Admixtures

Admixtures are ingredients other than water, aggregates, hydraulic cement, and fibers that are added to
the concrete batch immediately before or during mixing. A proper use of admixtures offers certain
beneficial effects to concrete, including improved quality, acceleration or retardation of setting time,
enhanced frost and sulfate resistance, control of strength development, improved workability, and
enhanced finishability. It is estimated that 80% of concrete produced in North America these days
contains one or more types of admixtures. According to a survey by the National Ready Mix Concrete
Association, 39% of all ready-mixed concrete producers use fly ash, and at least 70% of produced
concrete contains a water-reducer admixture.

Admixtures vary widely in chemical composition, and many perform more than one function. Two basic
types of admixtures are available: chemical and mineral. All admixtures to be used in concrete
construction should meet specifications; tests should be made to evaluate how the admixture will affect
the properties of the concrete to be made with the specified job materials, under the anticipated ambient
conditions, and by the anticipated construction procedures.

Ground Granulated Blast Furnace Slag

Chemical Admixtures

Chemical admixtures are added to concrete in very small amounts mainly for the entrainment of air,
reduction of water or cement content, plasticization of fresh concrete mixtures, or control of setting time.

Seven types of chemical admixtures are specified in ASTM C 494, and AASHTO M 194, depending on
their purpose or purposes in PCC. Air entraining admixtures are specified in ASTM C 260 and AASHTO
M 154. General and physical requirements for each type of admixture are included in the specification

Air-Entrainment

Air entrainment is the process whereby many small air bubbles are incorporated into concrete and
become part of the matrix that binds the aggregate together in the hardened concrete. These air bubbles
are dispersed throughout the hardened cement paste but are not, by definition, part of the paste (Dolch
1984). Air entrainment has now been an accepted fact in concrete technology for more than 45 years.
Although historical references indicate that certain archaic and early 20th century concretes were indeed
inadvertently air entrained, the New York State Department of Public Works and the Universal Atlas
Cement Company were among the first to recognize that controlled additions of certain naturally
occurring organic substances derived from animal and wood byproducts could materially increase the
resistance of concrete in roadways to attack brought on by repeated freeze-thaw cycles and the
application of deicing agents (Whiting 1983; ACI Comm. 212 1963; Rixom and Mailvaganam 1986).

Extensive laboratory testing and field investigation concluded that the formation of minute air bubbles
dispersed uniformly through the cement paste increased the freeze-thaw durability of concrete. This
formation can be achieved through the use of organic additives, which enable the bubbles to be stabilized
or entrained within the fresh concrete (Whiting 1983, ACI Comm. 212 1963). These additives are called
air-entraining agents.
Besides the increase in freeze-thaw and scaling resistances, air-entrained concrete is more workable
than non-entrained concrete. The use of air-entraining agents also reduces bleeding and segregation of
fresh concrete (Whiting 1983; ACI Comm. 212 1963; Rixom and Mailvaganam 1986).

Materials and Specifications. The most commonly used chemical surfactants can be categorized into four
groups: 1) salts of wood resins, 2) synthetic detergents, 3) salts of petroleum acids, and 4) fatty and
resinous acids and their salts (Dolch 1984; Whiting 1983).

Until the early 1980s, the majority of concrete air entrainers were based solely on salts of wood resins or
neutralized Vinsol resin (Edmeades and Hewlett 1986), and most concrete highway structures and
pavements were air entrained by Vinsol resin. Today, a wider variety of air-entraining agents is available
and competes with Vinsol resins.

Requirements and specifications of air-entraining agents to be used in concrete are covered in ASTM C
260 and AASHTO M 154. According to these specifications, each admixture to be used as an air-
entraining agent should cause a substantial improvement in durability and none of the essential
properties of the concrete should be seriously impaired. This provides a means to evaluate air entraining
admixtures on a performance basis.

Factors Affecting Air Entrainment. The air-void system created by using air-entraining agents in concrete
is also influenced by concrete materials and construction practice. Concrete materials such as cement,
sand, aggregates, and other admixtures play an important role in maintaining the air-void system in
concrete. It has been found that air content will increase as cement alkali levels increase (Pomeroy 1989;
Whiting 1983) and decrease as cement fineness increases significantly (ACI Comm. 212 1963).

