Aci 212.3R-91

ACI 212.
3R-91
(Reapproved 1999)
Chemical Admixtures for Concrete
Reported by ACI Committee 212
Edwin A. Decker Joseph P. Fleming
Chairman Secretary
John M. Albinger Bayard M. Call Richard C. Mielenz Dale P. Rech Paul R. Stodola*
Floyd Best David A. Hunt William F. Perenchio* Donald L Schlegel David A. Whiting*
Reid H. Brown Kenneth R. Lauer William S. Phelan* Raymond J. Schutz* Arthur T. Winters
W. Barry Butler Bryant Mather* Michael F. Pistilli Billy M. Scott J. Francis Young
Members of the committee voting on the 1991 revisions:
William F. Perenchio Joseph P. Fleming

Chairman Secretary
Greg Bobrowski Guy Detwiler William S. Phelan M. Roger Rixom Paul R. Stodola
Reid H. Brown Gunnar M. Idorn Michael F. Pistilli Donald L Schlegel David A. Whiting
W. Barry Butler Bryant Mather John H. Reber Raymond J. Schutz Arthur T. Winters
Bayard M. Call Richard C. Mielenz Dale P. Rech Billy M. Scott J. Francis Young
Edwin A. Decker
This sixth report of ACI Committee 212, now named Chemical Ad- Chapter 2-Air-entraining admixtures, p. 212.3R-7
mixtures for Concrete, updates the previous reports of 1944, 1954, 2.1-Introduction
1963, 1971, and 1981. Admixtures discussed herein are those known 2.2-Entrained-air-void system
as chemical admixtures; finely divided mineral admixtures have been 2.3-Effect on concrete properties
transferred to ACI Committee 226. Admixtures are classified into five 2.4-Materials for air entrainment
groups: (I) air-entraining; (2) accelerating; (3) water-reducing and set- 2.5-Applications
controlling; (4) admixtures for flowing concrete; and (5) miscella- 2.6-Evaluation, selection, and control of purchase
neous. 2.7-Batching, use, and storage
Preparation and batching, which had a separate chapter in the 1981 2.8-Proportioning of concrete
report, are included here in Chapter 1. Chapter 5, Admixtures for 2.9-Factors influencing amount of entrained air
No wing Concrete, is new, representing technology that has ma- 2.10-Control of air content of concrete
tured since 1981. Any of those admixtures possessing properties
identifiable with more than one group are discussed with the group Chapter 3-Accelerating admixtures, p. 212.3R-10
that describes its most important effect on concrete. 3.1-Introduction
3.2-Types of accelerating admixtures
3.3-Use with special cements
Keywords: accelerating agents; adhesives; admixtures: air-entraining agents; al- 3.4-Consideration of use
kali-aggregate reactions; bactericides; batching; calcium chlorides; colors (materials); 3.5-Effect on freshly mixed and hardened concrete
concretes; corrosion inhibitors; expanding agents; flocculating; foaming agents; 3.6-Wet- and dry-process shotcrete
fungicides; gas-forming agents; insecticides; permeability-reducing admixtures; pig- 3.7-Control of purchase
ments; plasticizers; pumped concrete; retardants; waterproofing admixtures; 3.8-Batching and use
water-reducing agents.
3.9-Proportions of concrete
3.10-Control of concrete
CONTENTS Chapter 4-Water-reducing and set-controlling

Chapter 1-General information, p. 212.3R-2 admixtures, p. 212.3R-14
1.1 -Introdu ction 4.1-General
1.2-Reasons for using admixtures 4.2-Classification and composition
1 .3-Specifications for admixtures 4.3-Application
1.4-Sampling 4.4-Typical usage
1.5-Testing 4.5-Effects on fresh concrete
1.6-Cost effectiveness 4.6-Effects on hardened concrete
1.7-Considerations in the use of admixtures 4.7-Preparationand batching
1.8-Decision to use 4.8-Proportioning
1.9-Classification of admixtures 4.9-Qualitycontrol
1.10 -Preparation and batching 4.10-Precautions
* Chairman of the task groups that prepared this report. The following former members of
committee 212 contributed to the preparatioo of the document: Sanford L. Bauman, Jr.; Roger
ACI Committee Reports, Guides, Standard Practices, and W. Black; Edward J. Hyland (chairman); Rolland L. Johns; and Herman G. Protze,III.
Commentaries are intended for guidance in designing, plan- The 1991 revisions became effective July1, 1991. A number of minor editorial revisions were
ning, executing, or inspecting construction and in preparing made to the report, including Section 5.8.7. The year designations of the recommended refer-
ences of standards-producing organizations have been removed so that the current editions
specifications. Reference to these documents shall not be made become the referenced version.
in the Project Documents. If items found in these documents Copyright 0 1991, American Concrete Institute.
are desired to be part of the Project Documents they should All rights reserved including the rights of reproduction and use in any form or by any means.
be phrased in mandatory language and incorporated into the including the making of copies by any photo process, or by any electronic or mechanical device
printed or written or oral, or recording for sound or visual reproduction or for use in any
Project Documents. knowledge or retrieval system or device, unless permission in writing is obtained from the copy-
right proprietors.
212.3R-1
212.3R-2 MANUAL OF CONCRETE PRACTICE
Chapter 5-Admixtures for flowing concrete, Increase workability without increasing water con-
p. 212.3R-19 tent or decrease the water content at the same work-
5.1-General ability
5.2-Materials Retard or accelerate time of initial setting
5.3-Evaluation and selection
5.4-Application
Reduce or prevent settlement or create slight expan-
5.5-Performance criteria sion
5.6-Proportioning of concrete Modify the rate and/or capacity for bleeding
5.7-Effect on fresh concrete Reduce segregation
5.8-Effect on hardened concrete Improve pumpability
5.9-Quality assurance Reduce the rate of slump loss
5.10-Control of concrete
To modify properties of hardened concrete, mortar,
Chapter 6-Miscellaneous admixtures, p. 212.3R-22 and grout so as to:
6.1-Gas-forming admixtures Retard or reduce heat evolution during early hard-
6.2-Grouting admixtures ening
6.3-Expansion-producing admixtures
6.4-Bonding admixtures
Accelerate the rate of strength development at early
6.5-Pumping aids ages
6.6-Coloring admixtures Increase strength (compressive, tensile, or flexural)
6.7-Flocculating admixtures Increase durability or resistance to severe conditions
6.8-Fungicidal, germicidal, and insecticidal admixtures of exposure, including application of deicing salts
6.9-Dampproofing admixtures Decrease permeability of concrete
6.10-Permeability-reducing admixtures
6.11-Chemical admixtures to reduce alkali-aggregate expansion Control expansion caused by the reaction of alkalies
6.12-Corrosion-inhibiting admixtures with certain aggregate constituents
Increase bond of concrete-to-steel reinforcement
Chapter 7-References, p. 212.3R-28 Increase bond between existing and new concrete
7.1-Recommended references Improve impact resistance and abrasion resistance
7.2-Cited references
Inhibit corrosion of embedded metal
CHAPTER 1-GENERAL INFORMATION Produce colored concrete or mortar
1.1-Introduction
An admixture is defined in ACI 116R and in ASTM
C 125 as: a material other than water, aggregates, hy- 1.3-Specifications for admixtures
draulic cement, and fiber reinforcement, used as an in- The following specifications cover the types or classes
gredient of concrete or mortar, and added to the batch that make up the bulk of current products:
immediately before or during its mixing. This report Air-entraining admixtures . . . . . . . . . . . . ASTM: C 260
deals with commonly used admixtures other than poz- AASHTO: M 154
zolans. Admixtures whose use results in special types of Water-reducing and set-controlling
concrete are assigned to other ACI committees, such as: admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ASTM: C 494
expansive-cement concrete (ACI Committee 223), insu- AASHTO: M 194
lating and cellular concretes (ACI Committee 523), and Calcium chloride.. . . . . . . . . . . . . . . . . . . . . . . ASTM: D 98
polymers in concrete (ACI Committee 548). Pozzolans AASHTO: M 144
used as admixtures are assigned to ACI Committee 226, Admixtures for use in producing
which also deals with ground granulated iron blast-fur- flowing concrete . . . . . . . . . . . . . . . . . . . . . ASTM: C 1017
nace slag (a latent hydraulic cement) added at the
mixer.
