ADMIXTURE

What is admixture for concrete ?

A
dmixtures are the chemicals which are used in concrete preparation other than cement,
aggregate and water. These admixtures serve different purposes depending upon the
type of admixture. For increasing the strength of concrete using admixtures, the Water-
Cement ratio is needed to be reduced and use of a combination of Superplasticizer and a retarder
is required, to reduce the water content and increase the strength. Few plasticizers have some
percentage of retarded as well, so there is no need of using a retarder. Following are types of
admixtures which are used for different purposes.

- Air-entraining admixtures
- Water-reducing admixtures
- Plasticizers
- Accelerating admixtures
- Retarding admixtures
- Hydration-control admixtures
- Corrosion inhibitors
- Shrinkage reducers Fig. 6-1. Liquid admixtures, from left to right: antiwashout
- Alkali-silica reactivity inhibitors admixture, shrinkage reducer, water reducer, foaming agent,
corrosion inhibitor,
- Coloring admixtures
- Miscellaneous admixtures such as workability, bonding, damp proofing, permeability
reducing, grouting, gas-forming, ant washout, foaming, and pumping admixtures.
AIR-ENTRAINING ADMIXTURES

Air-entraining admixtures(IS9103:1999;
ASTM:C494 Type F&A) are used to
purposely introduce and stabilize
microscopic air bubbles in concrete. Air-
entrainment will dramatically improve the
durability of concrete exposed to cycles of
freezing and thawing.

Air-entrained concrete contains minute air

bubbles that are distributed uniformly
throughout the cement paste. Entrained air can be produced in concrete by use of an
air-entraining cement, by introduction of an air- entraining admixture, or by a
combination of both methods. Air-entraining cement is a Portland cement with an
air-entraining addition interground with the clinker during manufacture. An air-
entraining admixture, on the other hand, is added directly to the concrete materials
either before or during mixing.

- Entrained air greatly improves concrete’s resistance to surface scaling

- The workability of fresh concrete is improved significantly, and segregation and bleeding are
reduced or eliminated.

The primary ingredients used in air-entraining admixtures are listed. Specifications and methods of
testing air-entraining admixtures are given.
WATER-REDUCING ADMIXTURES

Water-reducing admixtures are used to reduce the quantity of mixing water required to
produce concrete of a certain slump, reduce water-cement ratio, reduce cement content, or
increase slump. Typical water reducers reduce the water content by approximately 5% to 10%.
Adding a water-reducing admixture to concrete without reducing the water content can produce
a mixture with a higher slump. The rate of slump loss, however, is not reduced and in most
cases is increased. Rapid slump loss results in reduced workability and less time to place
concrete.

An increase in strength is generally obtained with water-reducing admixtures as the water-

cement ratio is cracks in concrete. Using a water reducer to reduce the cement and water
content of a concrete mixture while maintaining a constant water-cement ratio—can result in
equal or reduced compressive strength, and can increase slump loss by a factor of two or more .

- Water reducers decrease, increase, or have no

effect on bleeding, depending on the chemical
composition of the admixture.
- A reduction of bleeding can result in finishing
difficulties on flat surfaces when rapid drying
conditions are present.
- Water reducers can be modified to give varying
degrees of retardation while others do not signify
Reduced.
- For concretes of equal cement content, air
content, and slump, the 28-day strength of a
water-reduced concrete containing a water
reducer can be 10% to 25% greater than concrete
without the admixture.
- Despite reduction in water content, water-
reducing admixtures may cause increases in
drying shrinkage.
- Usually the effect of the water reducer on drying
shrinkage is small compared to other more
significant factors that cause shrinkage cantly
affect the setting time.
HIGH-RANGE WATER REDUCING ADMIXTURES

High-range water reducers, ASTM C 494 (AASHTO M 194) Types

F (water reducing) and G (water reducing and retarding), can be used to
impart properties induced by regular water reducers, only much more
efficiently. They can greatly reduce water demand and cement contents
and make low water-cement ratio, high-strength concrete with normal or
enhanced workability. A water reduction of 12% to 30% can be obtained
through the use of these admixtures. The reduced water content and
water-cement ratio can produce concretes with

- Ultimate compressive strengths in excess of 70 MPa (10,000 psi),

- Increased early strength gain,
- Reduced chloride-ion penetration,
- Other beneficial properties associated with low water-cement ratio
concrete
High-range water reducers are generally more effective than regular
water-reducing admixtures in producing workable concrete. A significant
reduction of bleeding can result with large reductions of water content; this
can result in finishing difficulties on flat surfaces when rapid drying
conditions are present. Some of these admixtures can cause significant
slump loss. Significant retardation is also possible, but can aggravate plastic
shrinkage cracking without proper protection and curing. This may be the
result of lower water cement ratios often associated with these concretes.
When the same chemicals used for high-range water reducers are used to
make flowing concrete, they are often called plasticizers or super
plasticizers
PLASTICIZERS FOR FLOWING CONCRETE