Fine aggregate serves as a three-dimensional screen and traps the air; the more median sand there is in
the total aggregate, the greater the air content of the concrete will be (Dolch 1984). Gradation has more
influence in leaner mixes. Median sand ranging from the No. 30 sieve to the No. 100 is the most effective
at entraining air . Excessive fines, minus No. 100 material, causes a reduction in air entrainment.

Because the use of chemical and mineral admixtures in addition to air-entraining agents has become
common practice, concrete users are always concerned about the effects of these admixtures on the air-
void system and durability of concrete. Effects of water reducers, retarders, and accelerators were widely
investigated by many researchers. In regards to gross air content obtained when water-reducing and
retarding admixtures are used in concrete, numerous studies have shown that for most of the materials,
less air-entraining agent is needed to achieve a given specified air content (Whiting 1983). Chemical
admixtures should be added separately from air entraining additives.

When lignosulfonate water reducers are used, less air-entraining agent is required because the
lignosulfonates have a moderate air-entraining capacity, although alone they do not react as air-
entraining agents (Dolch 1984; Rixom and Mailvaganam 1986). For a fixed amount of air-entraining
agent, the effect of added calcium chloride is to slightly increase the air content (Edmeades and Hewlett
1986). The effect is more pronounced as amounts greater than 1% of the weight of cement are used.
Some HRWR (superplasticizers) interact with cements and air-entraining agents, resulting in reductions in
specific surfaces and increases in air-void spacing factors (Whiting 1983; Whiting and Stark 1983;
Whiting and Dziedzic 1990).

Mineral admixtures such as fly ash and silica fume also affect the formation of void systems in concrete.
Gebler and Klieger (1983) showed, in their study on the effect of fly ash on air-void stability of concrete,
that concretes containing fly ash produced relatively stable air-void systems. However, the volume of air
retained is affected by fly ash types. In mixtures containing fly ashes, the amount of air-entraining agent
required to produce a given percentage of entrained air is higher, and sometimes much higher, than it is
in comparable mixtures without fly ash (Gebler and Klieger 1983). In a series of papers, researchers
presented the results of a study on factors that affect the air-void stability in concretes (Pigeon, Aitcin, and
LaPlante 1987; Pigeon and Plante 1989). They found that silica fume has no significant influence on the
production and stability of the air-void system during mixing and agitation. Bunke (1988) also indicated
that silica fume has no detrimental effects on the air-void system.

Temperature can also have a significant effect on air entrainment. Air entrainment varies inversely with
temperature. The same mix will entrain more air at 50° F (10°C) than at 100°F (38°C).

Air Content Control. Measurement of air content is an important checking "sensor" for the concrete user
to know whether concrete will resist freeze-thaw damage. Because average void spacing decreases as
air content increases, an "optimum" air content at which void spacing will prevent the development of
excessive pressure due to freezing and thawing will exist.

It is important to check the air content of fresh concrete regularly for control purposes. Air content should
be tested not only at the mixer but also at the point of discharge into the forms, because of losses of air
content due to handling and transportation.

Recommendations

1. Air entraining admixtures should be specified when concrete will be exposed to freeze/thaw
conditions, deicing salt applications or sulfate attack.
2. Although air entraining admixtures are compatible with most other admixtures, care should be
taken to prevent them from coming in contact during the mixing process.

Materials Group

Water-Reducing

Water-reducing admixtures are groups of products that are added to concrete to achieve certain
workability (slump) at a lower w/c than that of control concrete (Rixom and Mailvaganam 1986). Water-
reducing admixtures are used to improve the quality of concrete and to obtain specified strength at lower
cement content. They also improve the properties of concrete containing marginal- or low-quality
aggregates and help in placing concrete under difficult conditions (ACI Comm. 212 1963). Water reducers
have been used primarily in bridge decks, low-slump concrete overlays, and patching concrete.

