Although the current PCE technology already is in a highly advanced
state, it has by no means matured yet. Further significant developments
can be expected in the future. Here, as an example, one highly promis-
ing recent trend is presented.
2.4.1. PCE as cement additive
In the manufacture of cement it is common practice to add grinding
agents at the clinker mill to reduce the energy demand required to ob-
tain a certain particle fineness. Frequently used grinding agents include
alkanol amines (e.g. triethanol amine or triisopropanol amine) or
polyglycols (PEGs). Their working mechanism is well understood and
has been described recently [54]. Because the latter represent the side
chain of PCE, addition of liquid PCE during the grinding process was
tested for enhanced productivity of the mill and at the same time to
reduce the water demand of the cement obtained from this process

0.8 4500
4000
ECM4000 M23
3500
0.6 M9
3000
ECM6000 ECM6000
2500
0.4
BFS4000 2000
1500
OPC
0.2 BFS6000
1000
OPC 500 ECM4000
0 0
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
Dosage of superplasticizer / mass% Dosage of superplasticizer / mass%

Fig. 12. Adsorption of PCE M9 and the fluidity of paste with M9.
90 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99

[55–59]. Several cement producers have experimented with this tech- Table 2
nology, and after ~ 3 years of trial, mixed results were reported. In Properties of PCE samples.

some cases, a significantly higher throughput was achieved as a result Samples A B C

of PCE addition. While in other plants, only a minor or no effect at all
was observed. The reason behind these differences is still unknown
and requires investigation. A recent publication presented details on
laboratory and actual cement plant tests utilizing 40% liquid PCE admix-
tures [60]. There, it is shown that maximum effectiveness is achieved
when the PCE is blended with conventional alkanol amine based grind-
ing agents. At addition rates of 250–500 g PCE/to clinker which are typ-
ical for grinding agents, no plastification effect from PCE was observed.
To achieve this, significantly higher dosages (≥1 kg/to) need to be ap-
plied. In such case, a cement with reduced water demand and hence
higher strength is obtained. This concept would be particularly interest-
ing for blended cements such as CEM II/III.
If the use of PCE as cement additive continues to be successful, it can
provide a significant new demand for PCE products. However, further
progress in this field requires a thorough understanding of the surface
chemistry occurring during the grinding process. Additionally, the fu-
ture development of energy costs will play a key role for the economics
of this application.
2.4.2. Outlook
The question remains as to whether a completely new technology
will replace PCE in the future. At present, the answer to this question
clearly is “no”, because no such alternative with improved cost-
performance relationship is visible on the horizon. Therefore, one can
expect that PCE technology will continue to develop and even migrate
into new fields such as e.g. the refractory, the paints & coatings or the ce-
ramics industry while any substitution appears to be unlikely at this
time.
3. Chemical admixtures in low-carbon cement and concrete systems
3.1. Impact of the action of PCE superplasticizer on blended cements
Blended cement is extremely useful as a measure for reducing CO2
emissions [61]. The fluidity of blended cement paste is mainly con-
trolled by the packing fraction which is related to the particle-size distri-
bution and particle shape. The content of SO2− 4 in base cement depends
on the fluidity of the blended cement paste. In addition, C3A content, im-
purity, and adsorption properties of PCE depend on the fluidity of both
blended cement paste and concrete. The adsorption of PCE is an impor-
tant factor in controlling this fluidity.
3.1.1. Effect of C3A content
In replacing limestone powder or FA, the fluidity of paste or mortar
with PCE is improved [62,63]; moreover, if the replacement ratio of
fine blast-furnace slag smaller than 20 μm is increased, the fluidity of
the paste is improved as the replacement ratio increases [64]. This im-
provement in fluidity of limestone powder is greatest for pastes with
PCE, followed in order by blast-furnace slag and natural pozzolan [65].
Also, in cement for which the C 3 A content is increased with the
aim of increasing the amount of waste, replacement with blast-
furnace slag has the effect of diluting C3A with limestone powder.
The C 3 A reaction is then immediately suppressed after contact
with water, so the fluidity of the cement paste is improved [66,67].
When the blast-furnace slag replacement ratio exceeded 54%, the
adsorption onto the blast-furnace slag cement was slightly less
than for ordinary Portland cement (OPC), and was related to the di-
lution in C3A [68].
