Polycarboxylate Ether
High-Range Water-
Reducing Admixtures
What have we learned in the past 25 years?
by Ara A. Jeknavorian
A
lthough the first patent for a polycarboxylate ether
(PCE) high-range water-reducing admixture
(HRWRA) was issued in 1981,1 PCE admixtures were
not fully commercialized in the North American concrete
industry until the mid-1990s. Since then, however, PCE
admixtures have been widely applied to dramatically extend
the capabilities of concrete mixtures. Self-consolidating
concrete, ultra-high-strength concrete, and slump retention
beyond 2 hours without significant extension of setting time
are a few of the capabilities that have been made possible.
The rapid adoption of PCE HRWRA since commercialization
can be partially attributed to the industry’s successful use of
naphthalene sulfonate formaldehyde condensate sulfonate
(NSFC) and melamine sulfonate formaldehyde condensate
(MSFC) admixtures, which were introduced in the 1960s
and mid-1970s, respectively.2 This experience, along with
the improved rheology provided by PCEs, further
encouraged the production of mixtures with high flowability
or mixtures with low water-cementitious materials ratio (w/
cm) and enhanced workability. This article reviews the
diverse performance attributes of PCEs that have been
demonstrated over the past 25 years, as well as the
opportunities they provide to meet current and future needs
of the concrete construction industry.
Early Market HRWRAs
ASTM C494/C494M, “Standard Specification for
Chemical Admixtures for Concrete,” was revised in 1980 to
include a Type F HRWRA and Type G retarding HRWRA.
Even prior to the introduction of PCE products, the concrete
industry had already begun to realize the benefits of higher-
flow concretes and increased durability at lower w/cm made
possible by HRWRAs. However, the steady penetration of
NSFC- and MSFC-based products into the concrete
construction market established cost-performance targets as
well as certain performance shortcomings that polycarboxylates
would need to overcome to gain acceptance by concrete
producers and specifiers.
The Polycarboxylate Family
The term “polycarboxylate” represents an almost unlimited
number of water-soluble polymers that can be designed to
impart a wide range of specific properties to concrete
mixtures. Consider the basic repeating unit of the general
methoxypolyethylene glycol (MPEG) PCE structure in Fig. 1.
CH3
CH2 CH CH2 C
m n
O C CH2
O
CH2
Na
O CH2 CH2 O k H
Fig. 1: Simplified version of a general-purpose PCE polymer structure,
denoted as PC1 in this article. The –COONa portion of the polymer is
responsible for adsorption onto the surface of a cement particle,
while the –(CH2-CH2-O)– pendant group causes the dispersion of
flocculated hydrating cement particles and a subsequent slump
increase. The m to n ratio (m:n) controls the rate of polymer
adsorption and slump increase. The k value impacts the amount of
PCE adsorption, and thus the dosage rate for a given degree of
workability. For typical ready mixed concrete applications, m:n
ranges from 2.5 to 3.5 and k ranges from 22 to 50. For typical
precast concrete applications, m:n ranges from 3 to 7 and k ranges
from 50 to 70
www.concreteinternational.com | Ci | OCTOBER 2019 49
Such polymers in their full General purpose applications. A primary attribute of PCE
macromolecular configuration are often In North America, PCEs have admixtures relative to NSFC and MSFC
called comb polymers, as they feature a become the dominant HRWRA admixture technologies is the much
charged backbone and uncharged side technology. Table 1 summarizes a lower dosage needed to achieve
chains (Fig. 2).3 The backbone is comparison of a general-purpose PCE comparable workability of cementitious
primarily composed of carboxylate HRWRA versus a typical calcium mixtures—typically 1/4 to 1/3 the
groups (chemically expressed as NSFC-based product, based on what has dosage on a mass of polymer by mass of
–COOH). The carboxylate groups are been learned from both extensive lab cementitious materials (cm) basis.
responsible for polymer adsorption on and field testing and commercial Another major performance advantage
cement surfaces, mainly through
electrostatic interactions with the cement
hydration reaction products. The side
chains are primarily in the form of
polyethylene oxide (PEO), which is
expressed as –(CH2-CH2-O-)k. PEOs are
not adsorbed on cement particles. They Side chain 30 nm
induce steric repulsive forces between
agglomerated hydrating cement
5 nm
particles,4,5 and these forces result in a
rapid breakup of flocs of particles that Backbone
normally form upon mixing of cement 30 nm 20 nm
with water. The release of the water tied Mw 50,000 Mw 61,000
up in the flocs causes an increase in the
workability of the concrete. Fig. 2: Schematic representations of PCE polymer backbone and pendant (side chain)
Subsequent to the introduction of structures, dimensions, and molecular weights (Mw): (a) a typical PCE for ready mixed
concrete applications is designed with a longer backbone and a reduced charge that enhance
so-called general-purpose PCE
the persistence of the admixture; (b) a typical PCE for precast concrete applications is
HRWRAs into the North American
designed to have an enhanced steric effect over a shorter time period and thus impart faster
construction market, chemists learned workability increase and rapid strength gain
how to design and associate polymer
structures with various performance
features requested by concrete Table 1:
technologists. As a result, many new General comparison between NSFC and PCE HRWRAs
PCE products have been introduced over Property/Performance NSFC, 40%* PCE, 30%*
the past 25 years. Considering that about Introduced 1960s Mid-1990s
80% of the PCE polymer is composed of Water reduction 8 to 20% 5 to 40%
the PEO pendant groups, much research
520 to 1300 mL/100 kg 130 to 520 mL/100 kg
has been conducted to identify pendant- Typical addition rate range
(8 to 20 fl oz/cwt) (2 to 8 fl oz/cwt)
group chemistries that improve
Nonlinear; highly dependent
manufacturing processes or performance Slump/dosage response
on cement chemistry
Linear; less cement dependent
attributes.6 Pendant groups have been
Preferred addition mode Delayed Mixing water or delayed
synthesized using, for example,
isobutenyl polyethylene glycol (IPEG), Slump life < 0.75 hour < 1.5 hour
allyloxy polyethylene glycol (APEG), Setting time Neutral/slightly retarding Neutral to less than NSFC
isobutylene alcohol polyoxyethylene ASTM C494/C495M Type F;
Compressive strength ASTM C494/C494M Type F
ether (HPEG), and vinyl ethers (VPEG). greater or equal to NSFC
Compatible w/AEAs Avoid SDBS† No restrictions
Structuring PCEs for Specific Function of w/c
Performance Properties Cohesiveness Overdose results in
Function of w/c
Some thixotropy
The ability of PCE polymers to segregation
impart diverse performance Magnifies any effect that
Air content sensitivity Neutral
characteristics to cementitious mixtures creates air
can be demonstrated with the following Possible bugholes and Reduced bugholes, uniform
Finishability
three generic types of PCE polymers: blotchiness surface
general purpose, slump control, and high *
Oven-dry residue, %
early strength. †
Sodium dodecylbenzene sulfonate