Composition. Water-reducing admixtures can be categorized according to their active ingredients. There
are the following:

1. salts and modifications of hydroxylized carboxylic acids (HC type);

The basic role of water reducers is to deflocculate the cement particles agglomerated together and
release the water tied up in these agglomerations, producing more fluid paste at lower water contents.

Effect of Water-reducing Admixtures on Concrete. Use of water reducers usually reduces water demand
7-10%. A higher dosage of admixtures leads to more reduction; however, excess retardation may be
encountered (Admixtures and ground slag 1990). Many of the water-reducing admixtures tend also to
retard the setting time of the concrete. This effect is counteracted in Type A and Type E chemical
admixtures by adding other acceleration chemicals such as calcium chloride (Admixtures and ground slag
1990) or triethanolamine (TEA). HC admixtures tend to increase bleeding and should be used with care in
high-slump concrete. Lignosulfonate-based admixtures perform better in this regard because they entrain
air; normal dosages of lignin admixtures may add 1-2% of entrained air to the concrete. All water-reduced
concretes usually lose slump more quickly than do equivalent concretes without the admixtures.
However, this loss generally does not create problems when conventional water reducers (HC, PC, and
lignins types) are used (Admixtures and ground slag 1990; Previte 1977; Collepardi 1984).

It is well known now that using water-reducing admixtures increases concrete strength. Increases in
compressive strength are as much as 25% greater than would be anticipated from the decrease in w/c
(Mindess and Young 1981). For flexural strength, an increase of 10% for concrete at 7 days to 1 year has
been reported for lignosulfonate and hydroxycarboxylic admixtures (Collepardi 1984). Freeze-thaw
resistance and other durability aspects can also be improved when water-reducing admixtures are
properly used in concrete.

Although using admixtures in concrete improves concrete's properties, misusing any kind of admixtures
will negatively affect these properties. It is therefore important to follow the manufacturer's
recommendations whenever admixtures are used.

Recommendations

1. Verification tests should be performed on liquid admixtures to confirm that the material is the
same as that which was approved. The identifying tests include chloride and solids content, ph
and infrared spectrometry.
2. Water reducers and retarders may be used in bridge deck concrete to extend the time of set. This
is especially important when the length of placement may result in flexural cracks created by
dead load deflections during placement.
3. Increased attention needs to be placed on curing and protection due to the potential for shrinkage
cracks and bleeding when water reducers are used

Set-Retarding

Retarding admixtures (retarders) are known to delay hydration of cement without affecting the long-term
mechanical properties. They are used in concrete to offset the effect of high temperatures, which
decrease setting times, or to avoid complications when unavoidable delays between mixing and placing
occur (Mindess and Young 1981). Use of set retarders in concrete pavement construction 1) enables
farther hauling, thus eliminating the cost of relocating central mixing plants; 2) allows more time for
texturing or plastic grooving of concrete pavements; 3) allows more time for hand finishing around the
headers at the start and end of the production day; and 4) helps eliminate cold joints in two-course paving
and in the event of equipment breakdown (Amer. Concrete Pavement Assoc. 1975). Retarders can also
be used to resist cracking due to form deflection that can occur when horizontal slabs are placed in
sections (Mindess and Young 1981). Because of these advantages, set retarders are considered the
second most commonly used admixtures in the highway industry, especially in the construction of bridge
decks (U.S. Dept. Trans. 1990).

Composition and Mechanism of Retardation. Many water reducers have a retarding tendency. Therefore,
some of the ingredients in water reducers, such as lignosulfate acids and hydroxycarboxylic acids, are
also a basis for set-retarding admixtures. Other important materials used in producing set retarders are
sugars and their derivatives.

Mechanisms of set retardation were studied by many researchers. Several theories have been offered to
explain this mechanism. A review of these theories was presented by Young (1972). The role of retarding
admixtures can be explained in a simple way: the admixtures form a film around the cement compounds
(e.g., by absorption), thereby preventing or slowing the reaction with water. The thickness of this film will
dictate how much the rate of hydration is retarded. After a while, this film breaks down, and normal
hydration proceeds (Fattohi 1958). However, in some cases when the dosage of admixtures exceeds a
certain critical point, hydration of cement compounds will never proceed beyond a certain stage, and the
cement paste will never set. Thus, it is important to avoid overdosing a concrete with a retarding
admixture.