3.1.2. Influence of impurity
If limestone powder is used, the fluidity of cement and concrete with
PCE is usually improved. However, for limestone powder, if clay is pres-
ent then the PCE is selectively adsorbed onto the clay, and the fluidity is
Side chain length (mol) 25 25 25
Molecular weight 10,000 18,900 29,500
Acid ratio (mass%) 25 25 25
significantly reduced [43–45,49,69]. The content of Al2O3 in fine lime-
stone powder is related to the clay component included as an impurity
[70]. For methacrylic-type PCE in CEM I 52.5R and CEM IV/A (P) 42.5R
(FA), the amount of PCE adsorption was unchanged, but the amount
of adsorption of PCE was increased with natural pozzolan in CEM IV/
A(P) 42.5R (natural pozzolan). This is because the specific surface area
(SBET) of natural pozzolan is larger [71]. For industrial pozzolan such
as FA and other incinerator ash, the influence of unburned carbon
needs to be considered [72,73].
3.1.3. Molecular structure of PCE
The amount of adsorption of PCE by blast-furnace slag or limestone
powder per unit of area is less than that on cement [74]. However, the
authors have obtained a contradictory result by adding PCE with a dif-
ferent molecular structure and achieved greater adsorption onto blast-
furnace slag compared with cement [75]. Hermann and Rickert com-
pared the amount of adsorption of PCE on CEM III/B with 80% blast-
furnace slag replacement and CEM I, and found that there was some
PCE for which CEM III/B was greater, and some PCE which gave an oppo-
site result [76]. Apart from the molecular structure of PCE, the content of
SO2−
4 in base cement is also affected [76]. The adsorption of PCE having
the same molecular structure by CEM I 52.5R, CEM II/B-S 42.5N, and
CEM IV/A(P) 42.5R was the same. Also, the adsorption of the smallest
PCE is largest, whereas the adsorption for PCE having longer main and
side chains decreases [77]. Two types of PCE were investigated for
CEM II and CEM III using limestone powder and blast-furnace slag. It
was found that the adsorption of PCE at which the fluidity was a maxi-
mum depended on the content of the clinker [76]. Also, Alonso and
others have found that the amount of adsorption of PCE
(polycarboxylate/polyether-type superplasticizer) with different molec-
ular structures on CEM I 42.5R, CEM II/B-L 32.5 R with limestone powder,
and CEM II/A(V) 42.5R with FA was about the same [78].
Much research has been performed on the adsorption properties of
PCE onto various types of powders and blended cements, each reporting
different results. This is because PCE with different molecular structures
was used and the characterization of the cements and powders used
was not clear [79]. The amount of adsorption of PCE onto blended ce-
ments is affected by the types of blending materials, the replacement
rates of the blending materials, the base cement, and especially the
6000
. 5500
5000 C(29500)
4500
4000
3500 B(18900)
3000
2500
A(10000)
2000
0.3 0.4 0.5 0.6 0.7 0.8
Dosage of superplasticizer / mass%
Fig. 13. Fluidity of pastes with PCE superplasticizers at low water/powder ratio
(W/P:0.16).
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99 91

45
40 Dosage of GLNa
(mass%)
35
0
30 0.05

Fig. 14. Adsorption of PCE superplasticizers.
molecular structure of the PCE. For alkali-activated cement, the mole-
cule design of PCE has also been suggested as being important [40].
3.1.4. Interaction between PCE and high-volume slag cement
Two types of PCE of different side-chain lengths and the ratio of
methacrylic acid (MAA) were synthesized (Table 1). As the amount of
PCE increases, the amount of adsorption of M23 onto OPC, BFS, and
high-volume slag cement (ECM4000 and 6000: the number denotes
the fineness of BFS) increases and the apparent viscosity of either OPC
or ECM paste with M23 decreases (Fig. 11) [80]. In this high-volume
slag cement (ECM), the ratio of BFS, OPC, and anhydrite is 63:30:7 by
mass.
Also, BFS4000 and 6000 reach adsorption saturation at a lower dos-
age compared with OPC. No difference in the amount of adsorption per
unit of surface area is seen with fineness of BFS powder. M23 shows a
tendency to be more easily adsorbed onto OPC than BFS. However, in
ECM, the Ca2+ supplied from OPC is adsorbed onto the surface of BFS,
so the number of adsorption sites increases, and the adsorption of
M23 is increased compared with BFS on its own. Therefore, the reason
for the improved fluidity of ECM by the addition of M23 is because of
the adsorption of M23 onto OPC and BFS to which Ca2 + has been
adsorbed, so both particles are dispersed.
Fig. 12 shows the amount of adsorption of PCE M9, in which the de-
gree of polymerization of the ethylene oxide side chains is 9 and the
number of functional groups is small, onto ECM, BFS, and OPC, and the
fluidity of OPC and ECM pastes to which M9 has been added. Unlike
M23, the amount of adsorption onto OPC is remarkably small. As the
dosage of M9 increases the apparent viscosity reduces, but its value is
greater than that of M23. In ECM, the improvement in fluidity using
M9 is greater than for OPC. Therefore, M9 has almost no adsorption
onto cement, but is adsorbed onto BFS to which Ca2+ is adsorbed, and
hence the fluidity of ECM paste in which BFS particles are mainly dis-
persed is improved.