Plasticizers, often called superplasticizers, are

essentially high-range water reducers meeting
ASTM C 1017; these admixtures are added to
concrete with a low-to-normal slump and water-
cement ratio to make high-slump flowing
concrete (Fig. 6-9). Flowing concrete is a highly
fluid but workable concrete that can be placed
with little or no vibration or compaction while
still remaining essentially

Following are a few of the applications where

flowing concrete is used:
- thin-section placements
- areas of closely spaced and congested
reinforcing steel,
- tremie pipe (underwater) placements,
- pumped concrete to reduce pump
pressure, thereby increasing lift and
distance capacity,
- areas where conventional consolidation methods are impractical or can not be used, and
- for reducing handling costs. The addition of a plasticizer to a 75-mm
RETARDING ADMIXTURES

Retarding admixtures are used to delay the rate of setting of concrete. High
temperatures of fresh concrete (30°C [86°F]) are often the cause of an increased rate of
harden- ing that makes placing and finishing difficult. One of the most practical methods of
counteracting this effect is to reduce the temperature of the concrete by cooling the mixing
water and/or the aggregates. Retarders do not decrease the initial temperature of concrete.
The bleeding rate and bleeding capacity of concrete is increased with retarders. Retarding
admixtures are useful in extending the set- ting time of concrete, but they are often also used
in attempts to decrease slump loss and extend workability, especially prior to placement at
elevated temperatures.
Retarders are sometimes used to-
- offset the accelerating effect of hot weather on the setting of concrete;
- Delay the initial set of concrete or grout when difficult or unusual conditions of
placement occur, such as placing concrete in large piers and foundations, cementing
oil wells, or pumping grout or concrete over considerable distances;
- Delay the set for special finishing techniques, such as an exposed aggregate surface.

Concrete Admixtures: Accelerating:

Accelerating concrete admixtures are used to increase the rate of concrete strength
development, or to reduce concrete setting time. Calcium chloride could be named as the
most common accelerator component; however, it could promote corrosion activity of steel
reinforcement. Nonetheless, concrete best practices such as proper consolidation, adequate
cover and proper concrete mix design could prevent these corrosion issues. Accelerating
admixtures are especially useful for modifying the properties of concrete in cold weather.
Concrete Admixtures by Classification

Type of Desired effect Material

admixture
Accelerators (ASTM C Accelerate setting and early- Calcium chloride (ASTM D 98 and AASHTO M 144)
494 and AASHTO M strength development Triethanolamine, sodium thiocyanate, calcium formate,
194, Type C) calcium nitrite, calcium nitrate
Air detrainers Decrease air content Tributyl phosphate, dibutyl phthalate, octyl alcohol, water-
insoluble esters of carbonic and boric acid, silicones
Air-entraining Improve durability in Salts of wood resins (Vinsol resin), some synthetic detergents,
admixtures (ASTM C freeze-thaw, deicer, sulfate, salts of sulfonated lignin, salts of petroleum acids, salts of
260 and AASHTO M and alkali- proteinaceous material, fatty and resinous acids and their salts,
154) reactive environments alkylbenzene sulfonates, salts of sulfonated hydrocarbons
Improve workability
Alkali-aggregate Reduce alkali-aggregate Barium salts, lithium nitrate,
reactivity inhibitors reactivity expansion lithium carbonate, lithium hydroxide
Bonding admixtures Increase bond strength Polyvinyl chloride, polyvinyl acetate, acrylics,
butadiene-styrene copolymers
Corrosion inhibitors Reduce steel corrosion activity Calcium nitrite, sodium nitrite, sodium benzoate, certain
in a chloride-laden phosphates or fluosilicates, fluoaluminates, ester amines
Foaming agents environment
Produce lightweight, Cationic and anionic surfactants
foamed concrete with Hydrolized protein
Grouting admixtures low density
Adjust grout properties for See Air-entraining admixtures, Accelerators, Retarders, and
Hydration Suspend and reactivate cement Carboxylic acids
control hydration with stabilizer and Phosphorus-containing organic acid salts
admixtures activator
Pumping aids Improve pumpability Organic and synthetic polymers
Organic flocculents
Retarders (ASTM C Retard setting time Lignn Borx
494 and AASHTO M Sugas
194, Type B) Tartaric acid and salts
Shrinkage reducers Reduce drying shrinkage Polyoxyalkylene alkyl ether
Propylene glycol
Superplasticizers* Increase flowability of concrete Sulfonated melamine formaldehyde condensates
(ASTM C 1017, Type Reduce water-cement ratio Sulfonated naphthalene formaldehyde condensates
1) Lignosulfonates
Polycarboxylates
Superplasticizer* and Increase flowability with retarded See superplasticizers and also water reducers
Water reducer Reduce water content at least 5% Lignosulfonates
Hydroxylated carboxylic acids
Carbohydrates
Water reducer Reduce water content (minimum See water reducer, Type A (retarder is added)
5%)
Water reducer—high and retard
Reduce set content (minimum
water See superplasticizers and also water reducers
range—and retarder 12%) and retard set
(ASTM C 494 and
AASHTO M 194,
Water reducer— Reduce water content (between Lignosulfonates
mid range 6 and 12%) without retarding Polycarboxylates
Manufacturing process of concrete admixture