Other factors influencing the degree of retardation include the w/c, cement content, C3A and alkali
contents in cement, the type and dosage of the admixture, and the stage at which the retarder is added to
the mix. The effectiveness of retarder is increased if its addition to the fresh concrete is delayed for a few
minutes.

Effect on Concrete Properties and Application. In addition to their role in controlling setting time,
retarders—like any other admixtures—influence the properties of fresh and hardened concrete. Air
entrainment of concrete is affected and fewer air-entraining agents need to be used because some
retarders entrain air (see water reducers). Slump loss might increase even when abnormal setting
behavior does not occur.

Because of retarding action, the 1-day strength of the concrete is reduced. However, ultimate strength is
reported to be improved by using set-controlling admixtures. Rates of drying shrinkage and creep could
increase by using retarders, but the ultimate values cannot increase.

One of the most important applications of retarding admixtures is hot-weather concreting, when delays
between mixing and placing operation, may result in early stiffening (Fattuhi 1958). Another important
application is in prestressed concrete, where retarders prevent the concrete that is in contact with the
strand from setting before vibrating operations are completed. Set retarders also allow use of high-
temperature curing in prestressed concrete production without affecting the ultimate strength of the
concrete.

Recommendations

1. Verification tests should be performed on liquid admixtures to confirm that the material is the
same as that which was approved. The identifying tests include chloride and solids content, ph
and infrared spectrometry.
2. Water reducers and retarders may be used in bridge deck concrete to extend the time of set. This
is especially important when the length of placement may result in flexural cracks created by
dead load deflections during placement.
3. Increased attention needs to be placed on curing and protection due to the potential for shrinkage
cracks and bleeding when water reducers are used.

Accelerating

Accelerating admixtures are added to concrete either to increase the rate of early strength development
or to shorten the time of setting, or both. Chemical compositions of accelerators include some of inorganic
compounds such as soluble chlorides, carbonates, silicates, fluosilicates, and some organic compounds
such as triethanolamine.

Among all these accelerating materials, calcium chloride is the most common accelerator used in
concrete. Most of the available literature treats calcium chloride as the main accelerator and briefly
discusses the other types of accelerators. However, growing interest in using "chloride-free" accelerators
as replacement for calcium chloride has been observed. This is because calcium chloride in reinforced
concrete can promote corrosion activity of steel reinforcement, especially in moist environments.
However, the use of good practices, i.e. proper proportioning, proper consolidation, and adequate cover
thickness can significantly reduce or eliminate problems related to corrosion.
Calcium Chloride. Calcium chloride (CaCl2) is a byproduct of the Solvay process for sodium carbonate
manufacture.

CaCO3 + 2NaCI Na2CO3 + CaCI2

Calcium chloride is available in two forms. Regular flake calcium chloride (ASTM D 98 Type 1) contains a
minimum of 77% CaCl2; concentrated flake, pellet, or granular calcium chloride (ASTM D 98 Type 2)
contains a minimum of 94% CaCl2 (ACI Comm. 212 1963). A 29% solution of CaCl2 is the most frequent
form of liquid product commercially available. In solid or liquid form, the product should meet the
requirement for ASTM C 494, Type C and ASTM D 98 (Admixtures and ground slag 1990).

Calcium chloride has been used in concrete since 1885 (Rixom and Mailvaganam 1986) and finds
application mainly in cold weather, when it allows the strength gain to approach that of concrete cured
under normal curing temperatures (Rixom and Mailvaganam 1986). In normal conditions, calcium chloride
is used to speed up the setting and hardening process for earlier finishing or mold turnaround.

Effects of calcium chloride on concrete properties are also widely studied and quantified. Aside from
affecting setting time, calcium chloride has a minor effect on fresh concrete properties. It has been
observed that addition of CaCl2 slightly increases the workability and reduces the water required to
produce a given slump (Ramachandran 1984) and reduces bleeding. Initial and final setting times of
concrete are significantly reduced by using calcium chloride. Effects of calcium chloride on initial and final
setting of cement paste are shown in Figure 2.4 (Ramachandran 1984). The total effect of adding calcium
chloride depends on dosage, type of cement used, and temperature of the mix.