Admixtures are used to modify the properties of 1.4-Sampling
concrete or mortar to make them more suitable for the Samples for testing and inspection should be ob-
work at hand, or for economy, or for such other pur- tained by procedures prescribed for the respective types
poses as saving energy. In many instances, (e.g., very of materials in the applicable specifications. Such sam-
high strength, resistance to freezing and thawing, re- ples should be obtained by random sampling from
tarding, and accelerating), an admixture may be the plant production, from previously unopened packages
only feasible means of achieving the desired result. In or containers, or from fresh bulk shipments.
other instances, certain desired objectives may be best
achieved by changes in composition or proportions of
the concrete mixture if so doing results in greater econ- 1.5-Testing
omy than by using an admixture. Admixtures are tested for one or more of three rea-
sons: (a) to determine compliance with specifications;
1.2-Reasons for using admixtures (b) to evaluate the effect of the admixture on the prop-
Some of the more important purposes for which ad- erties of the concrete to be made with job materials un-
mixtures are used are: der the anticipated ambient conditions and construc-
To modify properties of fresh concrete, mortar, and tion procedures; and (c) to determine uniformity of
grout so as to: product.
CHEMICAL ADMIXTURES FOR CONCRETE 212.3R-3
The manufacturer of the admixture should be re- ter-reducing and set-retarding admixtures permit place-
quired to certify that individual lots meet the requirement Of large volumes of concrete over extended
ments of applicable standards or specifications. periods, thereby minimizing the need for forming,
It is important that quality control procedures be placing, and joining separate units. Accelerating ad-
used by producers of admixtures to insure product mixtures reduce finishing and forming costs. Required
compliance with uniformity and other provisions of physical properties of lightweight concrete can be
ASTM specifications and with the producers own fin- achieved at lower densities (unit weight) by using air-
ished-product specifications. Since such test methods entraining and water-reducing admixtures.
may be developed around a particular proprietary
product, they may not be applicable to general use or 1.7-Considerations in the use of admixtures
use by consumers. Admixtures should conform to ASTM or other ap-
Although ASTM tests afford a valuable screening plicable specifications. Careful attention should be
procedure for selection of admixtures, continuing use given to the instructions provided by the manufacturer
of admixtures in production of concrete should be pre- of the admixture. The effects of an admixture should
ceded by testing that allows observation and measure- be evaluated whenever possible by use with the partic-
ment of the performance of the chemical admixture ular materials and conditions of use intended. Such an
under concrete plant operating conditions in combina- evaluation is particularly important when (1) the ad-
tion with concrete-making materials then in use. Uni- mixture has not been used previously with the particu-
formity of results is as important as the average result lar combination of materials; (2) special types of ce-
with respect to each significant property of the admix- ment are specified; (3) more than one admixture is to be
ture or the concrete. used; and (4) mixing and placing is done at tempera-
tures well outside generally recommended concreting
1.6-Cost effectiveness temperature ranges.
Economic evaluation of any given admixture should Furthermore, it should be noted that: (1) a change in
be based on the results obtained with the particular type or source of cement or amount of cement, or a
concrete in question under conditions simulating those modification of aggregate grading or mixture propor-
expected on the job. This is highly desirable since the tions, may be desirable; (2) many admixtures affect
results obtained are influenced to an important degree more than one property of concrete, sometimes ad-
by the characteristics of the cement and aggregate and versely affecting desirable properties; (3) the effects of
their relative proportions, as well as by temperature, some admixtures are significantly modified by such
humidity, and curing conditions. factors as water content and cement content of the
In evaluating an admixture, its effect on the volume mixture, by aggregate type and grading, and by type
of a given batch should be taken into account. If add- and length of mixing.
ing the admixture changes the yield, as often is the case, Admixtures that modify the properties of fresh con-
the change in the properties of the concrete will be due crete may cause problems through early stiffening or
not only to direct effects of the admixture, but also to undesirable retardation, i.e., prolonging the time of
changes in the yield of the original ingredients. If the setting. The cause of abnormal setting behavior should
use of the admixture increases the volume of the batch, be determined through studies of how such admixtures
the admixture must be regarded as effecting a displace- affect the cement to be used: Early stiffening often is
ment either of part of the original mixture or of one or caused by changes in the rate of reaction between tri-
another of the basic ingredients-cement, aggregate, or calcium aluminate and sulfate. Retardation can be
water. All such changes in the composition of a unit caused by an overdose of admixture or by a lowering of
volume of concrete must be taken into account when ambient temperature, both of which delay the hydra-
testing the direct effect of the admixture and in esti- tion of the calcium silicates.
mating the benefits resulting from its use. Another important consideration in the use of ad-
The increase in cost due to handling an additional mixtures relates to those cases where there is a limit on
ingredient should be taken into account, as well as the the amount of chloride ion that is permitted in concrete
economic effect the use of the admixture may have on as manufactured. Such limits exist in the ACI 318
the cost of transporting, placing, and finishing the con- Building Code, the recommendations of ACI Commit-
crete. Any effect on rate of strength gain and speed of tees 201, 222, 226, and others. Usually these limits are
construction should be considered. An admixture may expressed as maximum percent of chloride ion by
permit use of less expensive construction methods or weight (mass)* of cement. Sometimes, however, it is
structural designs to more than offset any added cost chloride ion per unit weight (mass) of concrete, and
due to its use. For example, novel and economical de- sometimes it is water-soluble chloride ion per unit
signs of structural units have resulted from the use of weight (mass) of cement or concrete.
water-reducing and set-retarding admixtures (Schutz Regardless of how the limit is given, it is obvious that
1959). to evaluate the likelihood that using a given admixture
In addition, placing economies, ability to pump at
greater heads, and economies of concrete cost versus *In this report, when reference is made to mass it is called weight because
the committee believed this would be better understood; however, the correct
competitive building materials have been realized. Wa- term mass is given in parentheses.
will jeopardize conformance of concrete with a specifi- 1.10-Preparation and batching

cation containing such a limit, one needs to know the 1.10.1 Introduction-The successful use of admix-
chloride-ion content of the admixture that is being con- tures depends upon the use of appropriate methods of
sidered for use expressed in terms relevant to those in preparation and batching. Neglect in these areas may
which the specification limit is given. If in using the affect properties, performance, and uniformity of the
available information on the admixture and the pro- concrete significantly.
posed dosage rate it is calculated that the specification Certain admixtures such as pigments, expansive
requirement will be exceeded, alternate admixtures or agents, pumping aids, and the like are used in ex-
procedures should be considered for achieving the re- tremely small dosages and most often are batched by
sults that were sought through the use of the admixture hand from premeasured containers. Other hand-added
that cannot be used in the originally intended amount. admixtures may include accelerators, permeability re-
The user should be aware that in spite of such terms ducers, and bonding aids, which often are packaged in
as chloride-free, no truly chloride-free admixture amounts sufficient for proper dosage per unit volume
exists since admixtures often are made with water that of concrete.
contains small but measurable amounts of chloride ion. Most admixtures usually are furnished in ready-to-
use liquid form. These admixtures are introduced into
1.8-Decision to use the concrete mixture at the concrete plant or into a
Although specifications deal primarily with the in- truck-mounted admixture tank for introduction into the
fluence of admixtures on standard properties of fresh concrete mixture at the jobsitc. Although measurement
and hardened concrete, the concrete supplier, contrac- and addition of the admixture to the concrete batch or
tor, and owner of the construction project are inter- into the truck-mounted tank often is by means of a so-
ested in other features of concrete construction. Of pri- phisticated mechanical or electromechanical dispensing
mary concern may be workability, pumping qualities, system, a calibrated holding tank should be part of the
placing and finishing qualities, early strength develop- system so that the plant operator can verify that the
ment, reuse of forms or molds, appearance of formed proper amount of admixture has been batched into the
surfaces, etc. These additional features often are of concrete mixer or into the truck-mounted tank.
great importance when the selection and dosage rate of 1.10.2 Conversion of admixture solids to liq-
an admixture are determined. uids-Most admixtures are furnished in liquid form
Specific guidance for use of accelerating admixtures, and do not require dilution or continuous agitation to
air-entraining admixtures, water-reducing and set-con- maintain their solution stability.
trolling admixtures, admixtures for flowing concrete, The preparation of admixtures may involve making
and admixtures for other purposes is given in the rele- dilutions of the various concentrations to facilitate ac-
vant chapters of this report. Those responsible for con- curate batching or dispensing. As a result, the recom-
struction of concrete structures should bear in mind mendations of the manufacturer should be followed if
that increasing material costs and continuing develop- there is any doubt about procedures being used.
ment of new and improved admixtures warrant reeval- Some chemical admixtures are supplied as water-sol-
uation concerning the benefits of admixture use. uble solids requiring job mixing at the point of use.