Fig : Flow Chart Showing manufacturing oF admixture

Key Point of manufacturing process

- Weighing of all RM separately as per composition follow by mixing for 45 Min.
- Checking the perameter like PH , specified Gravity .
- IF any problem regarding parameters modified it by respective material.
- Mix all the batches as per Dispatch requirement.
Manufacturing Process of SNF

Melting of
START Naphthalene at - 110
℃

Filtation for 5 min. to (GLS) Sulphonation of

confirm the melting of molten Napthalene by
Naphthalene adding sulfuric acid

Transfer complete Polymerization by

sulphonated mass from addition of
GLS to GLK formaldehyde

Control Kettle Temp. to Transfer batch from GLK

120 ℃ using hot water to neutralizer

Agitation and Filtration

for 30 min. followed by
transfer of filtered
produce to storage tank

Flow Chart Showing Manufacturing of SNF

 Cement and Concrete Composites20 (1998) 103-112
0 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0958-9465/98/.$19.00
ELSEVIER
PII:SO958-946.5(98)00071-l

Admixtures Used to Enhance Placing

Characteristics of Concrete
M. Collepardi
Enco Engineering Concrete, Spresiano (TV), Italy

Abstract INTRODUCTION

Placing characteristics of concrete can be Plasticizers and superplasticizers can be used in

enhanced by using plasticizing and supelplasticiz- concrete mixtures for three different purposes
ing admixtures without any change in the or a combination of these’:
wlater-cement ratio with respect to the plain mix-
1. to increase workability without changing the
ture. The main ingredients used in
mix composition in order enhance placing
superplasticizers are based on sulfonated mela-
characteristics of concrete (Fig. 1A).
mine formaldehyde (SMF) condensate or
2. to reduce the mixing water and the water-
naphthalene formaldehyde (SNF) condensate.
cement ratio (w/c) in order to increase
More recently, a new family of products, based on
strength and improve durability at a given
uclylic polymers (AP), has been proposed. These
workability (Fig. 1B);
polymers are more effective than those based on
3. to reduce both water and cement at a given
SMF or SNF in terms of lower base water-cement
workability in order to save cement and
ratio at a given slump and lower slump loss.
reduce creep, shrinkage and thermal strains
Moreover; the effectiveness of the AP-based super-
caused by heat of cement hydration (Fig.
plasticizers does not depend significantly on the
1C).
mode of addition, whereas the slump level of con-
crete mixes with SMF- and SNF-based admixtures In the present report, super-plasticizers will be
_ . ._
ic much higher with a delayed addition of super- examined primarily as admixtures to increase
plasticizer with respect to that of mixing water the workability level (Fig. 1A).
The dispersion of cement particles responsible for The main difference between plasticizers and
the fluidity increase, caused by the superplasticizer superplasticizers is in the extent rather than in
uddition, is not necessarily related to the electro- the type of performances. The slump increase at
static repulsion associated with zeta potential a given mix composition is about 150-200 mm
measurements, as it was found for SMF- and for the latter and about Xl-70 mm for the for-
SNF-based admixtures. For the AP-based super- mer. On the other hand, a super-plasticizer is
plasticizers, the polymer adsorption, rather than capable of reducing water requirements at a
the electrostatic repulsion, is responsible for the given slump by about 20-30%, whereas a plasti-
dispersion of large agglomerates of cement par- cizer can reduce water contents by only about
ticles into smaller ones, which results in a 5-12%.
remarkable increase in the fluidity of cement Further reductions in mixing water or higher
mixes. 0 1998 Elsevier Science Ltd. All rights slump increases can be obtained by using plasti-
reserved. cizers at higher dosages (as those normally
adopted for super-plasticizers), but this may
Keywords: admixtures, concrete, superplasti- result in adverse effects on setting, air volume
cizer, acrylic polymers, sulfonated melamine and strength of concrete. Therefore, from a
formaldehyde, sulfonated naphthalene formal- practical point of view, the main difference
dehyde. between plasticizers and superplasticizers is in
103
104 M. Collepardi