Compressive and flexural strengths of concrete are substantially improved at early ages by using calcium
chloride. Laboratory tests have indicated that most increases in compressive strength of concrete
resulting from the use of 2% of calcium chloride by weight of cement range from 400 to 1,000 psi (2.8 to
6.9 MPa) at 1 through 7 days, for 70° F (21° C) curing (ACI Comm. 212 1963). Long-term strength is
usually unaffected and is sometimes reduced, especially at high temperatures (Admixtures and ground
slag 1990).

There is evidence that drying shrinkage of mortar or concrete is increased by using calcium chloride,
especially at early ages. The large shrinkage at earlier periods may be attributed mainly to more
hydration. Some work has shown that it is possible to reduce drying shrinkage by the addition of sodium
sulfate (Ramachandran 1984). At early ages concrete with 2% CaCl2 shows a higher resistance to
freezing and thawing than that without the accelerator, but this resistance is decreased with time. It has
been found, however, that addition of CaCl2 up to 2% does not decrease the effectiveness of air
entrainment (Ramachandran 1984).

Because of its corrosion potential, calcium chloride—especially in prestressed concrete—has been strictly
limited in use. ACI Committee 222 (1988) has determined that total chloride ions should not exceed
0.08% by mass of cement in prestressed concrete. British Standard CP.110 strongly recommends that
calcium chloride should never be added to concrete containing embedded metals.

Nonchloride Accelerators Although calcium chloride is an effective and economical accelerator, its
corrosion-related problem limited its use and forced engineers to look for other options, mainly
nonchloride accelerating admixtures. A number of compounds—including sulfates, formates, nitrates, and
triethanolamine—have been investigated. These materials have been researched and successfully used
in concrete. Triethanolamine (N(C2H4OH)3) is an oily, water-soluble liquid with a fishy odor and is
produced by the reaction between ammonia and ethylene oxide. It is normally used as a component in
other admixture formulations and rarely, if ever, as a sole ingredient (Rixom and Ramachandran 1986).
Calcium formate is another type of nonchloride accelerator used to accelerate the setting time of
concrete. At equal concentration, calcium formate (Ca[OOOCH] 2) is less effective in accelerating the
hydration of C3S than calcium chloride and a higher dosage is required to impart the same level of
acceleration as that imparted by CaCl2 (Ramachandran 1984). An evaluation study of calcium formate as
an accelerating admixture conducted by Gebler (1983) indicated that the composition of cement, in
particular gypsum (SO3) content, had a major influence on the compressive strength development of
concretes containing calcium formate. Results showed that the ratio of C 3A to SO3 should be greater than
4 for calcium formate to be an effective accelerating admixture; and that the optimum amount of calcium
formate to accelerate the concrete compressive strength appeared to be 2-3% by weight of cement
(Gebler 1983). Calcium nitrate and calcium thiosulfate are also considered accelerators.

Calcium nitrite accelerates the hydration of cement, as shown by the larger amounts of heat developed in
its presence. Calcium nitrite and calcium thiosulfate usually increase the strength development of
concrete at early ages (Ramachandran 1984).

Recommendations

1. Verification tests should be performed on liquid admixtures to confirm that the material is the
same as that which was approved. The identifying tests include chloride and solids content, ph
and infrared spectrometry.
2. Calcium chloride should not be used where reinforcing steel is present.
3. Calcium chloride should not be used in hot weather conditions, prestressed concrete or steam
cured concrete.
4. In applications using calcium chloride, the dosage rate should be limited to 2 percent by weight of
cement.
5. Care must be taken in selecting non-calcium chloride accelerators since some may be soluble
salts which can also aggravate corrision.

Superplasticizers

The use of superplasticizers (high range water reducer) has become a quite common practice. This class
of water reducers were originally developed in Japan and Germany in the early 1960s; they were
introduced in the United States in the mid-1970s.