Such job mixing may require that low-concentration
1.9-Classification of admixtures solutions be made due to difficulty in mixing. In some
In this report, admixtures are classified generically or cases, it is convenient to prepare standard solutions of
with respect to the characteristic effects of their use. uniform strength for easier use. Since many low-con-
Information to characterize each class is presented centration solutions contain significant amounts of
along with brief statements of the general purposes and finely divided insoluble materials or active ingredients,
expected effects of the use of materials of each group. which may or may not be readily soluble, it is impor-
The wide scope of the admixture field, the continual tant that precautions be taken to insure that these be
entrance of new or modified materials into this field, kept in uniform suspension before actual batching.
and the variations of effects with different concreting 1.10.3 Storage and protection-Because admixtures
materials and conditions preclude a complete listing of furnished as dry powders sometimes are difficult to
all admixtures and their effects on concrete. dissolve, admixtures supplied as ready-to-use liquids
Commercial admixtures may contain materials that may be of much higher concentrations than job-mixed
separately would belong in two or more groups, or solutions. As a result, any finely divided insoluble mat-
would be covered by two or more ASTM standards or ter, if present, will tend to stay in suspension, and con-
ACI committees. For example, a water-reducing ad- tinuous agitation usually is not required. Admixture
mixture may be combined with an air-entraining ad- manufacturers ordinarily can furnish either complete
mixture, or a pozzolan may be combined with a water- storage and dispensing systems or at least information
reducing admixture. Those admixtures possessing regarding the degree of agitation or recirculation re-
properties identifiable with more than one group or one quired with their admixtures. Timing devices com-
committee are considered to be in the group or commonly are used to control recirculation of the contents
mittee that is concerned with their most important ef- of storage tanks to avoid settlement or, with some
fect. products, polymerization.
In climates subject to freezing, the storage tank and ample, a vinsol resin-based air-entraining admixture
its contents must be either heated or placed in a heated and a water-reducing admixture containing a lignosul-
environment. The latter is preferred for the following fonate should never come in contact prior to actual
reasons: mixing into the concrete because of their instant floc-
1. If the storage tank contains pipe coils for heating culation and loss of efficiency of both admixtures. It is
the contents by means of hot water or steam, care must important, therefore, to avoid intermixing of admix-
be taken to avoid overheating the admixture since high tures prior to introduction into the concrete unless tests
temperatures can reduce the effectiveness of certain ad- indicate there will be no adverse effects or the manu-
mixture formulations. facturers advice permits it. It generally is better to in-
2. Some heating probes can overheat the admixture troduce the various admixtures into the batch at differ-
locally, pyrolize certain constituents, and produce ex- ent times or locations during charging or mixing.
plosive gases. It is important that batching and dispensing equip-
3. Electrical connections to heating probes, bands, or ment meet and maintain tolerance standards to mini-
tapes can be disconnected, allowing the admixture to mize variations in concrete properties and, con-
freeze and damage equipment. sequently, better performance of the concrete.
4. The cost of operating electric probes, bands, tapes, Tolerances of admixture batching equipment should be
etc. is normally higher than the cost of maintaining checked carefully. ASTM C 94 requires that volumetric
above-freezing temperatures in a heated storage room. measurement of admixtures shall be accurate, to +3
5. A heated admixture storage room protects not percent of the total volume required or plus or minus
only storage tanks, but pumps, meters, valves, and ad- the volume of dose required for 94 lb (43 kg, or one
mixture hoses from freezing and from other problems bag) of cement, whichever is greater. ASTM C 94 re-
such as dust, rain, ice, and vandalism. Further, since quires that powdered admixtures be measured by
the storage temperature is subject to less widespread weight (mass), but permits liquid admixtures to be
variation throughout the year, admixture viscosity is measured by weight (mass) or volume. Accuracy of
more constant and dispensers require less frequent cal- weighed admixtures is required to be within + 3 per-
ibration. cent of the required weight (mass).
6. If plastic storage tanks or hoses are used, care 1.10.5 Batching equipment
must be taken to avoid heating these materials to the 1.10.5.1 General-In terms of batching systems,
point of softening and rupture. admixtures may be grouped in two categories: (a) those
Storage tanks should be vented properly so that for- materials introduced into the batch in liquid form,
eign materials cannot enter the tank through the open- which may be batched by weight (mass) or volume; and
ing. Likewise, fill nozzles and any other tank openings (b) powdered admixtures that normally are batched by
should be capped when not in use to avoid contamina- weight (mass). The latter case includes such specialty
tion. materials as pumping aids and others that are added in
1.10.4 Batching-Batching of liquid admixtures and extremely small amounts and, thus, often are intro-
discharging into the batch, mixer, or truck-mounted duced by hand in premeasured packages. When high-
tank generally is accomplished by a system of pumps, volume usage of these admixtures is contemplated, the
meters, timers, calibration tubes, valves, etc., generally manufacturer of the admixture normally supplies a
called the admixture-dispensing system or dispenser. suitable bulk dispensing system.
Dispensing of admixtures into a concrete batch in- 1.10.5.2 Liquid batching systems-Liquid admix-
volves not only accurately measuring the quantity of ture dispensing systems are available for manual, sem-
admixture and controlling the rate of discharge but also iautomatic, and automatic batching plants. Simple
the timing in the batching sequence. In some instances, manual dispensing systems designed for low-volume
changing the time at which the admixture is added dur- concrete plants depend solely on the care of the con-
ing mixing can vary the degree of effectiveness of the crete plant operator in batching the proper amount of
admixture. For example, Bruere (1963) and Dodson, admixture into a calibration tube and discharging it
Farkas, and Rosenberg (1964) reported that the retard- into the batch.
ing effect of water-reducing retarders depends on the More sophisticated systems intended for automated
time at which the retarder is added to the mixture. The high-volume plants provide automatic fill and dis-
water requirement of the admixture also may be af- charge of the sight or calibration tube. It is necessary to
fected significantly. interlock the discharge valve so that it will not open
For any given condition or project, a procedure for during the filling operation or when the fill valve is not
controlling the time and rate of the admixture addition closed fully. Usually, the fill valve is interlocked with
to the concrete batch should be established and ad- the discharge valve so that it will not open unless the
hered to closely. To insure uniform distribution of the discharge valve is closed fully. A low-level indicator in
admixture throughout the concrete mixture during the the calibration tube often is used to prevent the dis-
charging cycle, the rate of admixture discharge should charge valve from being closed before all the admixture
be adjustable. is dispensed into the batch.