50 OCTOBER 2019 | Ci | www.concreteinternational.com

with PCEs is a shorter setting time associated with the
increased workability they provide.
Figure 3 shows the concrete slump versus initial setting
time plotted for four polymers: PCE, NSFC, a calcium
lignosulfonate, and corn syrup. The concrete mixture
comprised 362 kg/m3 cement, 163 kg/m3 water, 800 kg/m3
coarse aggregate, and 1020 kg/m3 sand (611, 275, 1350, and
1725 lb/yd3, respectively). The dosages of the polymers are
listed in Table 2. Note the lower impact on setting time per
increase in slump by PCE. The PCE HRWRA can help
produce higher early concrete strengths because it has
relatively small impact on setting time resulting from a lower
polymer coverage required on the cement surface.6 Another
major performance advantage of the PCE admixture is the
combination of longer slump life but with setting times
comparable to concretes admixed with an ASTM C494/494M
NSFC product. In Fig. 4, the average slump retention of a
PCE-based HRWRA was obtained from a compilation of 10
ready mixed concrete field tests. Slump retention was far
superior to that of an ASTM C494/C494M Type F NSFC
HRWRA, and it was comparable to that obtained using an
ASTM C494/C494M Type G retarding NSFC HRWRA.
However, the average setting times of the PCE admixed
concrete were about 2 hours shorter than the setting times
obtained with the Type G HRWRA.
One of the earliest projects where the combined slump-
retention setting-time advantage was observed was during
rehabilitation of a cement silo. The concrete producer was
required to use an ASTM C494/C494M Type G retarding
HRWRA to achieve adequate workability at the time of
concrete placement. Upon converting to a general PCE-based
product, the slipform equipment was able to move 30% faster
because it provided shorter setting times yet workability
remained adequate. In another early demonstration of the
capabilities of PCE-based admixtures, a PCE HRWRA was used
to improve the production of railroad ties (sleepers). An ASTM
C494/C494M Type A water reducer was replaced with a PCE
HRWRA, and this allowed material cost savings and faster
production, as the cement content was reduced by 40 kg/m3
(70 lb/yd3) and the sleeper separators were removed 90 minutes
earlier than with the Type A water reducer. This performance
was possible because of the water-reducing capability at
relatively low addition rates of the PCE-based admixture.
Admixtures must be accurately dosed and thoroughly
mixed prior to discharge of the concrete. PCE admixtures
provide the flexibility of being added with the mixing water at
the batch plant. This eliminates delays commonly associated
with adding NSFC-based admixtures at the jobsite.
PCE admixtures also provide more consistent results than
NSFC admixtures. In Fig. 5, the dosages of NSFC and PCE
admixtures required to obtain a 160 to 200 mm (6.5 to 8 in.)
slump in concrete mixtures produced with four different
250
NSFC Type G: 8.4, 10.2 hr
200
Slump, mm