Superplasticizers are linear polymers containing sulfonic acid groups attached to the polymer backbone
at regular intervals (Verbeck 1968). Most of the commercial formulations belong to one of four families:

 Sulfonated melamine-formaldehyde condensates (SMF)

The sulfonic acid groups are responsible for neutralizing the surface charges on the cement particles and
causing dispersion, thus releasing the water tied up in the cement particle agglomerations and thereafter
reducing the viscosity of the paste and concrete (Mindess and Young 1981).

ASTM C 494 was modified to include high-range water-reducing admixtures in the edition published in
July 1980. The admixtures were designated Type F water-reducing, high range admixtures and Type G
water-reducing, high-range, and retarding admixtures (Mielenz 1984).
Effect of Superplasticizers on Concrete Properties. The main purpose of using superplasticizers is to
produce flowing concrete with very high slump in the range of 7-9 inches (175-225 mm) to be used in
heavily reinforced structures and in placements where adequate consolidation by vibration cannot be
readily achieved. The other major application is the production of high-strength concrete at w/c's ranging
from 0.3 to 0.4 (Ramachandran and Malhotra 1984).

The ability of superplasticizers to increase the slump of concrete depends on such factors as the type,
dosage, and time of addition of superplasticizer; w/c; and the nature or amount of cement. It has been
found that for most types of cement, superplasticizer improves the workability of concrete. For example,
incorporation of 1.5% SMF to a concrete containing Type I, II and V cements increases the initial slump of
3 inches (76 mm) to 8.7, 8.5, and 9 inches (222, 216, and 229 mm), respectively.

The capability of superplasticizers to reduce water requirements 12-25% without affecting the workability
leads to production of high-strength concrete and lower permeability. Compressive strengths greater than
14,000 psi (96.5 MPa) at 28 days have been attained (Admixtures and ground slag 1990). Use of
superplasticizers in air-entrained concrete can produce coarser-than-normal air-void systems. The
maximum recommended spacing factor for air-entrained concrete to resist freezing and thawing is 0.008
inch (0.2 mm). In superplasticized concrete, spacing factors in many cases exceed this limit (Malhotra
1989; Philleo 1986). Even though the spacing factor is relatively high, the durability factors are above 90
after 300 freeze-thaw cycles for the same cases (Malhotra 1989). A study conducted by Siebel (1987)
indicated that high workability concrete containing superplasticizer can be made with a high freeze-thaw
resistance, but air content must be increased relative to concrete without superplasticizer. This study also
showed that the type of superplasticizer has nearly no influence on the air-void system.

One problem associated with using a high range water reducer in concrete is slump loss. In a study of the
behavior of fresh concrete containing conventional water reducers and high range water reducer, Whiting
and Dziedzic (1989) found that slump loss with time is very rapid in spite of the fact that second-
generation high range water reducer are claimed not to suffer as much from the slump loss phenomenon
as the first-generation conventional water reducers do. However, slump loss of flowing concrete was
found to be less severe, especially for newly developed admixtures based on copolymeric formulations.

The slump loss problem can be overcome by adding the admixture to the concrete just before the
concrete is placed. However, there are disadvantages to such a procedure. The dosage control, for
example, might not be adequate, and it requires ancillary equipment such as truck-mounted admixture
tanks and dispensers. Adding admixtures at the batch plant, beside dosage control improvement, reduces
wear of truck mixers and reduces the tendency to add water onsite (Wallace 1985). New admixtures now
being marketed can be added at the batch plant and can hold the slump above 8 inches (204 mm) for
more than 2 hours.

Recommendations

1. Verification tests should be performed on liquid admixtures to confirm that the material is the
same as that which was approved. The identifying tests include chloride and solids content, ph
and infrared spectrometry.
2. If transit mix trucks are used to mix high slump concrete, it is recommended that a 75 mm slump
concrete be used at a full mixing capacity to ensure uniform concrete properties.
3. If transit mix trucks are used to mix low w/c ratio concrete, it is recommended that the load size
be reduced to ½ to 2/3 the mixing capacity to ensure uniform concrete properties.
4. If freeze-thaw testing as described by ASTM C 666 indicates this to be a problem, it is
recommended that the air content be increased by 1 ½ percent.