Accordingly, the completely different adsorption behavior of PCE
onto OPC and BFS observed by the authors and Ohta et al. is caused by
the molecular structure of PCE superplasticizers used [75,81]. Also,
40
35 A(10000)
T1 / hr
25 0.1
20 0.15
15 0.2
10
5 plain
0
0 2 4 6 8
.
Fig. 16. Influence of Mg(NO3)2·6H2O on the hydration of cement with GLNa.
Ohta et al. reported that the polymer had a high ratio of side chains of
high density. Hence the proportion of oxygen in the molecular structure
was low so the number of carboxyl groups that can adsorb was small
[81]. In addition, under an alkaline environment, it was difficult for
the molecular chains to extend, so adsorption onto the cement surface
was difficult.
Therefore, in blended cement such as ECM with low OPC clinker [82],
adsorption is mainly onto BFS rather than OPC, and hence superplas-
ticizers with a high ratio of side chains are considered useful in estab-
lishing properties and initial strengths.
3.2. PCE superplasticizers for high durability concrete
3.2.1. PCE for ultra-high strength cement with silica fume
Ultra-high strength concrete with ultra-fine particles such as silica
fume (SF) can also be used as high durability material [83]. By ensuring
durability for a long period of time, the life of cementitious materials
and the service life of structures can be extended, thereby reducing
the environmental load. In Japan, ultra-high strength concrete is used
in combination with low heat Portland cement, which has low C3A
and high C2S content. There is then good fluidity and no concerns over
reduction in long-term strength due to temperature rises and SF. Also,
SF cement is used in which both are blended in advance. Naturally,
PCE plays an important role. PCE-type superplasticizer containing cat-
ionic groups with high dispersion performance in low water powder
has been proposed as dispersing agent for high strength [7]. It has
been reported that the amount of adsorption onto the cement is
Residual concentration of GLNa / mass%
5 0.02
4
0.015
. 3
0.01

30
B(18900) 2
C(29500)
25
0.005
20 1
15
10
5
0 0
0 1 2 3 4
0
0 0.2 0.4 0.6 0.8 1 .
Dosage of Superplasticizer / mass%
Fig. 17. Influence of Mg(NO3)2·6H2O on the residual concentration of GLNa and the
Fig. 15. Residual concentration of PCE superplasticizers in liquid phase. specific surface area of hydrated samples.
92 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99

Fig. 18. The hydrostatic pressure as a function of specimen age for (a) portlandite and (b) ettringite, calculated using the saturation index of solid phase in pore solution with or without
SRA. Adapted from [117].

increased by introducing cationic groups [84]. In ultra-high strength
concrete with SF, the dispersibility of ultrafine particles is important,
and for allyl-ether-based PCE and MAA ester-based PCE, it has been re-
ported that both are easily adsorbed onto SF, and the latter is easily
adsorbed onto hydrating cement [85]. Therefore, in high strength ce-
ment systems using SF, a mixture of both of these dispersing agents is
effective. In addition, it has been reported that sodium gluconate
(GLNa) is easily adsorbed onto SF, so this combination is effective [86].
The authors have already reported that for ultra-high strength
concrete with SF, it is difficult to ensure fluidity unless about 50 to
60% of the PCE remains in the liquid phase; hence non-adsorbed poly-
mer is important [87]. When cement only is used with a water cement
ratio of about 0.3, the action of the non-adsorbed polymer in the liquid
phase has been reported as important [88]. Also, when low heat
Portland cement which has low C3 and SF is used and the water to pow-
der ratio is 0.16, the effect of the non-adsorbed polymer is significant
[83].
3.2.2. Effect of non-adsorbed PCE
The three types of PCE were used as shown in Table 2 [89]. The
fluidity has been reported to vary depending on the quality of the SF,
which is an industrial by-product. To eliminate the effect of this proper-
ty, fused silica having an average particle diameter of 106 nm and a
shape that is almost spherical was used as model for ultrafine particles.
The mass ratio of low heat Portland cement and fused silica was 9:1 and
the packing fraction of this sample was 0.9 as obtained in calculation of
packing simulations [90].