the optimum dosage, which is about 0.2-0.4% dehyde (SMF) condensate or sulfonated
by mass of cement for plasticizers and l-2% for naphthalene formaldehyde (SNF) condensate.
superplasticizers. The actual dosage of the Alternative water soluble synthetic polymers
active ingredients in both these admixtures is have been recently proposed2-” to reduce the
really much lower than the above figures since slump-loss drawback, which can partly or com-
they are generally available in a form of pletely cancel the initial technical advantage
30-40% aqueous solution in order to facilitate associated with the use of super-plasticizers (low
accurate, reliable and automatic dispensing at w/c ratio or high slump level). In the absence of
the batching plant. these new low slump loss superplasticizing
admixtures-based on acrylic polymers (AP)-
COMPOSITION OF PLASTICIZERS AND the slump loss problem has been approached by
SUPERPLASTICIZERS using retarding admixtures as secondary ingred-
ients to partly compensate for the stiffening
From a compositional point of view plasticizers process of the fresh concrete before its place-
and superplasticizers may be quite different ment.’ In some cases, chloride-free inorganic
(Table 1). The main ingredients in the super- salts are used as secondary ingredients to com-
plasticizers are synthetic water-soluble pensate for the retarding effect associated with
polymers, such as sulfonated melamine formal- heavily dosed superplasticizer systems (2%).

SAME STRENGTH
DURABILITY AND
OTHER PROPERTIES

-
CONTROL f
CONCRETE HIGHER STRENGTH

MIX DURABILITY
(WATER REDUCTION)
+ & WATERTIGHTNESS

WITHOUT l-0 REDUCE W/C RATIO

SAME WORKABILITY
ADMIXTURE

LOWER DRYING
SHRINKAGE, CREEP
ND THERMAL STRESS
(CAUSED BY HEAT
OF HYDRATION)

SAME STRENGTH
DURABILITY AND
WORKABILITY

Fig. 1. The effect of plasticizers and superplasticizers on the properties of concretes.’

 Admixtures used to enhance placing characteristics of concrete 105

Table 1. Main and secondary ingredients in plasticizing and superplasticizing admixtures’

Superplasticizers Plasticizers

Main ingredients Seconda y ingredients Main iqredients Secondary ingredients

SNF MLS LS/MLS TEA

SMF Retarders HC Inorganic salts
AP Inorganic salts CH Defoaming agents
Others TEA Others Anti-bacterial products

SMF, sulfonated melamine formaldehyde; SNF, sulfonated naphthalene formaldehyde; AP, acrylic polymers; MLS, mod-
ified form; TEA, triethanolamine; LS, lignosulfonic acid; HC, hydroxycarboxylic acids; CH, carbohydrates.

The main ingredients used in the manufac- the adsorption of anionic polymers, such as
ture of plasticizers are organic products and can SNF or SMF, by the presence of SO, groups
be divided into four groups. The first contains on the surface of cement particles. The disper-
salts of lignosulfonic (LS) acid, which can also sion of cement particles would be related to the
be used as an important ingredient of super- electrical repulsion produced by the adsorption
plasticizers when available in a modified form of negatively charged groups.
(MLS), and consists mainly of a de-sugarized Additional experimental results have not con-
product with reduced retarding effects. The firmed this mechanism for the superplasticizing
second group contains salts of hydroxycarboxylic action of the acrylic polymers.3’8-‘1 To study the
acids (HC). The carbohydrates (CH) belong to dispersion and superplasticizing effects of
the third group, whereas the fourth group con- acrylic and sulfonated polymers, the fluidity of
tains miscellaneous compounds such as glycerol, Portland cement mortar mixes with w/c of 0.40
polyvinyl alcohol, etc.’ Other secondary ingred- and sand/cement of 3 was measured (at 5 min)
ients in plasticizers may be accelerating in the absence or in the presence of different
products such as triethanolamine (TEA), or cal- dosages of CAE or SNF admixtures (O.O-0.6%
cium and sodium of inorganic acids, as well as of dry polymer to mass of cement). Figure 3
defoaming agents, anti-bacterial and anti-fungal shows the flow table measurements of these
materials to avoid gas development caused by mortars and indicates that the CAE copolymer
the transformation of the organic main ingred- performs much more effectively than the SNF
ients. polymer.
Figure 2 shows the chemical structure of the The aqueous phase of Portland cement
most important sulfonated (SNF, SMF, AS, LS) pastes (w/c = 2) was analyzed by the total
and acrylic polymers - such as copolymers of organic content (TOC) technique14 to deter-
carboxylic acrylic acids (CAE), polycarboxylate mine the residual concentration of polymer
ester (PC) and cross-linked acrylic polymer after 5 min of agitation, so that the content of
(CLAP) - used as active ingredients of super- admixture adsorbed onto cement could be cal-
plasticizing admixtures. culated. Figure 4 shows the percentage of
polymer adsorbed as a function of the admix-
ture dosage expressed as the percentage of dry
ACTION MECHANISM OF polymer by mass of cement. The adsorption of
SUPERPLASTICIZERS CAE copolymer (about 85%) appears to be
higher than that recorded for the SNF polymer
Superplasticizers cause dispersion into smaller (75%). Figure 5 shows the results of zeta poten-
agglomerates of cement particles, which pre- tial measurements on the same Portland cement
dominate in the cement paste of the concrete pastes determined by a multi-angle electropho-
mix. Because of the dispersion effect, there is a retie light scattering (ELS) technique.15 The
fluidity increase in the cement mixture. In the zeta potential of cement particles treated with
past, the dispersion effect was ascribed to the CAE appeared to be much lower than those
development of the electrostatic (negative) recorded in the presence of SNF. In particular,
charge on the cement particles.12,‘” The attrac- when 0.3% of CAE by mass of cement was
tive forces existing among cement particles that used, the cement particles appeared to be elec-
cause agglomeration would be neutralized by trically neutral even though the corresponding
106 M. Collepardi