Foster (1966) noted that two or more admixtures Several methods of batching liquid admixtures are in
often are not compatible in the same solution. For ex- common use. All require a visual volumetric container,
called a calibration tube, to enable the plant operator to Often, the calibration tube is emptied either by grav-
verify the accuracy of the admixture dosage. The sim- ity or by air pressure and the admixture may have a
plest consist of a visual volumetric container, while considerable distance to flow through a discharge hose
others include positive volumetric displacement, and a or pipe before it reaches its ultimate destination.
very limited number use weigh-batching systems. Some Therefore, the dispenser control panel should be
of these can be used readily with manual, semiauto- equipped with a timer-relay device to insure that all ad-
matic, and automatic systems. mixture has been discharged from the conveying hoses
Positive volumetric displacement devices are well or pipes. If the admixture dispenser system is operated
suited for use with automatic and semiautomatic manually, the plant operator should be furnished a
batchers because they may be operated easily by re- valve with a detente discharge side to prolong the dis-
mote control with appropriate interlocking in the charge cycle until it is ascertained that all admixture is
batching sequence. They include flow meters and mea- in the concrete batch.
suring containers equipped with floats or probes. Most When more than one admixture is intended for the
meters are calibrated for liquids of a given viscosity. same concrete batch, the dispenser must be designed so
Errors caused by viscosity changes due to variations in that: (1) an appropriate delay is built into the system to
temperature can be avoided by recalibration and ad- prevent the admixtures from becoming intermingled; or
justment made by observation of the visual volumetric (2) each is batched separately so as to be properly
container or calibration tube. maintained apart before entering into the mixer. Like-
Flow meters and calibration tubes equipped with wise, in a manual system, the operator must be in-
floats or probes often are combined with pulse-emit- structed in methods to prevent such comingling of ad-
ting transmitters that give readouts on electromechani- mixtures.
cal or electronic counters. Often they are set by input- Weigh batching (batching by mass) of liquid admix-
ting the dosage per unit of cementitious material. The tures ordinarily is not used because the weigh batching
amount of cementitious material input to the panel devices are more expensive than volumetric dispensers.
combined with the dosage rate sets the dispensing sys- In some cases, it is necessary to dilute admixture solu-
tem to batch the proper amount of admixture. tions to obtain a sufficient quantity for accurate weigh-
Timer-controlled systems involve the timing of flow ing (determination of mass).
through an orifice. There are a number of variables as- Because of the high rate of slump loss associated with
sociated with these systems that can introduce consid- certain high-range water-reducing admixtures (super-
erable error. These variables include changes in power plasticizers), jobsite introduction of such admixtures
supply, partial restrictions of the measuring orifice, and has become common. Such addition may be from
changes in viscosity of the solution due to temperature. truck-mounted admixture tanks or jobsite tanks or
Timer-controlled systems must be recalibrated fre- drums. When using drums, the dispensing system often
quently, and the plant operator must be alert to verify is similar to that used in concrete plants, e.g., pumps,
the proper admixture dose by observation of the cali- meters, pulse transmitters, and counters to dispense the
bration tube. Although timer-controlled systems have proper admixture volume to the truck mixer at the job-
been used successfully, because of these inherent dis- site.
advantages, their use, in general, is not recommended, If truck-mounted tanks are used, the proper dosage
except perhaps for dispensing calcium chloride. of admixture for the concrete in the truck is measured
A number of different methods are used by admix- at the batch plant and discharged to the truck-mounted
ture manufacturers to fill and discharge calibration tank at a special filling station. At such a station, a se-
tubes. A major objective is to insure that the fill valve ries of lights or other signals tells the driver when the
will not open until the discharge valve is completely admixture batching is complete and when his tank con-
closed and to provide that, in the event of electrical or tains the proper amount. At the jobsite, the driver sets
mechanical malfunction, the admixture cannot be ov- the mixer at mixing speed and discharges the entire
erbatched. amount of admixture from the truck-mounted tank into
Power-operated valves are used frequently; a vac- the concrete.
uum release also may be provided to prevent venturi Care should be taken that the mixer remain in the
action from the concrete plants water line, causing an mixing mode until the admixture has been thoroughly
overbatching. Prior to installation of the dispenser, the distributed throughout the concrete. The condition of
system should be analyzed carefully to determine what the mixer and its blades influences the distribution. To
possible batching errors could occur and, with the help insure that all the admixture is introduced, air pressure
of the admixture supplier, they should be eliminated. should be used to force the admixture into all parts of
Discharge of the admixture from the calibration tube the mixer drum. To shorten the mixing time, the truck
to the concrete batch should be to the point where the mixer should operate at maximum speed, preferably
admixture achieves the greatest dispersion throughout over 19 rpm.
the concrete. Thus, for example, the discharge end of 1.10.5.3 Maintenance-Batching systems require
the water line leading to the mixer is a preferred loca- routine periodic maintenance to prevent inaccuracies
tion, as is the fine-aggregate weigh hopper or the belt developing from such causes as sticky valves, buildup
conveyor carrying fine aggregate. of foreign matter in meters or in storage and mixing
tanks, or worn pumps. It is important to protect com- The cement paste in concrete normally is protected
ponents from dust and temperature extremes, and they against the effects of freezing and thawing if the spac-
should be readily accessible for visual observation and ing factor (Powers 1949) is 0.008 in. (0.20 mm) or less
maintenance. as determined in accordance with ASTM C 457. Addi-
Although admixture batching systems usually are in- tional requirements are that the surface of the air voids
stalled and maintained by the admixture producer, be greater than 600 in?/in? (23.6 mm2/mmJ) of air-void
plant operators should thoroughly understand the sys- volume, and that the number of air voids per 1 in. (25
tem and be able to adjust it and perform simple main- mm) of traverse be significantly greater than the nu-
tenance. For example, plant operators should recali- merical value of the percentage of air in the concrete.
brate the system on a regular basis, not to exceed 90 The air content and the size distribution of air voids
days, noting any trends that indicate worn parts need- produced in air-entrained concrete are influenced by
ing replacement. many factors (Mielenz et al. 1958), the more important
Tanks, conveying lines, and ancillary equipment of which are the (1) nature and quantity of the air-en-
should be drained and flushed on a regular basis, and training admixture; (2) nature and quantity of the con-
calibration tubes should have a water fitting installed to stituents of the concrete admixture; (3) type and dura-
allow the plant operator to water flush the tube so that tion of mixing employed; (4) slump; and (5) kind and
divisions or markings may be clearly seen at all times. degree of consolidation applied in placing the concrete.
Because of the marked effect of admixtures on con- The factors are discussed in more detail in Section
crete performance, care and attention to the timing and 2.9.1. Vibration applied to air-entrained concrete re-
accuracy of batching admixtures is necessary to avoid moves air as long as the vibration is continued (Mielenz
serious problems. et al. 1958); however, laboratory tests have shown that
the resistance of concrete to freezing and thawing is not
CHAPTER 2-AIR-ENTRAINING ADMIXTURES reduced by moderate amounts of vibration.
2.1-Introduction Most investigators (Tynes 1977; Mather 1979; Schutz
ACI 116R defines an air-entraining agent as an 1978; Whiting 1979; Litvan 1983) have found in labo-
addition for hydraulic cement or an admixture for con- ratory tests that the addition of high-range water re-
crete or mortar which causes entrained air to be incor- ducers to air-entrained concrete may increase the spac-
porated in the concrete or mortar during mixing, usu- ing factor and decrease the specific surface area of the
ally to increase its workability and frost resistance. air-void systems. However, early reports of a reduction
This chapter is concerned with those air-entraining in frost resistance of such concretes (Tynes 1977;
agents that are added to the concrete batch immedi- Mather 1979) have not been substantiated by later re-
ately before or during its mixing, and are referred to as search. Nevertheless, it would be prudent to evaluate
air-entraining admixtures. the effect a specific high-range water reducer on the
Extensive laboratory testing and long-term field ex- frost resistance of a concrete mixture if this is a signif-
perience have demonstrated conclusively that concrete icant factor and if the manufacturer cannot supply such
must be properly air entrained if it is to resist the ac- an evaluation.
tion of freezing and thawing (Cordon et al. 1946; For a discussion of the mechanism of protection by
Blanks and Cordon 1949). Air entrainment should al- air entrainment, other sources should be consulted
ways be required when concrete must withstand many (Cordon 1966; Litvan 1972; MacInnis and Beaudoin
cycles of freezing and thawing, particularly where the 1974; Powers 1975).