10 250 150
PCE
NSFC
9 100
Lignin
PCE: 6.1, 8.3 hr
8 200
Corn NSFC Type F: 6.3, 8.4 hr
Slump, mm

50
Slump, in.

syrup
7
MSFC Type F: 5.75, 7.6 hr
6 150 0
0.25 0.5 0.75 1.00 1.25 1.5 1.75 2.0
5 Time, hr
4 100 Fig. 4: Slump as a function of time for concrete mixtures produced
with PCE, NSFC, and MSFC HRWRAs. Initial and final setting times
3 are indicated with each admixture label. While the Type G admixture
0 2 4 6 8 10 12 14 provided similar slump performance to the PCE, its setting times
Initial setting time, hr were extended by about 2 hours. While the Type F admixtures
Fig. 3: Concrete slump as a function of initial setting time for four resulted in about the same setting times as the PCE admixture, the
cement-dispersing technologies slump loss was much more rapid

Table 2:
Dosage and associated concrete slumps for four water-reducing admixtures
PCE NSFC Calcium lignosulfonate (lignin) Corn syrup
Dosage, % cm Slump, mm Dosage, % cm Slump, mm Dosage, % cm Slump, mm Dosage, % cm Slump, mm
0.00 100 0.00 100 0.00 100 0.00 90
0.06 150 0.25 150 0.20 160 0.15 140
0.12 200 0.37 210 0.30 175 0.25 180
0.15 240 0.45 220 0.50 220 — —

www.concreteinternational.com | Ci | OCTOBER 2019 51

 cements (refer to Table 3 for cement properties) were
017-I-II

normalized by the actual slump value and expressed as a

dosage-slump ratio. Note that the normalized dosage-slump
values are far more consistent for the PCE-based HRWRA
006-I

than for the NSFC HRWRA, which can be partially attributed

Cement

NSFC to the primarily steric repulsion mechanism of cement

PCE dispersion compared to the primary electrostatic interparticle
170-I

repulsive forces contributed by the NSFC polymer.