Fig. 13 shows the relationship between each PCE dosage and the ap-
parent viscosity of paste for a water/powder ratio of 0.16. The lowest
value obtained for the apparent viscosity was about 0.6 mass% for
each of the superplasticizers used. The paste to which PCE-A was
added having the smallest molecular weight exhibited fluidity from
the lowest dosage. In contrast, the worst fluidity results were obtained
from PCE-C with the highest molecular weight. Fig. 14 shows the
amount of adsorption of each type of PCE onto the powder. The amount
of adsorption was greatest for PCE-C, with the values becoming smaller
in the order PCE-B, PCE-A. At normal water/cement ratios, dispersion is
related to the adsorption of PCE or the size of the molecule, the disper-
sion action of particles being greater the larger the amount of adsorp-
tion and the larger the molecule. However, at low water/powder
ratios, the relationship between the amount of adsorption and the size
of the molecule to the fluidity of the paste has an opposite tendency.
In other words, the paste to which PCE-A was added for which both
the amount of adsorption and the size of the molecule were small exhib-
ited the best fluidity. Fig. 15 shows the relationship between the con-
centration of PCE remaining in the liquid phase and the dosage. For a
water/powder ratio of 0.16, the calculated concentration in the liquid
phase remained the same. Conversely, the residual concentration of

Fig. 19. Application of shrinkage reducing agent in Gongbo Gorge hydroelectric station to mitigate dying shrinkage. Adapted from [119].
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 20. Hydration and expansion models of MgO- based expansive agent (MEA) with (a) high reactivity and (b) low reactivity. Adapted from [124].
PCE-A showed the largest value of adsorption. For a paste with a low
water/powder ratio to flow, non-adsorbed polymer in the liquid phase
needs to be greater than a certain value. This is believed to be due to fric-
tion between polymer particles remaining in the liquid phase. By fur-
ther examining the effect of non-adsorbed polymer from the point of
view of shape and size of the molecules in the liquid phase, designing
the ideal PCE molecule for ultra-high strength concrete with SF may
be possible. In addition, analyzing the interaction of the polymer–poly-
mer surface or adsorbed polymer and non-adsorbed polymer is neces-
sary, as is shape and size of the polymer [91,92].
3.3. Fresh concrete sludge recycling system using retarders
Various organic and inorganic retarders are known, but the retarders
used in practice are hydroxylic acid salts and saccharide derivatives. The
mechanisms of these retarders have long ago been classified by Young
[93], there being four categories: adsorption, precipitation, nucleation
control, and complexing. Also, these mechanisms have been organized
following the recent research by Cheung and others [94]. They sug-
gested that the modeling of retarders for chelating, poisoning of
nucleation and growth by CH or C–S–H is necessary to clarify the mech-
anisms. On this point, when nitrilotris(methylene) triphosphonate is
added the precipitation of Ca salts is generated and hydration of the
cement is suppressed. However, when sodium hexametaphosphate is
added, soluble Ca complexes are generated, so the precipitates are dis-
persed and retardation is suppressed [95]. The development of such a
new retarder is useful in clarifying the action of retarders.
Retarders are very useful for low carbon concrete systems. Gluco-
nate salts are one of the main components of retarders in technology
using sludge generated at ready mix concrete factories as sludge
water when producing new concrete. If sludge water is added to con-
crete, the fluidity of the concrete is reduced and the mechanical strength
is decreased. To counter this behavior, a method has been proposed to
temporarily halt cement hydration in sludge water using a retarder
such as GLNa. In this method, even if cement is replaced with sludge
solids at ratios of 5–10%, the properties of the concrete are virtually
unchanged compared with concrete without sludge [96]. The retarded
cement in the sludge water starts to hydrate again when mixed with
new cement during production of the concrete.
In this method, about 80% unreacted cement remains, and can
be recycled. Therefore, this concrete system falls under the category of
low-carbon technology. It is necessary to obtain a method of rapidly
and conveniently measuring the amount of cement having hydration
activity in sludge water from the evening of the previous day up to
the morning of the following day at a concrete factory or a ready-
mixed concrete plant. Hydration of the cement in the sludge water is
halted using a retarder. There is a very high correlation between the
93
amount of cement (C3S) remaining in sludge water and the integrated
heat of hydration for rehydration over a 24 h period. It is possible to de-
termine the amount of cement by measuring the heat liberated using a
conduction calorimeter. However, while retarders stop cement hydra-
tion, a method is needed to restart GLNa hydration and to develop a sys-
tem to determine the amount of cement by predicting the heat of
hydration for a 24 h period from the hydration reaction in about 10 h.
Fig. 6 shows the effect of Mg(NO3)2·6H2O [97] on the heat of hydra-
tion of cement in sludge water to which GLNa was added. T1 is the time
at which cement exhibits the maximum rate of heat liberation. OPC in
suspension with a water/cement ratio of 4.0 was used as a model sludge
water. T1 of plain paste is about 11 h (Fig. 16).