use of such chemical deicing agents as sodium or cal-
cium chlorides is anticipated. Highway pavements, ga-
rage floors, and sidewalks placed in cold climates 2.3-Effect on concrete properties
probably will be exposed to such conditions. 2.3.1 Fresh concrete -Air entrainment alters the
The mechanism of air entrainment in concrete has properties of fresh concrete. These changes should be
been discussed in the literature (Powers 1968) but is be- considered in proportioning a mixture (ACI 211.1 and
211.2; Powers 1964). At equal slump, air-entrained
yond the scope of this report. The resistance of con-
concrete is considerably more workable and cohesive
crete to freezing and thawing also is affected by plac-
than similar non-air-entrained concrete except at higher
ing, finishing, and curing procedures; therefore,
cement contents. Segregation and bleeding are reduced.
acceptable practice in these respects must be followed
The reduction in bleeding, in turn, helps to prevent the
(ACI 304R-85, ACI 308-81).
formation of pockets of water beneath coarse-aggre-
2.2-Entrained-air-void system gate particles and embedded items such as reinforcing
Improvements in frost resistance are brought about steel, and also to prevent the accumulation of laitance
by the presence of minute air bubbles dispersed uni- or weak material at the surface of a lift. At high ce-
formly through the cement-paste portion of the con- ment contents, air-entrained concrete becomes sticky
crete. Because of their size and great number, there are and difficult to finish.
literally billions of such bubbles in each cubic yard of 2.3.2 Hardened concrete-Air-entrainment usually
air-entrained concrete. The void size must be small to reduces strength, particularly in concretes with moder-
provide adequate protection with a relatively low total ate to high cement contents, in spite of the decreased
volume of void space. water requirements. The reduction is generally propor-
tional to the amount of air entrained, but the rate of Particulate air-entraining admixtures have the ad-
reduction increases with higher amounts. Therefore, vantage of complete stability of the air-void system.
while a proper air-void system must be provided, ex- Once added to the fresh concrete, changes in mixing
cessive amounts of air must be avoided. A detailed dis- procedure or time; changes in temperature, workabil-
cussion of air requirements is included in ACI 211.1. ity, or finishing procedures; or the addition of other
When the cement content and slump are maintained admixtures such as fly ash, or other cements such as
constant, the reduction in strength is partially or en- ground slag, will not change the air content, as may be
tirely offset by the resulting reduction in water-cement the case with conventional air-entraining admixtures.
ratio (w/c) and fine-aggregate content. This is particu-
larly true of lean mass concretes or those containing a 2.5-Applications
large maximum-size aggregate. Such concretes may not The use of entrained air in concrete is recommended
have their strength reduced; strengths even may be infor several reasons. Because of its greatly improved re-
creased by the use of air entrainment. sistance to frost action, air-entrained concrete must be
used wherever water-saturated concrete is exposed to
freezing and thawing, especially when salts are used for
2.4-Materials for air entrainment deicing. Its use also is desirable wherever there is a need
Many materials are capable of functioning as air-en- for watertightness.
training admixtures. Some materials, such as hydrogen Since air-entrainment improves the workability of
peroxide and powdered aluminum metal, can be used to concrete, it is particularly effective in lean mixtures that
entrain gas bubbles in cementitious mixtures but are not otherwise may be harsh and difficult to work. It is
considered to be acceptable air-entraining admixtures, common practice to provide air-entrainment in various
since they do not necessarily produce an air-void sys- kinds of lightweight aggregate concrete, including not
tem that will provide adequate resistance to freezing only insulating and fill concrete (ACI 523.1R-67) but
and thawing. also in structural lightweight concrete. However, ad-
2.4.1 Liquid or water-soluble powdered air-entrain- mixtures for cellular concrete are not covered in this
ing agents-These agents are composed of salts of report since ACI Committee 523 covers that subject.
wood resins, synthetic detergents, salts of sulfonated There is no general agreement on benefits resulting
lignin, salts of petroleum acids, salts of proteinaceous from the use of air-entraining admixture in the manu-
materials, fatty and resinous acids and their salts, and facture of concrete block (Farmer 1945; Kennedy and
organic salts of sulfonated hydrocarbons. Not every Brickett 1986; Keunning and Carlson 1956). However,
material that fits the preceding description will produce satisfactory results using air-entraining admixtures have
a desirable air-void system. been reported in the manufacture of cast stone and
Any material proposed for use as an air-entraining concrete pipe.
admixture should be tested for conformance with
ASTM C 260. This specification is written to assure 2.6-Evaluation, selection, and control of
that the admixture functions as an air-entraining ad- purchase
mixture, that it causes a substantial improvement in the To achieve the desired improvement in frost resis-
resistance of concrete to freezing and thawing, and that tance, intentionally entrained air must have certain
none of the essential properties of the concrete are se- characteristics. Not only is the total volume of air sig-
riously impaired. Air-entrained concrete also can be nificant but, more importantly, the size and distribu-
made by using an air-entraining portland cement meet- tion of the air voids must be such as to provide effi-
ing ASTM C 150, Type IA, IIA, or IIIA. cient protection to the cement paste.
2.4.2 Particulate air-entraining admixtures-Solid To assure that an air-entraining admixture produces
particles having a large internal porosity and suitable a desirable air-void system, it should meet the require-
pore size have been added to concrete and seem to act ments of ASTM C 260. This specification sets limits on
in a manner similar to that of air voids. These particu- the effects that any given air-entraining admixture un-
late materials may be composed of hollow plastic der test may exert on bleeding, time of setting, com-
spheres or certain crushed bricks, expanded clay or pressive and flexural strength, resistance to freezing and
shale, or spheres of certain diatomaceous earths. These thawing, and length change on drying of a hardened
materials currently are not being used extensively. concrete mixture in comparison with a similar concrete
Research has indicated that when using inorganic mixture containing a standard-reference air-entraining
particulate materials, the optimum particle size should admixture such as neutralized vinsol resin. The method
range between 290 and 850 pm, total porosity of the by which these effects may be determined is given in
particles should be at least 30 percent by volume, and a ASTM C 233.
pore-size distribution should be in the range of 0.05 to Extensive testing and experience have shown that
3 pm (Gibbons 1978; Sommer 1978). Inclusion of such concrete having total air contents in the range of those
particulates in the proper proportion has produced recommended in ACI 211.1 generally will have the
concrete with excellent resistance to freezing and thaw- proper size and distribution of air voids when the air-
ing in laboratory tests using ASTM C 666 (Litvan and entraining admixture used meets the requirements of
Sereda 1978; Litvan 1985). ASTM C 260. Use of ASTM C 457 to determine the
actual characteristics of the air-void system in hard- procedures of ACI Committee 211. These procedures
ened concrete in investigations of concrete proportion- incorporate the reduction in water and fine aggregate
ing provides greater assurance that concrete of sat- permitted by the improved workability of air-entrained
isfactory resistance to freezing and thawing will be concrete.
obtained.
Most commercial air-entraining admixtures are in 2.9-Factors influencing amount of entrained air
liquid form, although a few are powders, flakes, or 2.9.1 Effects of materials and proportions-There
semisolids. The proprietary name and the net quantity are numerous factors that can influence the amount of
in pounds (kilograms) or gallons (liters) should be air entrained in concrete. The amount of air-entraining
indicated plainly on the containers in which the admix- admixture required to obtain a given air content will
ture is delivered. The admixture should meet require- vary widely depending on the particle shape and grad-
ments on allowable variability within each lot and ing of the aggregate used. Organic impurities in the ag-
between shipments (see ASTM C 260). Acceptance gregate usually decrease the air-entraining admixture
testing should be as stated in ASTM C 233. requirements, while an increase in the hardness of wa-
ter generally will increase the air-entraining admixture
2.7-Batching, use, and storage requirements.