Slump control
051-I-II

Another class of polycarboxylates features a chemical

composition that is intentionally designed to have very
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
minimal impact on initial slump (Fig. 6). A built-in time-
Dosage/mm slump
release function allows the PCE polymer to become activated
Fig. 5: Slump response of concrete mixtures produced using four during mixing, and cement dispersion slowly begins causing
cements, plotted as a function of unit dosage of NSFC and PCE an increase in slump in a generally predictive manner as a
HRWRAs function of mixing time.
Figure 7 illustrates increasing addition rates of slump-
retaining polymer, denoted as PC4, to a concrete mixture
Table 3: featuring a relatively rapid-stiffening cement and a general-
Chemical composition, compounds, and properties of
portland cements and slag cement (% by mass unless
noted otherwise) R R R R
CH2 C CH2 C C C
Portland cement m n l
Compound Slag COO(EO)pR R COOR
COOM
or property 170-I 006-I 051-I-II 017-I-II cement
Fig. 6: Structure of a slump-retaining PCE. The proportions of m, n,
SiO2 21.11 19.00 20.09 21.81 34.3
and l control the activation rate and degree to which the polymer will
Al2O3 4.59 5.23 4.8 3.30 16.1 absorb onto cement surfaces and cause an increase in slump.
Fe2O3 3.30 2.51 3.09 3.48 1.2 Typically, l > m + n, and m:n can generally range from l.5 to 3.0. “M”
is normally sodium or potassium. “R” represents an alkyl group. EO
CaO 64.39 62.55 62.65 63.7 38.5 corresponds to an ethylene oxide unit, and p indicates the number of
MgO 2.86 2.81 3.72 3.24 8.3 EO groups, typically 20 to 50

SO3 2.32 4.21 3.01 2.42 0.2

10 250
Na2O 0.23 0.28 0.27 0.33 —
9
K2O 0.39 1.18 0.45 0.35  —
8 200
TiO2 0.19 0.20 0.25 0.22 —
7
Slump, in.

Slump, mm
P2O5 0.11 0.10 0.06 0.08 — 6 150
PC1 + PC4, 0.07%cm
5:45 setting time
Mn2O3 0.09 0.07 0.06 0.08 — 5
PC4
SrO 0.08 0.09 0.08 0.07 — 4 100
PC1 + PC4, 0.03%cm
5:30 setting time
C3S* 57 57 53 60 — 3 PC1, 0.12%cm
4:50 setting time
2 50
C2S *
17 12 20 18 — 0:00 0:15 0:30 0:45 1:00 1:15 1:30 1:45 2:00

C3A* 7 11 7 3 — Elapsed time, hr:min

Fig. 7: Impact of slump-retaining PCE, denoted PC4, on slump
C4AF* 10 8 9 11 —
retention of concrete mixtures comprising rapid slump-loss cement
Total alkali (cement, stone, sand, and water proportions were 445, 745, 1000,
0.45 1.06 0.58 0.56 —
Na2O eq* and 175 kg/m3, respectively). In all cases, PCE PC1 dosage was 0.12%
Free CaO* 0.58 0.19 0.64 0.67 — PCE actives by weight of cementitious materials (0.12% cm). In
addition to the PC1 dosage, PC4 dosages were 0.03 and 0.07% cm
L.O.I.
0.83 1.59 1.54 0.91 0.07 as noted. Initial setting times are also noted for each mixture
(950°C)*
containing PC1. While rapid slump loss associated with PC1 can be
C3A/SO3* 3.02 3.10 2.33 1.24 — overcome with successively higher dosages of PC4, slump can be
*
Compounds and properties per ASTM C150/C150M extended up to 2 hours with minimal impact on setting time

52 OCTOBER 2019 | Ci | www.concreteinternational.com

purpose PCE, denoted as PC1. The slump retention is Table 4:
progressively increased, with minimal impact on setting time. Properties of PC500 and PC1 PCE HRWRAs
Slump-retaining PCEs can be added separately to any
PCE designation PC500 PC1
concrete mixture to somewhat predictably extend slump
Ready mixed
retention as a function of cement chemistry and job conditions General application Precast concrete
concrete
(haul time, temperature, and cement alkali content).7
Total solids, % 30 35
Alternately, multiple slump-retaining PCEs can be formulated
with a general-purpose PCE to achieve a combined Defoamer effect Minor Minor
performance of both early strength and long slump life. COOH/PEO *
2 to 4 4 to 7
Testing slump-retaining PCEs under simulated job conditions PEO Mw 1000 to 2500 2000 to 3600
is required to determine the correlation between dosage and *
Ratio of Mw of carboxylate (backbone) and Mw of polyethylene oxide
slump retention for a given set of materials. (side chain) structures

High early strength

Another major variation of the PCE polymer structure— 8.0
namely, a relatively short backbone coupled with relatively PC1
long sidechains (Fig. 2(b))—has been found to be especially PC500
7.0