mortar mix, with the same percentage of admix- responsible for the dispersion of large agglom-
ture (0.3%) was much more fluid than the plain erates of cement particles into smaller ones and
mix and that with the SNF polymer (Fig. 3). for the remarkable increase in the fluidity (Fig.
All these results indicate that the dispersion 3) of cement mixes.
of cement particles, responsible for the fluidity The dispersion mechanism performed by the
increase caused by superplasticizer, is not CAE polymer could be related to a steric hind-
necessarily related to the electrostatic repulsion rance effect rather than to the presence of
associated with zeta potential measurements. It negatively charged anionic groups (COO-). In
would seem that, at least for the CAE admix- other words, the polymer molecules of CAE on
ture, the polymer adsorption (Fig. 4) rather the surface of cement might themselves hinder
than the electrostatic repulsion (Fig. 5), is flocculation into large and irregular agglomer-

e--m- 30,M
CHZ

R=H, CH.3, C,Hj

1M=1Ua
SNF
0
S6,iM
!

n
H -fH2 -7
I
i
50:
T=O
%H3
-+cH~-:H

E~hl;lcne oxide
1:
II
c=o
-

OCH~CH~(EO)
&H2CH20H

(Sulfonated naphtalene formaldehyde) PPColycarboxylateester)

H CH,
HO
t
R-CH, - Hz
M=Na
L
M=Na
SMF 8 i
(Sulfonated melamine formaldehyde) CAE
[Copolymer of carboxylic acrylic
acid with acrylic ester)
R

H -hi, -
AS
(Amino-sulfonate polymer) i
(Xl, - Crcsslinkd point

i :=o, , R \

R
i

CLAP
(Cross-linked acrylic polymer)

Fig. 2. Chemical structure of sulfonated and acrylic polymers.‘-‘02 ’ ’

 Admixtures used to enhance placing characteristics of concrete 107

c
.
,
c

SNF
CAE , ’ ’ ’
,
,
,
.
/
/
,l
,
,
/
I /
,
8
I
I

CAE
_- _ _t__“”

I I
0.6 0.
0.2 0.4 0.6 % OF POLYMER BY MASS OF CEMENT
% OF POLYMER BY MASS OF CEMENT Fig. 5. Zeta potential of CAE or SNF cement pastes as
Fig. 3. Influence of CAE or SNF polymers on the a function of polymer dosage?
fluidity of portland cement mortar mixes with w/c = 0.4.3

should be taken into account to explain the

ates of cement particles.” This mechanism
action mechanism of the AP-based superplasti-
would be in agreement with the relatively
cizers, whereas the electrostatic repulsion
smaller number of negative anionic groups
mechanism is the predominating effect for sul-
(COO -) in the CAE copolymer in comparison
fonated polymer-based (SMF, SNF, AS)
with those present as SO, in the SMF and SNF
superplasticizers. Moreover, additional mechan-
polymers (Fig. 2).
isms of the superplasticizing action include
The results by Uchikawa’” and Tanaka et
dispersion of cement particles by reduction in
al. ’ ’ indicate that the steric hindrance effect
surface tension of mixing water”’ and a
decrease in friction resistance because of the
line-up of linear polymers along the concrete
flow direction and lubrication properties pro-
duced by low molecular weight polymers.”
According to Tanaka et al.” the segregation
resistance of superplasticized concrete mixtures
is primarily caused by the coagulation effect of
higher molecular weight polymers-from hun-
dreds of thousands to millions-to bridge
different cement particles. This could explain
why AP-based superplasticizers, with higher
SNF molecular weight with respect to SMF or SNF,
m perform better in terms of higher segregation
resistance in fresh concrete mixtures.