T1 of paste is prolonged by addition of GLNa. This is because GLNa is
adsorbed onto the surface and hydration is suppressed. Also, control of
the reaction with cement is possible by controlling the GLNa dose. If
Mg(NO3)2·6H2O is added to this and if for example the added dosage
of GLNa is 0.1 mass% and that of Mg(NO3)2·6H2O is 2.0 mass%, then T1
is 11 h; a value of T1 that is virtually the same as that of plain paste.
From the above results, if a portion of the sludge water in which the
hydration is controlled by GLNa is sampled and Mg(NO3)2·6H2O
added to it, GLNa retardation is stopped, and the heat of hydration can
be measured. Also, in this recycling system, the residual concentration
of GLNa in sludge water is controlled, so the quantity of Mg(NO3)2·6H2O
added can be determined based on this residual concentration.
Fig. 17 shows the variation in the residual GLNa concentration of
the liquid phase and the specific surface area of the solid component
of the sludge water when Mg(NO3)2·6H2O is added to sludge water
to which 0.1 mass% GLNa has been added. When the dosage of
Mg(NO3)2·6H2O is increased, the GLNa concentration in the liquid
phase is dramatically reduced, and the specific surface area rapidly
increases. When Mg(NO3)2·6H2O is added, a gel-type hydrate, as-
sumed to be Mg(OH)2 , is formed, and the specific surface area of
the solid component in the sludge water increases significantly.
The residual GLNa remaining in the liquid phase is adsorbed into
this generated hydrate, and the residual concentration of GLNa in
the liquid phase is reduced. In this way, we infer that adsorbed
GLNa on the cement is released, hydration suppression stopped,
and cement hydration is restarted.
Next the heat of hydration of the cement that was released from the
suppression of the hydration reaction is measured with a conduction
Table 4
Heat liberated in cement over one and two-day periods (J/g).
Time 24 h 48 h
Actual measurement 162.2 233.8
Predicted value 163.5 223.0
94 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Table 3
Replacement of joints between fresh and old concrete in diversion tunnel of Xiangjiaba
Dam, monitored in field condition.
Dosage of MgO Replacement of joints/mm
Maximum Minimum
0% 1.29 0.51
4% 0.63 0.02
5% 0.25 −0.12
calorimeter. The 24 h heat of hydration is predicted from measurement
results taken at about 10 h; it is necessary to obtain the amount of
cement from this value. A model for simulating the initial reaction of ce-
ment has been proposed by Tomosawa [98]. The rate of heat liberation
of cement measured by conduction calorimeter can be derived from this
model. Using Tomosawa's equation (1), it is possible to substitute the
amount of reactant of the various types of Portland cement for the
heat liberated, and to determine each of the parameters from the
amount of heat generated in 10 h [99]. In addition, it is possible to esti-
mate the rate of heat liberated over periods of about 24 h using these pa-
rameters and Tomozawa's equation. Table 2 lists the results. The actual
measurements and the estimated value for a 24 h period correspond
well, but the actual measurements for the 48 h period is slightly larger
than estimated values. This is caused by the hydration of belite. If a
part of the sludge water is sampled in which the hydration of cement
has been stopped by the addition of GLNa, and Mg(NO3)2·6H2O is
subsequently added, the hydration of cement is restarted. The heat
liberated from this sludge water is then measured for up to about
10 h. There is a strong correlation between the amount of heat
liberated and the amount of unreacted cement. Hence from this
measurement, it is possible to evaluate the amount of cement
remaining in the sludge water. From this test system, it is possible to
measure the amount of cement in the sludge water in which the
hydration was controlled, up to the time of producing concrete the
following morning [99].
4. Chemical admixtures for durability improvement and their
application in China
4.1. Air entraining agents
Since the air-entrained concrete was developed in the mid-1930s,
air entrainment has been recommended for nearly all concretes, princi-
pally to improve freeze–thaw resistance when exposed to water and
deicing chemicals. Most air-entraining admixtures consist of one or
more of the following materials: vinsol resin, saponin, sulfonated hydro-
carbons, and synthetic alkyl-aryl ethoxylate materials. The mechanism
of air entrainment was fully reviewed by Du [100], which helped to
Fig. 21. Application of CaO–MgO based expansive agent in Xiangjiaba Dam.
understand the role of air entraining agent in air bubble production
and stability process.