Initial setting time, hr

effective in enabling faster cement hydration per unit of slump
increase at a fixed w/cm. This performance is made possible
because of the high cement dispersion efficiency of these
so-called high-early-strength (HES) PCE polymers. Upon
adsorption, these polymers leave a very small footprint on the
cement surface, thus allowing more rapid cement hydration.
This effect of polymer structure on rate of cement hydration
has been observed from the setting time results for mortar
mixtures made with several blends of portland cement and
slag cement (Table 3) and two different PCE polymers: PC1
(general purpose) and PC500 (HES). The structural properties
of the two PCE polymers are reported in Table 4. Mortars
produced with PC1 had longer setting times than mortars
produced with PC500, and the differences increased with
increasing slag cement content (Fig. 8).
Strength Synergy with Calcium-Based Set
Accelerators
When PCE-based HRWRAs are used with set accelerators
and corrosion inhibitors comprised of calcium salts,
unexpected strength gains have been observed compared to a
similar concrete mixture admixed with an NSFC-based
product.8 This synergy in strength gain was first observed in a
concrete mixture containing a calcium nitrite-based corrosion
inhibitor. The producer also noted a 50% drop in the amount
of air-entraining admixture needed with the PCE-admixed
concrete. Quite often, changing from an NSFC HRWRA to a
PCE HRWRA can allow reductions in cement contents while
still meeting strength specifications. Interestingly, the strength
difference does not seem to be associated with increased heat
of hydration, but rather is related to a denser microstructure
produced by the polycarboxylate-based admixture.9
Surface Finish
Formed surfaces can be affected by the HRWRA type. For
example, a producer of precast concrete prison modules noted
a 70% reduction in bugholes and blotchy patches after
switching from an NSFC HRWRA to a PCE HRWRA. While
6.0
5.0
4.0
0, 0.13 16, 0.11 16, 0.15 40, 0.11 40, 0.15
Slag content and PCE content, %cm
Fig. 8: Initial setting time (per ASTM C403/C403M) for mortar
mixtures prepared with PCE HRWRAs PC1 and PC500 and cured at
22°C. Mixtures included 500 g cm (cement 051 plus slag cement—
refer to Table 3 for properties), 1350 g CEN-EN 196-1 standard sand,
and 200 g water (1.1, 3.0, and 0.4 lb, respectively). Slag cement
contents and PCE admixture dosages are indicated as % cm
the exact factors responsible for the improvement in surface
finish are not clear, it is understood that the PEO pendant
groups on the PCE polymer tend to attract water molecules
through hydrogen bonding and are therefore highly
hydrophilic. This behavior can result in increased
cohesiveness of the concrete (tendency to remain uniform),10
thus minimizing segregation that could create air and water
pockets as well as cause irregular levels of hydration of the
cement at the formed surface.
Special Applications
PCE technology has been customized for a very diverse
range of plastic and hardened concrete properties, allowing
suppliers and producers to create:
•• Zero-slump concrete mixtures for pervious concrete and
dry-cast concretes6;
•• Ultra-high-strength concrete mixtures11;
•• A grinding aid and performance-enhancing cement additive12;
•• Dispersants for nanomaterials such as nanosilica and
nano-CSH composites13;