TO achieve the greatest uniformity in a concrete mix- As the cement content or the fineness of a cement in-
ture and in successive batches, it is recommended that creases, the air-entraining potential of a given amount
water-soluble air-entraining admixtures be added to the of an admixture will tend to diminish. Thus, larger
mixture in the form of solutions rather than solids. amounts of air-entraining admixture generally are re-
Generally, only small quantities of air-entraining ad- quired in concrete containing high early strength (Type
mixtures (about 0.05 percent of active ingredients by III, ASTM C 150) or Portland-pozzolan cement (Type
weight [mass] of cement) are required to entrain the IP, ASTM C 595). High-alkali cements generally re-
desired amount of air. If the admixture is in the form quire a smaller amount of air-entraining admixture to
of powder, flakes, or semisolids, a solution must be obtain a given air content than do low-alkali cements.
prepared prior to use, following the recommendations Increasing the amount of finely divided materials in
of the manufacturer. concrete by the use of fly ash or other pozzolans, car-
If the manufacturers recommended amounts of air- bon black or other finely divided pigments, or benton-
entraining admixture do not result in the desired air ite usually decreases the amount of air entrained by an
content, it is necessary to adjust the amount of admix- admixture. As concrete temperature increases, higher
ture added. For any given set of conditions and mate- dosages of air-entraining admixtures will be required to
rials, the amount of air entrained is roughly propor- maintain proper air content. A given amount of an air-
tional to the quantity of agent used. However, in some entraining admixture generally produces slightly more
cases, a ceiling may be reached. The ceiling may occur air where calcium chloride is used as an accelerator.
in low-slump, high cement-content mixtures made in Similarly, the amount of air-entraining admixture re-
hot weather with finely ground cements and containing quired to produce a given air content may be reduced
fine aggregate with large amounts of material passing one-third or more when used with certain water-reduc-
the 75 pm (No. 200) sieve. A change in the fundamen- ing admixtures. Various types of admixtures can influ-
tal type of material used to make the air-entraining ad- ence the air content and quality of the air-void system;
mixture or a change in the cement or fine aggregate or therefore, special care should be taken when such ad-
an increase in slump may be necessary to obtain the re- mixtures are used in conjunction with air-entraining
quired air content. admixtures to assure that there is compatibility.
Attention should be given to proper storage of air- Increasing the air content of concrete generally
entraining admixtures. The manufacturers storage rec- increases the slump. However, relatively high-slump
ommendations should be obtained and followed. Air- mixtures may have a larger spacing factor and are
entraining admixtures usually are not damaged by therefore less desirable than low-slump mixtures. An
freezing, but the manufacturers instructions should be increase in w/c is likely to result in an increase in air
followed regarding the effects of freezing on the prod- content and in larger air voids. As the temperature of
uct. An admixture that is stored at the point of manu- the concrete increases, less air is entrained.
facture for more than six months after completion of 2.9.2 Effect of mixing, transporting, and consolidat-
tests prior to shipment, or an admixture in local stor- ing-The amount of air entrained varies with the type
age in the hands of a vendor or contractor for more and condition of the mixer, the amount of concrete
than six months, should be retested before use and re- being mixed, and the mixing speed and time. The effi-
jected if it fails to conform to any of the requirements ciency of a given mixer will decrease appreciably as the
of ASTM C 260. blades become worn or when mortar is allowed to ac-
cumulate in the drum and on blades.
2.8-Proportioning of concrete There also may be changes in air content if there is a
The proportioning of air-entrained concrete is simi- significant variation in batch size for a given mixer, es-
lar to that of non-air-entrained concrete. Methods of pecially if the batch size is markedly different from the
proportioning air-entrained concrete should follow the rated capacity of the mixer. Adams and Kennedy (1950)
found in the laboratory that, for various mixers and has been shown, however, that the air content of a
mixtures, air content increased from a level of about 4 concrete mixture generally is indicative of the adequacy
percent to as much as 8 percent, as the batch size was of the air-void system when the air-entraining admix-
increased from slightly under 40 percent to slightly over ture used meets the requirements of ASTM C 260.
100 percent of rated mixer capacity. The properties of the concrete-making materials, the
The amount of entrained air increases with mixing proportioning of the concrete mixture, and all aspects
time up to a point beyond which it slowly decreases. of mixing, handling, and placing should be maintained
However, the air-void system, as characterized by spe- as constant as possible so that the air content will be
cific surface and spacing factors, generally is not uniform and within the range specified for the work.
harmed by prolonged agitation. If more water is added This is important because too much air may reduce
to develop the desired slump, the air content should be strength without a commensurate improvement in du-
checked since some adjustment may be required; addi- rability, whereas too little air will fail to provide de-
tion of water without thorough or complete mixing may sired workability and durability.
result in nonuniform distribution of air and water Proper inspection should insure that air-entraining
within the batch. See ACI 304R for further details. admixtures conform to the appropriate specifications,
The methods used to transport concrete after mixing that they are stored without contamination or deterio-
can reduce the air content. Pumping the concrete gen- ration, and that they are accurately batched and intro-
erally will reduce the air content. duced into the concrete mixture as specified. The air
The type and degree of consolidation used in placing content of the concrete should be checked and con-
concrete can reduce the air content. Fortunately, air- trolled during the course of the work in accordance
void volume lost by these manipulations primarily con- with the recommendations of ACI Committee 311 as
sists of the larger bubbles of entrapped air that con- reported in the ACI Manual of Concrete Inspection
tribute little to the beneficial effects of entrained air. (ACI SP-2). Practices causing excessive air loss should
be corrected or additional compensating air should be
2.10-Control of air content of concrete entrained initially.
To achieve the benefits of entrained air in a consis- CHAPTER 3-ACCELERATING ADMIXTURES
tent manner requires close control of the air content. 3.1-Introduction
For control purposes, samples for determination of air An accelerating admixture is a material added to
content should be obtained at the point of placement. concrete for the purpose of reducing the time of setting
Tests for air content of freshly mixed concrete should and accelerating early strength development.
be made at regular intervals for control purposes. Tests Accelerators should not be used as antifreeze agents
also should be made when there is reason to suspect a for concrete; in the quantities normally used, accelera-
change in air content. tors lower the freezing point of concrete only a negligi-
The air content of importance is that present in con- ble amount, less than 2 C (3.6 F). No commonly used
crete after consolidation. Losses of air that occur due accelerators will substantially lower the freezing point
to handling, transportation, and consolidation will not of water in concrete without being harmful to the con-
be reflected by tests for air content of concrete taken at crete in other respects.
the mixer (see ACI 309). This is why air content in the The best-known accelerator is calcium chloride, but
sample should be checked at the point of discharge into it is not recommended for use in prestressed concrete,
the forms. in concrete containing embedded dissimilar metals, or
There are three standard ASTM methods for mea- in reinforced concrete in a moist environment because
suring the air content of fresh concrete: (1) the gravi- of its tendency to promote corrosion of steel. Proprie-
metric method, ASTM C 138; (2) the volumetric tary nonchloride noncorrosive accelerating admixtures,
method, ASTM C 173; and (3) the pressure method, certain nitrates, formates, and nitrites afford users al-
ASTM C 231, which, however, may not be applicable ternatives, although they may be less effective and are
to lightweight concretes. An adaptation of the volu- more expensive than calcium chloride. Other chemicals
metric method using the so-called Chace Air Indicator that accelerate the rate of hardening of concrete in-
(Grieb 1958), in which a small sample of mortar from clude triethanolamine and a variety of soluble salts such
the concrete is used, has not been standardized and as other chlorides, bromides, fluorides, carbonates, sil-
should not be used to determine compliance with spec- icates, and thiocyanates.
ification limits.