The improvement of freeze–thaw resistance of concrete is a primary
benefit of air entraining agent, and its mechanism was firstly proposed
Average by Powers and his co-workers [101–103]. More recently, based on the
theory of Powers and Helmuth, it was suggested that the ice crystals
0.94
0.24 formed in the voids of air-entrained concrete create suction in the sur-
0.13 rounding mesopores which could offset the crystallization pressure of
ice, resulting in a net contraction [104, 105]. The contraction of samples
was quantitatively predicted by poromechanics [106]. This contraction
accounts for the beneficial effect of air entrainment on freeze and
thaw. Besides improving freeze–thaw resistance, air entraining agents
also improve the workability of fresh concrete by mitigating segregation
and bleeding, especially for self-consolidating concrete [107]. With the
advancement of computer science, the entrained air-void parameters
in hardened concrete can be automatically determined based on
image analysis [108–110]. However, there seems still a potential oppor-
tunity to improve or at least refine methods for assessing the quality of
air entrainment in concrete [111], especially for air bubble size and dis-
tribution in fresh concrete. This could be of great significance for under-
standing and controlling the air-void system in field concrete.
Owing to its benefits in both durability and workability, air
entraining agents have been applied in all kinds of concrete construc-
tion projects in China.
4.2. Shrinkage reducing agents
Since their introduction approximately three decades ago, shrinkage
reducing admixtures have been extensively advocated as a method for
reducing shrinkage and cracking in cementitious systems [112–114].
Shrinkage reducing admixtures are composed of non-ionic organic sur-
factants, which can be classified as monoalcohols, glycols, alkylether
oxyalkylene glycols, and grafted polymers comprising hydrophilic side
chains and hydrophobic spacer units. The addition of these organic sur-
factants is designed to decrease the surface tension of pore solution,
then correspondingly the capillary stress due to the loss of moisture ac-
cording to the Kelvin–Laplace equation. The decreasing of capillary
stress will then lead to a reduction of drying shrinkage for cementitious
materials. Besides drying shrinkage, studies had examined the effect of
SRAs on plastic shrinkage and autogenous deformation at early ages
[115,116]. These studies indicated that SRA could also reduce capillary
stress development and water evaporation in plastic systems. Sant
[117] indicated that SRA increased the portlandite oversaturation level
in solution, resulting in higher crystallization stresses which could
lead to an expansion, as shown in Fig. 18.
It was also pointed out that the addition of SRA retarded the hydra-
tion of C3S. This retardation had been previously attributed to the re-
duced alkali content in the pore solution in the presence of the SRA
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 22. (a) 3D representation of the superabsorbent polymer particles within the cement paste sample at approximately 4, 8, 12.5 and 20.5 h after mixing; (b) average signal from the SAP
particles as a function of time, normalized to the signal at 3 h. Adapted from [133].
[118]. Eberhardt [113] suggested that this retardation effect was proba-
bly due to the adsorption of molecules onto portlandite which limited
the growth rates of crystals.
The shrinkage reducing agents are widely used in construction pro-
jects of China, especially tunnels and hydroelectric station, in which
concretes of higher cracking resistance are required. Application of
shrinkage reducing agent in Xuanwu lake tunnel, Jiuhua mountain tun-
nel (Nanjing), Dushu lake Tunnel (Suzhou), and Li lake tunnel (Wuxi)
showed that the shrinkage and cracking risk of concrete were efficiently
reduced. For Gongbo Gorge hydroelectric station which is located in the
east part of Qinghai–Tibet plateau, the shrinkage reducing agent was
also applied to reduce the drying shrinkage and cracking risk of large
scale panel concrete. According to the data monitored under field condi-
tion (Fig. 19), the drying shrinkage of concrete containing shrinkage re-
ducing was decreased by 40% after 180 days.
4.3. Expansive agents
Expansion produced due to the hydration of expansive components
contained in cement clinker, such as calcium sulfo-aluminate, free calci-
um and periclase, has been widely used to compensate for the shrinkage
of the cementitious materials [120,121]. Based on the types of expansive
component selected, expansive agent can be simply classified as CaO-
based, ettringite-based and MgO- based expansive agent.
4.3.1. CaO- and ettringite-based expansive agents
CaO- and ettringite-based expansive agents have been successfully
applied in engineering projects to produce shrinkage compensated con-
crete. The crystallization pressure generated from oversaturation of
30
Control
25
Water evaporation / g
20
15
10
Monolayer
5
0 0
0 25 50 75
Time (min)
Fig. 23. The effect of monolayer water evaporation retardant on the water evaporation amount and plastic shrinkage of mortars. Adapted from [143].
95
crystals (portlandite and ettringite) would cause significant expansion
to compensate the shrinkage. However, due to the fast hydration of
CaO and the relatively high solubility of portlandite, the application of
CaO-based expansive agent in normal concrete has been limited.