www.concreteinternational.com | Ci | OCTOBER 2019 53

•• Gypsum slurry with reduced water content ; and
14
•• PCE technology
Shotcrete with enhanced rheology. 15
has enabled the construction of
remarkable concrete structures. Consider the 820 m (2690 ft)
Burj Khalifa skyscraper in Dubai, United Arab Emirates,
where parts of the structure required Grade C80 concrete
(80 MPa [11,600 psi]). One concrete mixture was produced
with a PCE HRWRA and a set-retarding admixture. The
resulting mixture had a slump life of 3 hours at ambient
temperatures up to 50°C (122°F), allowing it to be pumped
for a record height of 650 m (2130 ft).
Limitations
PCE technology does have some performance limitations.
Use of PCE- and NSFC-based products in the same concrete
mixture can result in rapid stiffening of the concrete and thus
should be avoided. Additional issues arise in managing air
content and minimizing the negative effects of clay fines that
may be present in aggregates.
Managing air content and quality
All PCE HRWRAs are formulated with one or more
defoamers. Without a defoamer system, a typical PCE
polymer can produce a relatively unstable air content of 5 to
10% in concrete mixtures. Admixture companies have done a
remarkable job in formulating water-insoluble defoamers with
PCEs and other components. For non-air-entrained concrete,
defoamer systems can help maintain air content below 2%.
A greater challenge can occur when concrete mixtures are
intentionally air-entrained, as the air-entraining admixture
(AEA) must overcome the air-detraining effect of the
defoamer.16 Even so, air-entrained concrete mixtures with
PCE admixtures have performed quite well in environments
subject to cyclic freezing and thawing.
In general, compared to NSFC-based HRWRAs, PCE-
based products can make AEAs more efficient, meaning a
lower AEA addition rate may be used to achieve the same air
content. While air-entrained concrete mixtures admixed with
PCE HRWRAs may possibly have slightly coarser air void
parameters than similar concretes with NSFC HRWRA,
spacing factor and specific surface values will generally
comply with ACI guidelines.16
Extra caution is warranted in controlling the air content in
concrete mixtures containing fly ash, as formulated defoamer
components have the potential to be absorbed by the unburnt
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54 OCTOBER 2019 | Ci | www.concreteinternational.com
carbon in ash.17 Variations in carbon content can cause
load-to-load changes in air content.
Minimizing the impact of clays
Unlike NSFC HRWRAs, a PCE polymer will readily and
irreversibly be adsorbed by certain clay fines that could be
present in various aggregate sources.18 Studies have shown
that the workability of PCE-treated mortar decreases at a
much faster rate than the workability of NSFC-treated mortar.
The backbone of the PCE polymer has been found to adsorb
on the surface of clay, and the PEO pendant groups can
intercalate within the clay layers.19 When clays are present in
certain sands, the dosage required for a PCE HRWRA can be
expected to be about 75% or greater than the dosage of an
NSFC HRWRA compared to the expected 1/4 to 1/3 the
amount on an admixture solids by mass of cement basis.
Therefore, if the required dosage of a PCE HRWRA were to
unexpectedly increase, the aggregate supply should be
checked for clay content.
The negative impact of clays can be mitigated by formulating
PCEs with sacrificial agents such as polyethylene glycols18 and
cationic surfactants.20,21 These agents can preferentially adsorb
on clay surfaces, thus reducing the capacity of clays to adsorb
the PCEs. The negative impact of clays can also be mitigated
through chemical modifications of the PCE polymer.22
Final Thoughts
Working with concrete technologists, HRWRA chemists
continue to modify the PCE polymer structure to achieve new
production and placement capabilities of concrete mixtures.
Significant focus is being placed on designing PCEs with:
•• Reduced clay adsorption;
•• Uniform response to variations in the chemistry of cm;
•• Reduced or zero surfactancy;
•• Reduced concrete viscosity at w/cm values below 0.30; and
•• Additional functionality such as shrinkage reduction.
Papers presented at recent conferences held in China and
Germany provide strong evidence that polycarboxylate
admixtures continue to be the subject of intense research and
development on these topics and more. Thus, though the
concrete industry has learned much about harnessing the
versatility and understanding the limitations of PCE-based
HRWRAs, further progress can be expected.
References
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R.J, “Understanding the Effectiveness of Polycarboxylates as Grinding
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Concrete Institute, Farmington Hills, MI, 2012, pp. 235-249.
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Note: Additional information on the ASTM and CEN standards
discussed in this article can be found at www.astm.org and www.cen.eu,
respectively.
Selected for reader interest by the editors.
Ara A. Jeknavorian, FACI, serves
the concrete construction industry
as an independent consultant on
the development and application of
chemical admixtures. Prior to starting
Jeknavorian Consulting Services,
Jeknavorian completed a 34-year
career as a Research Fellow with the
Construction Products Division of W.R.
Grace, Cambridge, MA. He holds 19 patents for concrete and
masonry admixtures and was responsible for polycarboxylate
product development with W.R. Grace. Jeknavorian is a member
of the American Chemical Society and a Fellow of ASTM
International, where he chaired the subcommittee on chemical
admixtures and served on ASTM Committee C09, Concrete and
Concrete Aggregates. He has authored 51 publications related to
chemical admixtures for concrete, and he has received several
industry awards for his contribution to standards and technology
development for concrete admixtures. Jeknavorian received his
PhD in analytical chemistry from the University of Massachusetts.
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