These methods measure only air volume and not the 3.2-Types of accelerating admixtures
air-void characteristics. The spacing factor and other For convenience, admixtures that accelerate the
significant parameters of the air-void system in hard- hardening of concrete mixtures can be divided into four
ened concrete can be determined only by microscopical groups: (1) soluble inorganic salts, (2) soluble organic
methods such as those described in ASTM C 457. The compounds, (3) quick-setting admixtures, and (4) mis-
use of these methods in coordination with investiga- cellaneous solid admixtures.
tions of proportioning of concrete for new projects Accelerators purchased for use in concrete should
provides greater assurance that concrete of satisfactory meet the requirements for Type C or E in ASTM
resistance to freezing and thawing will be obtained. It C 494. Calcium chloride also should meet the require-
ments of ASTM D 98. Forms of calcium chloride are Table 3.2 - Calcium chloride - Amounts of
shown in Table 3.2. chloride ion introduced per 100 lb cement
3.2.1 Soluble inorganic salts-Studies (Edwards and Amount of
Angstadt 1966; Rosskopf, Linton, and Peppler 1975) chloride
have shown that a variety of soluble inorganic salts, Liquid form, ion
Percent calcium 29 percent added to
such as chlorides, bromides, fluorides, carbonates, thi- Solid form, lb solution*
chloride by concrete,
ocyanates, nitrites, nitrates, thiosulfates, silicates, alu-
minates, and alkali hydroxides, will accelerate the set-
ting of portland cement.
Research by numerous investigators over recent years
has shown that inorganic accelerators act primarily by
accelerating the hydration of tricalcium silicate; com-
prehensive calorimetric data illustrating this point have *Commercial flake products generally have an assay of 77 to 80 percent cal-
cium chloride, which is close to the dihydrate.
been reported. Commercial anhydrous calcium chloride generally has an assay of 94 to 97
percent calcium chloride. The remaining solids usually are chlorides of magne-
Calcium chloride is the most widely used accelerator sium, sodium, or potassium, or combinations thereof. Thus, with regard to the
since it is the most cost effective. chloride content, assuming that the material is 100 percent, calcium chloride
introduces very little error.
It has been postulated (Tenoutasse 1969; Ramachan- A 29 percent solution often is the concentration of commercially used liquid
forms of calcium chloride, and is made by dissolving 1lb dihydrate to make 11
dran 1972) that in portland cement concrete mixtures qt of solution.
containing calcium chloride (C&l,), gypsum combines
with the calcium aluminate to form ettringite (calcium formate to accelerate the early-age strength of con-
trisulfoaluminate [3CaO - A&O, 3CaS0, 32H,O]) and
l l
crete. If the value for C,A/SO, is greater than 4.0, cal-
the calcium chloride combines with the calcium cium formate has a good potential for accelerating the
aluminate to form calcium chloroaluminate strength of concrete.
(3CaO.CaCl,* lOH,O). 3.2.3 Miscellaneous solid admixtures-In certain in-
3.2.2 Soluble organic compounds-The most com- stances, hydraulic cements have been used in place of
mon accelerators in this class are triethanolamine and accelerating admixtures. For example, calcium-alumi-
calcium formate, which are used commonly to offset nate cement can shorten the time of setting of portland
the retarding effects of water-reducing admixtures or to cement concrete (Robson 1952).
provide noncorrosive accelerators. Accelerating prop- The seeding of portland cement concrete with 2
erties have been reported for calcium acetate (Washa percent by weight (mass) of the cement with finely
and Withey 1953), calcium propionate (Arber and Vi- ground hydrated cement has been reported (Baslazs,
vian 1961), and calcium butyrate (RILEM 1968), but Kelmen, and Kilian 1959; Duriex and Lezy 1956) to be
salts of the higher carboxylic acid homologs are retard- equivalent to the use of 2 percent calcium chloride. The
ers (RILEM 1968). effects of seeding, in addition to calcium chloride, are
A number of organic compounds are found (Bash said to be supplementary.
and Rakimbaev 1969) to accelerate the setting of port- Various silicate minerals have been found (Angstadt
land cement when low water-cement ratios are used. and Hurley 1967; Kroone 1968) to act as accelerators.
Organic compounds reported as accelerators include Finely divided silica gels and soluble quaternary am-
urea (RILEM 1968), oxalic acid (Bash and Rakimbaev monium silicates have been found (Nelson and Young
1969; Djabarov 1970), lactic acid (Bash and Rakim- 1977) to accelerate strength development, presumably
baev 1969; Lieber and Richartz 1972), various ring through the acceleration of tricalcium-silicate hydra-
compounds (Lieber and Richartz 1972; Wilson 1927), tion (Stein and Stevels 1974). Very finely divided mag-
and condensation compounds of amines and formal- nesium carbonate has been proposed (Ulfstedt and
dehyde (Rosskopf, Linton, and Peppler 1975; Kossivas Watesson 1961) for accelerating time of setting of hy-
1971). However, severe retardation can be experienced draulic binders. Finely ground calcium carbonate tends
when the amounts of these compounds used in a mix- to accelerate time of setting (RILEM 1968).
ture are excessive.
Recent reports (Ramachandran 1973, 1976) indicate 3.3-Use with special cements
that triethanolamine accelerates the hydration of trical- It has been reported (USBR 1975) that the effective-
cium aluminate but retards tricalcium silicate. Thus, ness of calcium chloride in producing accelerated
triethanolamine can act as a retarder of cement hydra- strength of concrete containing pozzolans is propor-
tion as well as an accelerator. Other organic accelera- tional to the amount of cement in the mixture. Various
tors may behave in a similar fashion. effects may be produced when calcium chloride is used
Studies have shown that production of ettringite is as an admixture in concrete containing shrinkage-com-
greater in mixtures containing calcium formate pensating cement (ACI 223). The limited and conflict-
(Bensted 1978). Also, other data (Gebler 1983) have ing data available on the effect of acceleration on the
shown that the effectiveness of formates is dependent expansion of concrete containing shrinkage-compen-
on the sulfate content of the cement and the tricalcium sating or self-stressing cements suggest that the con-
aluminate-to-sulfate ratio (CJA/SOj). Cements that are crete proposed for use should be evaluated with the ac-
undersulfated provide the best potential for calcium celerating admixture to determine its effect.
Calcium chloride should not be used with calcium- tures, for patching, and for emergency repair, The ul-
aluminate cement since it retards the hydration of the timate strength of such mortars will be much lower
aluminates. Similarly, calcium chloride and potassium than if no accelerator had been added.
carbonate increase the time of setting and decrease the The concentration of an admixture may determine its
early strength development of rapid-hardening cements behavior. For example, at high rates of addition (6 per-
based on calcium fluoroaluminate (C11A7 . CaF2). How- cent by weight [mass] of cement), calcium nitrate be-
ever, strengths after one day are improved by these gins to show retarding properties (Murakami and Tan-
additions. The effects of calcium chloride on blended aka 1969). Ferric chloride is a retarder at additions of 2
cements are similar to those for portland cements, the to 3 percent by weight (mass) but is an accelerator at 5
effects being greater for cements using ground granu- percent (Rosskopf, Linton, and Peppler 1975). The use
lated blast-furnace slag than for those using pozzolanic of calcium-aluminate cement as an admixture may
additions (Collepardi, Marcialis, and Solinas 1973). cause flash set depending on dosage rate.
The usual tests should be made for the control of Temperature also may be an important parameter
concrete, such as slump, unit weight, and air content. since calcium chloride is stated (RILEM 1968) to have
If the concrete stiffens rapidly and difficulty is encoun- a greater accelerating effect at 0 to 5 C (32 to 41 F) than
tered in achieving proper consolidation or finishing of at 25 C (77 F).
the concrete, the accelerator used should be investi- 3.5.2 Air entrainment-Less air-entraining admix-
gated ture may be required to produce the required air con-
tent when an accelerator is used. However, in some
3.4-Consideration of use cases, large bubble sizes and higher spacing factors are
Accelerating admixtures are useful for modifying the obtained, possibly reducing the beneficial effects of
properties of concrete, particularly in cold weather, to: purposely entrained air. Evaluation of concrete con-
(a) expedite the start of finishing operations and, where taining the specific admixture(s) may be performed to
necessary, the application of insulation for protection; ascertain air-void parameters or actual resistance to
(b) reduce the time required for proper curing and pro- freezing and thawing using tests such as ASTM C 457
tection; (c) increase the rate of early strength develop- and C 666, respectively.
ment to permit earlier removal of forms and earlier 3.5.3 Heat of hydration-Earlier heat release is ob-
opening of construction for service; (d) permit more tained, but there is no appreciable effect on the total
efficient plugging of leaks against hydrostatic pressure; heat of hydration.
and (e) accelerate time of setting of concrete placed by 3.5.4 Strength -- When calcium chloride is used,
shotcreting. compressive strength may be increased substantially at
The use of accelerators in cold-weather concrete usu- early ages; later strength may be reduced slightly. The
ally is not sufficient in itself to counteract effects of low percentage increase in flexural strength usually is less
temperature. Recommendations for cold-weather con- than that of the compressive strength.
creting usually include such practices as heating the in- The effects of other accelerating admixtures on
gredients, providing insulation, and applying external strength development are not completely known, al-
heat (see ACI 306R). Accelerators should not be used though a number of salts that accelerate setting may
as antifreeze agents for concrete. decrease concrete strengths even as early as one day.