Ettringite-based expansive additives can produce rapid expansion at
early age, mainly within 14 days. Researchers also tried to process
high-temperature carbonation pretreatment on CaO-based/ettringite-
based expansive agent, in order to suppress the early age expansion
and reduce the potential loss [122]. However, there remains some chal-
lenges. The effectiveness of ettringite expanding agent relies on the free
access of outer supplied water, which is not able to be fully ensured in
the high performance concrete due to the low permeability. Moreover,
the ettringite would be decomposed when the temperature is higher
than 70 °C, which becomes a limitation for the usage in mass concrete
with high temperature rise [123].
4.3.2. MgO- based expansive agent (MEA)
The effect of shrinkage compensation by MgO was found by accident
in China about 40 years ago, when the thermal shrinkage of mass con-
crete in the Baishan Dam was effectively compensated by the expansion
generated from the slow hydration of periclase in the cement clinker. In
comparison to the traditional expansive agents, MgO has its own advan-
tages: (1) hydration product Mg(OH)2 is chemically stable, (2) relatively
low water is required for the hydration of MgO, and (3) the expansion
property is designable. The hydration and expansion behaviors of MEA
are influenced by its microstructure, particle size, dosage in concrete,
curing temperature, relative humidity, and also the supplementary ma-
terials used in concrete, for example the type of fly ash [121,124,125].
1400
Control
1200
-6
Plastic shrinkage / 10
1000
800 Monolayer
600
400
200
100 0 50 100 150 200
Time / min
96 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
Fig. 24. Application of water evaporation retardant in (a) airport pavement in north-west China. (b) Girder and track slab of Lanzhou–Urumqi High speed railway.
Fig. 20 shows the hydration and expansion models of MEA with high
and low reactivity.
Considering the various expansion process of expansive agents, MgO
and CaO with different hydration relativities were mixed intentionally
to acquire a combined effect on shrinkage compensating [126]. The
results indicated a promising foreground of new expansive system in
controlling both early age and long term volume stability for concrete.
4.3.2.1. Application in China. MEA was mainly used in dam concrete to
compensate the thermal shrinkage of the mass concrete, resulting in
the minimization or complete elimination of the relatively expensive
temperature control measures in construction. In those construction
projects, the MgO concrete was mainly used in the restrained regions
of gravity dam, roller concrete, backfill concrete of diversion tunnel,
and sometimes for the whole dam concrete. Table 3 shows a case
study of MEA applied in diversion tunnel of Xiangjiaba Dam (Yunnan
and Sichuan province, Fig. 21). The data monitored in field shows that
the addition of MEA could compensates the thermal shrinkage of large
scale concrete, resulting in a decrease of replacement of joints between
fresh and old concrete (see Table 4).
4.4. Curing agents
4.4.1. Superabsorbent polymers
High-performance concrete (HPC) with low water to cement ratio
experiences a considerable chemical shrinkage and self-desiccation
during its hydration process, resulting in a high autogenous shrinkage
during hardening. Application of superabsorbent polymers (SAP)
which were first proposed by Jensen and Hansen [127,128] has been
proved to be effective to mitigate autogenous shrinkage of HPC [129].
SAPs are cross-linked polyelectrolytes which start to swell upon con-
tact with water or aqueous solutions resulting in the formation of a hy-
drogel. They can be produced through either bulk polymerization or
inverse suspension polymerization. For its application in concrete,
SAPs absorb pore solution during mixing of concrete and release it
when cement paste self-desiccates. The water released from SAPs
would then help to prevent self-desiccation and reduce the autogenous
shrinkage of concrete. Therefore, the kinetics of water migration in and
out of the SAP is essential for understanding and optimizing internal
curing of concrete. Various techniques have been applied to monitor
the water adsorption and desorption behaviors of SAP in pore solution
[130–132]. Trtik [133] applied neutron tomography to monitor the
water adsorption/release of large SAP particles in a hydrating cement
paste with w/c of 0.25 in the first day of hydration. The SAP started emp-
tying around setting time and released about 80% of the water in the
first day of hydration (Fig. 22). These technologies seem to be quite
helpful to understand the mechanisms of water release in cement
pastes and the distance of water transport from SAP.
Recently, the influence of SAPs on workability, mechanical proper-
ties and durability was investigated [134–141]. It was pointed out that
the usage of SAPs in a proper way would not alter the mechanical prop-
erties of concrete. While the workability and durability of concrete are
strongly dependent on the chemical structure, size and dosage of SAPs
in the system.
For SAPs, most studies have been conducted in the laboratory while
very few field applications can be found. The SAPs have been successful-
ly applied as internal curing agent for the concrete shear wall and shores
in the basement of Yintai wisdom Garden (Wuhan) in 2009. The shear
wall in basement with a length of 110 m, height of 4.5 m and thickness
of 0.3 m was casted by pump concrete containing SAPs with a slump loss
of 220 mm. It has been proven that the usage of SAPs will improve the
crack resistance of concrete and meanwhile save the cost of external
curing.