METHOD OF ADDITION
601 0.4 0,
0 0.2 0.6 The SMF- or SNF-based superplasticizers are
% OF POLYMEFt BY MASS OF CEMENT available as a 40% aqueous solution. Both are
Fig. 4. of CAE or cement as able to transform a no-slump concrete into a
of polymer dosage.’ self-leveling mix with a slump increase of about
108 M. Collepardi

200 mm. However, the method of addition of seems that addition of superplasticizers with
these superplasticizers affects the slump- mixing water causes a strong incorporation of
increase effect. Figure 69 shows that an the polymer molecules into the C,A-gypsum
immediate addition procedure (SNF superplas- system, and leaves only small amounts of poly-
ticizer with gauging water) produced a less mer for dispersion of C3S and C$.
workable mix compared with delayed addition Consequently, the adsorption of SMF or SNF
of the same superplasticizers (after an initial polymer molecules on the prehydrated cement
mixing period of 1 min). surface is reduced and the subsequent dispers-
The influence of the time of addition on the ing action appears to be much more effective
effect of superplasticizer has been ascribed to than that recorded in the absence of the pre-
the different capabilities of SMF or SNF poly- liminary water treatment.
mer molecules to be adsorbed on anhydrous or A superplasticizer that could perform inde-
hydrated cement particles.16 For instance, a pre- pendently of the method of addition would be
liminary treatment of cement, even with a small much appreciated at the batching plant of
amount of water (l-2%), produces superplasti- ready-mixed or precast concrete, in order to
cized concrete mixes that, independently of the reduce the variability in the slump of fresh mix
method of addition of the super-plasticizer, or in the strength of hardened concrete caused
always perform as well as the best concrete pro- by a change in the procedure of superplasticizer
duced by delayed addition.17 This effect seems addition. The acrylic polymer-based superplasti-
to be related to the production of an ettringite cizers seem to be very interesting admixtures
coating on the surface of cement particles because they perform without depending on the
during the preliminary water treatment. It addition procedure. Table 2 shows the slump of
concrete mixes as a function of the superplasti-
cizer procedure addition (delayed or
immediate) when SMF- and SNF- or CAE-
based polymers are used (Table 3).”
Results by Uchikawa’” confirm that the NSF
polymer is adsorbed more, particularly on the
C3A hydration products, when the immediate
250. addition procedure is adopted. Moreover,
according to Uchikawa,‘” the superplasticizing
effect is improved with a delayed NSF-polymer
addition because of the lower adsorption of the
200. polymer on the &A hydration products; on the
other hand, the adsorption of the PC acrylic
z
polymer (Fig. 2) does not depend on the
method of addition (immediate or delayed).
!$ 150-

i SLUMP LOSS

The slump loss problem appears to be even

more serious than that related to the different

Table 2. Comparitive costs of superplasticizers as a per-

centage compared with 1 kg of dry acrylic polmer

Concentration of Cost of aqueous cost of

aqueous solution (%) solution dry polymer

Fig. 6. Effect of the SNF superplasticizer (0.45% as dry 30% AP 100

polymer) addition procedure on the change of properties 40% SMF :: 80
with respect to the reference mix (w/c = 0.45). R, refer- 40% SNF 16 40
ence mix (without superplasticizer); D, superplasticized
mix (delayed addition); I, superplasticized mix (immediate SMF, sulfonated melamine formaldehyde; SNF, sulfona-
addition). ted naphthalene formaldehyde; AP, acrylic polymers.
 Admixtures used to enhance placing characteristicsof concrete 109

Table 3. Effect of addition of mono-component copoly-

mer (CAE), sulfonated melamine formaldehyde (SMF)
and sulfonated naphthalene formaldehyde (SNF) super-
plasticizers on the slump of Portland cement concrete
250
mixes’ t w/c:

Admixture Concrete mixture

Tvpe Dosage Mode of WIG Slump

(%) addition” ratio (mm)

CAE 0.30 Immediate 0.39 230 \\

CAE 0.30 Delayed 0.39 235
SMF 0.30 Immediate 0.41 100 50 SUPERPLASTICIZED’
SMF 0.30 Delayed 0.41 215 t MIX ‘4.
^I NW
SNF 0.30 Immediate 0.40 100 u
30 60 9’0 120
SNF 0.30 Delayed 0.40 230
TIME, min

“Immediate: admixture with mixing water. Delayed: Fig. 7. Slump-loss at 20°C for plain and superplasticized
admixture after 1 min of mixing. mix at the same initial slump. SupeTlasticizer: 0.4% as
dry SNF polymer by weight of cement.