4.4.2. Water evaporation retardant
Plastic shrinkage cracks of concrete are generally attributed to the
rapid evaporation of water, which creates menisci and high tensile
stresses in the capillary water near the surface, especially under the
conditions of high temperature and low humidity. Therefore, the most
effective way to prevent plastic shrinkage cracking is to mitigate
water evaporation on plastic concrete surface. However, conventional
methods such as spraying water, plastic cover, wet burlap and chemical
membrane technology are proved to be not appropriate in specific cir-
cumstances, for example the shortage of water supply and requirement
on appearance. According to the study by Li [142,143], the monolayers
constructed from amphiphilic molecules formed on the surface of plas-
tic concrete has been applied to reduce water evaporation and therefore
the plastic shrinkage (Fig. 23).
 J. Plank et al. / Cement and Concrete Research 78 (2015) 81–99
The water evaporation retardant prepared from poly(lauryl methac-
rylate) emulsions was firstly applied in Taizhou Bridge across Yangtze
River in 2009 [144]. Compared to the control sample, the plastic-
shrinkage cracks and crust of concrete blocks covered with monolayer
were successfully eliminated, which ensured an improved durability
for the construction. Later on, these monolayers were applied in con-
crete pavement of airport and girder of Lanzhou–Urumqi high speed
rail, both located in the north-west region of China, as shown in
Fig. 24. The weather in north-west China is characterized as high tem-
perature, low humidity and strong wind. Compared with conventional
curing methods such as plastic cover, the application of water evapora-
tion retardant shows an improved performance in reducing water evap-
oration and plastic shrinkage, and more importantly appears to be
energy and labor saving in that region due to the shortage of water
supply.
5. Conclusions
Topics for chemical admixtures such as PCEs and retarders are de-
scribed. In addition, the improvement of durability was summarized
from the viewpoint of the change in microstructures with admixtures.
Firstly an overview of current PCE compositions and synthesis
methods is provided, followed by novel applications for PCEs including
C–S–H-PCE nanocomposites and a description of still unresolved chal-
lenges for PCE technology such as e.g. robustness against various ce-
ment compositions or improved tolerance for clay minerals occurring
as impurity in aggregates. The invention of PCE superplasticizers in
1981 has brought about numerous technological advances which are
indispensible for the modern concrete industry. It presents a perfect ex-
ample for the key role which the chemical industry and the admixtures
developed there play in modern building materials. In the future, more
contributions from the chemical and admixture industry to PCE tech-
nology can be expected.
Secondly, the action mechanisms of retarder and the recycling sys-
tem of sludge water by using retarder are introduced. It is demonstrated
that combinations of gluconate and magnesium nitrate allow successful
recycling of fresh concrete sludge. Furthermore, the improved perfor-
mance of PCE resulting from fluoride ion addition during clinker calci-
nation and the effectiveness of PCE polymers in blended cements are
presented. The amount of adsorption of PCE onto blended cements is af-
fected by the types of blending materials, the replacement rates of the
blending materials, the base cement, and the molecular structure of
the PCE. For low calcination temperature cement, the fluidity of cement
paste with PCE is reduced by adding fluoride ions, but the amount of
superplasticizer adsorbed is increased. The formation of ultra-fine parti-
cles is influenced. DSP materials can also be used as high durability
materials. At low water/powder ratios, the relationship between the
amount of adsorption and the size of the molecule to the fluidity of
the paste has the opposite tendency as in the case of normal water to
powder ratio. In high strength or high durable cement and concrete it
is necessary for non-adsorbed polymer in the liquid phase to be greater
than a certain amount.
The recent research progress of air entraining agent, shrinkage re-
ducing agent, expansive agent and curing agent, and their application
in construction projects of China are reviewed. Better insights on the
working mechanism of these chemical admixtures are provided based
on the advancement of modern techniques in microstructure analysis.
Owing to the extensive development of infrastructure construction in
China, these innovative materials and technologies have been applied
in field conditions and proved to be effective in improving the durability
of concrete structure. Despite there are still many unclear areas in the
knowledge of above mentioned chemical admixtures and their impact
on the microstructure and related property of concrete, there is increas-
ing interest in the use of chemical admixtures to improve durability of
concrete which highlights the demand for more research progress and
its transformation into field application.
97
Acknowledgments
E. Sakai gratefully acknowledges the support of this work by Garce-
Chemicals K.K., NOF Corporation, Takemoto Oil & Fat Co., Ltd., and
Nippon Shokubai Co., Ltd.
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