performances caused by the superplasticizer

plasticizer addition would be too stiff at the
addition procedure. When a concrete mix must
placement when a high-quality concrete (with
be transported for a long peroid, particularly in
low w/c) is produced. Moreover, dosing the
hot weather, it should keep as moist as possible
superplasticizer at the work site consumes too
in the initial slump level to avoid redosing the
much time and does not allow an accurate con-
concrete with water above and beyond that
trol of the final slump and admixture dosage.
required in the mix design. Results of investiga-
Other methods to control slump loss include
tions of retempered concrete indicate that many
adding a higher than normal dosage of super-
of the properties of the hardened concrete
plasticizer or using some type of retarding
(strength, durability, abrasion resistance, etc.)
admixture in the formulation. However, there
are significantly affected, since retempered con-
are some limits of this approach, because some-
crete does not perform as well as concrete that
times the final effect is to produce concrete with
has not been retempered.” However, slump
an unacceptably low early strength or to aggra-
loss is un-avoidable because of the intrinsic
vate slump loss more seriously. For instance,
requirement for cement mixes, which should set
slump loss accompanied by a surprisingly quick
and harden in a relatively short time. Therefore,
set may be recorded by using retarders such as
J right and proper compromise would be a
sugar, sucrose, corn syrup or calcium lignosulfo-
Lero-slump-loss concrete mix for about 1 hour.
nate.” The cement content, as well as the
By using traditional superplasticizers based on
chemical and mineralogical composition of
SNF or SMF polymers it is not easy to achieve
cement, play an important role in determining
this target, because in general, slump loss is
higher in superplasticized concrete with respect
to the corresponding plain mix at a given initial
slump (Fig. 7). The lower the w/c, the higher W/C= 0.60 w/c = 0.45

the slump loss for the same initial slump level.

It seems that the lower w/c in superplasticized
concrete and the consequent lower distance
among cement particles causes a more signifi-
cant slump loss when the same amount of water
IS lost through evaporation or by reaction with
cement during the transportation time (Fig. 8).
Several methods have been adopted to con-
trol the rate of slump loss. One method it to
add the superplasticizer at the point of dis-
charge but there are some practical problems I HYliRATED CEMENT

associated with this approach. For instance, the Fig. 8. Schematic picture of cement paste in a plain
concrete into the truck-mixer before the super- (w/c = 0.60) and superplasticized concrete (w/c = 0.45).8
110 M. Collepardi

such a singular slump loss, although the as a slump loss reducer. The OH - anions,
detailed mechanism is not clear. It seems that generated by cement hydration, attack the
the content of C3A, gypsum and alkali, as well insoluble reactive polymer. This is transformed
as the form of calcium sulfate used as set regu- into a water-soluble dispersant that contributes
lator, can affect the rate of slump-loss. to the stabilization of the dispersion and
Also redosing the superplasticizer at different reduces slump loss. The slump loss is negligible
intervals of time has been suggested12 to reduce up to 60 min (Fig. 9) with a dosage of super-
slump-loss, but this method appears to be not plasticizer in the range of 1.5-3.5% (by mass of
always easy to adopt in practice. Moreover, the cement), which appears to be much higher than
total dosage of super-plasticizer, as well as the the normal dosage (1%). Because of the negli-
relative cost, cannot be kept under control gible slump loss, both the required workability
according to the given plan. at the work site (160-200 mm) and the designed
Therefore a superplasticizer is required, 28-day compressive strength (43 or 54 MPa) can
which by itself is capable of maintaining the be attained with a very small variation in quality
slump for a long period of time independently (Fig. 10) since retempering of concrete with
of the temperature or the type and content of additional water on the work site is avoided.
cement. Fujiu et aL4 have developed a polymer This means that ready-mixed concrete can be
(with ester, amides and acid anhydrides as func-
tional groups), which by itself is not soluble in
mixing water, but under the alkaline environ-
ment formed in the aqueous phase in contact
with cement, is slowly transformed into an
aqueous soluble product that has a superplasti-
cizing effect. The mechanism of this method is
based on the principle that the effectiveness of
superplasticizers is significantly reduced by
rapid adsorption in the early periods of cement
hydration.
Fukuda et aL5 and Yamakawa et ~1.~ have
examined the slump loss performance of a com-
mercial superplasticizer that has two different
components: a SNF polymer that acts immedia- TIME, mln
tely as a dispersing agent and a reactive Fig. 9. Slump-loss curves with a bicomponent super-
polymer (in the form of an insoluble precursor) plasticizer.”

DAY OF TEST RESULTS

Fig. 10. Slump and 2%day compressive strength of 49 concrete batches produced in 7 different days.’
 Admixtures used to enhance placing characteristicsof concrete 111

manufactured under quality controls that are responsible for the dispersion of cement
approach those adopted in the industrial pro- particles and the fluidizing action of the admix-
cess of other construction materials such as ture. The low slump-loss effect of this
steel, polymer, ceramics, etc. superplasticizer should be related with the pro-
Mitsui et ~1.~ examined the performance of a truding side chains of the acrylic polymer, which
bi-component superplasticizer, based on the would prolong the dispersion of hydrated
combined action of a SNF polymer as a dispers- cement particles through a steric hindrance
ing agent and a copolymer (with sulfonic and effect.
carboxylic functional groups) as slump loss
reducer. The authors have found negligible
slump loss at temperatures in the range of CONCLUSIONS
IO-30°C up to 60 min with a dosage of super-
plasticizer of about l-2% in concrete without Superplasticizers are able to enhance the plac-
silica fume and 2.55% in the presence of silica ing characteristics of concrete mixtures by
fume. increasing the workability level at a given w/c.
Collepardi et al.” studied the effects of a Therefore they allow easier placement of con-
water soluble mono-component copolymer crete mixtures, even with low w/c when required
(CAE) on the properties of ready-mixed con- for strength or durability reasons.
crete mixtures. This superplasticizer acts both as Two drawbacks of superplasticized concrete
an immediate dispersant and as a slump loss mixtures can occur when traditional sulfonated
reducing agent. The concentration of the active polymer-based (SMF and SNF) admixtures are
CAE ingredient in the aqueous phase of this
superplasticizer is lower than that of traditional
NSF based superplasticizer (30% versus 40%).
However, although both of these superplasti-
cizers have been used at the same dosage (1%
by mass of cement), and therefore with dif-
ferent contents of active polymer (0.30% s/s
versus 0.40% s/s), the CAE-based superplasti-
A
cizer was more effective than that based on
SNF for water-reducing capability (w/c = 0.43
versus 0.47) as well as for maintenance of initial !x-
slump level (Fig. 11). The compressive strength
of the CAE superplasticized concrete was 30 60
u
90
I

120
I

150
OO
higher than that of the corresponding concrete
with the SNF-based superplasticizer at early and AGITATION TIME, min
especially at longer ages, because of the lower Q
w/c: the retarding effect of the CAE superplasti-
I
cizer, which was beneficial to the reduction in
slump loss, did not reduce the l-day compres-
sive strength with respect to the concrete that
contained the less retarding SNF superplasti-
cizer (Fig. 11B). B
Tanaka et al.” studied the effect of an AP-
based superplasticizer on the slump-loss of a
concrete mixture. This superplasticizer is a par- m 0.43
tially cross-linked copolymer of acrylic acid and . 0.47
polyethylene glycol mono-a&y1 ether (Fig. 2). I
28
.4ccording to Tanaka and co-workers the cross-
linked polymer is hydrolyzed by the alkaline CURING TIME, days
water phase of the cement paste and than con- Fig. 11. Slump-loss (A) and compressive strength (B) at
verted into an acrylic polymer. Both the steric 21°C of superplasticized concretes with OPC and CAE or
SNF polymer-based admixtures. The figures on the slump-
hindrance effect and the electrical repulsive loss curves indicate the percentage of the superplasticizer
force caused by the negative carboxylic groups active ingredient x mass of cement.’
112 M. Collepardi

used: the effectiveness of the fluidizing action posium on Admixtures for Concrete. Improvement of
Properties, ed. E. Vasquez. Chapman and Hall,
depends on the addition procedure (immediate
London, 1990, pp. 94-105.
or delayed); the slump-loss can reduce or cancel 8. Collepardi, M., Advances in Chemical Admixtures for
the advantage of using these super-plasticizers, Concrete, Proceedings of the Advances in Cement and
particularly in hot weather, with long transport- Concrete, eds M. W. Grutzeck & S. L. Sarkar, Dur-
ham, 1994, pp. 257-291.
ation times and reactive cements. 9. Collepardi, M., Superplasticizers and air-entraining
A new family of superplasticizers-all based agents: State of the art and future needs. Proceedings
on acrylic polymers-is available with improved of the VM. Malhotra Symposium. Concrete Technology:
placing characteristics: (i) flowing concretes can Past, Present, Future, ed. P. K. Mehta. S. Francisco,
1994, pp. 399-416.
be produced at lower w/c with respect to con- 10. Uchikawa, H., Hydration of cement and structures
crete mixtures containing sulfonated formation and properties of cement paste in the
superplasticizers; (ii) the effectiveness does not presence of organic admixtures. Proceedings of the
Concrete in The Service of Mankind, eds R. K. Dhir &
depend on the addition procedure (immediate M. J. McCarthy, 1995, pp. 3-47.
or delayed); and (iii) the slump-loss is much 11. Tanaka, Y. O., Matsuo, S., Ohta A. & Veda, M., A
more reduced with respect to concrete mixes new admixture for high performance concrete. Pro-
with traditional sulfonated superplasticizers. ceedings of the Concrete in The Service of Mankind, eds
R. K. Dhir & M. J. McCarthy, 1996, pp. 291-300.
12. Malhotra, V. M. & Ramachandran, V. S., Superplasti-
cizers. In Concrete Admixtures Handbook. Properties,
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