Accelerators should be used with care in hot weather. Some carbonates, silicates, and aluminates are in this
Some of the detrimental effects that may result are very category. Organic accelerators, such as triethanolamine
rapid evolution of heat due to hydration, rapid setting, and calcium formate, appear to be sensitive in their ac-
and increased shrinkage cracking. celerating action to the particular concrete mixture to
which they are added.
3.5-Effect on freshly mixed and hardened The addition of 2 percent calcium chloride by weight
concrete (mass) of cement, the 77-percent dihydrate type, in-
The effects of accelerators on some properties of creases strength at one day in the range of 100 to 200
concrete include the following: percent depending on the cement used.
3.5.1 Time of setting-Initial and final times of set- The compressive strength at one day of neat cement
ting are reduced. The amount of reduction varies with paste, mortar, or concrete prepared with mixtures of
the amount of accelerator used, the temperature of the portland and calcium-aluminate cements generally will
concrete, the ambient temperature, and characteristics be materially lower than those obtained with either of
of other materials used in the concrete. Excessive the two cements alone.
amounts of some accelerators may cause very rapid Seeding of portland cement with 2 percent by weight
setting; also, excessive dosage rates of certain accelera- (mass) of cement with finely ground hydrated cement
tors may cause retardation. has been reported to increase 90-day compressive
Times of setting as short as 15 to 30 sec can be at- strengths by 20 to 25 percent (Baslazs, Kelmen, and
tained. There also are ready-to-use mixtures of cement, Kilian 1959, Duriex and Lezy 1956).
sand, and accelerator that have an initial set of 1 to 4 3.5.5 Durability
min and a final set of 3 to 10 min. Mortars thus pre- 3.5.5.1 Volume change-Accelerators have been
pared are employed to seal leaks in below-grade struc- reported to increase the volume changes that occur un-
der both moist curing and drying conditions. Calcium tion, particularly when the concrete is exposed to chlo-
chloride is reported to increase creep and drying rides during service. Adherence to the limits just men-
shrinkage of concrete (Shideler 1942). A discussion of tioned does not guarantee absence of corrosion if good
literature relating to the presumed association of the use construction practices are not followed.
of calcium chloride with increased drying shrinkage Thus, admixtures have been sought that emulate the
with an alternative hypothesis has been advanced accelerating properties of calcium chloride without
(Mather 1964). having its corrosive potential. Formulations based on
More recent work (Bruere, Newbegin, and Wilson calcium formate with a corrosion inhibitor have been
1971) has indicated that such changes depend on the patented (Dodson, Farkas, and Rosenberg 1965). The
length of curing prior to beginning measurements, the use of stannous chloride, ferric chloride, and sodium
length of the drying or loading periods, and the com- thiosulfate (Arber and Vivian 1961), calcium thiosul-
position of the cement used. Also, changes in the rate fate (Murakami and Tanaka 1969), ferric nitrite (RI-
of deformation are greater than changes in the total LEM 1968), and calcium nitrite (Bruere 1971) are re-
amount of deformation. It has been suggested (Berger, ported to inhibit the corrosion of steel while still accel-
Kung, and Young 1967) that the influence of calcium erating setting and hardening.
chloride in drying shrinkage may be the result of However, all accelerators that do not contain chlo-
changes in the size distribution of capillary pores due to ride are not necessarily noncorrosive. Manns and Ei-
the effect of calcium chloride on hydration of the ce- chler (1982) reported that thiocyanates may promote
ment. corrosion. Until additional published data become
Drying shrinkage and swelling in water are higher for available, the Committee recommends that users re-
mixtures containing both portland and calcium-alumi- quest suppliers of admixtures containing thiocyanates
nate cements, and their durability may be affected ad- to provide test data regarding the corrosion of steel in
versely by use of an accelerating admixture (Feret and concrete made with these admixtures. The test data
Venuat 1957). provided should include corrosion results associated
3.5.5.2 Frost damage-The resistance to deterio- with the dosage range.
ration due to cycles of freezing and thawing and to 3.5.5.6 Discoloration of flatwork-Discoloration
scaling caused by the use of deicing salts may be in- of concrete flatwork has been associated with the use of
creased at early ages by accelerators but may be de- calcium chloride (Greening and Landgren 1966). Two
creased at later ages (see comments in previous section major types of mottling discoloration can result from
on air entrainment). the interaction between cement alkalies and calcium
3.5.5.3 Sulfate resistance-The resistance to sul- chloride. The first type has light spots on a dark back-
fate attack is decreased when portland cement concrete ground and is characteristic of mixtures in which the
mixtures contain calcium chloride (USBR 1975). ratio of cement alkalies to calcium chloride is relatively
3.5.5.4 Alkali-silica reaction-The expansion pro- low. The second consists of dark spots on a light back-
duced by alkali-silica reaction is greater when calcium ground and is characteristic of mixtures in which the
chloride is used (USBR 1975). This can be controlled by ratio of cement alkalies to chlorides is relatively high.
the use of nonreactive aggregates, low-alkali cement, or Available evidence indicates that the magnitude and
certain pozzolans. permanence of discoloration increases as the calcium
3.5.5.5 Corrosion of metals-One of the major chloride concentration increases from 0 to 2 percent by
disadvantages of calcium chloride is its tendency to weight (mass) of cement. This type of discoloration can
support corrosion of metals in contact with concrete be aggravated by high rates of evaporation during cur-
due to the presence of chloride ions moisture, and ing and improper placement of vapor barriers. Use of
oxygen. In accordance with ACI 222, the maximum continuous fog spray or curing compounds can help al-
acid-soluble chloride contents of 0.08 percent for pre- leviate this problem.
stressed concrete and 0.20 percent for reinforced con- 3.5.6 Quick-setting admixtures-Some of the admix-
crete, measured by ASTM C 114 and expressed by tures in this category are used to produce quick-setting
weight (mass) of the cement, are suggested to minimize mortars or concretes suitable for shotcreting opera-
the risk of chloride-induced corrosion. tions, sealing leaks, or other purposes. Quick-setting
Values for water-soluble chloride ion are given as admixtures are believed to act by promoting the flash
maxima in ACI 318-83, Table 4.5.4: prestressed con- setting of tricalcium aluminate (Schutz 1977). Among
crete-0.06; reinforced concrete exposed to chloride in those admixtures used (Mahar, Parker, and Wuellner
service-0.15; reinforced concrete that will be dry or 1975) or purported to produce quick set are ferric salts,
protected from moisture in service-1.00; other rein- sodium fluoride, aluminum chloride, sodium alumi-
forced concrete-0.30. nate, and potassium carbonate. However, many pro-
The user should exercise good judgment in applying prietary formulations are mixtures of accelerators.
these limits, keeping in mind that other factors (mois- These proprietary compounds are available in liquid or
ture and oxygen) always are necessary for electrochem- powder form to be mixed with cement.
ical corrosion. 3.5.7 Rapid accelerators for shotcrete-Rapid accel-
The use of calcium chloride as an accelerator will ag- erators for shotcrete are employed extensively in both
gravate the effects of poor-quality concrete construc- dry- and wet-process shotcrete (ACI 506-66).
Rapid shotcrete accelerators traditionally are based contributed by normal impurities (NaCl, KCl, MgCl,)
on soluble aluminates, carbonates, and silicates. These in technical-grade products.
materials are highly caustic and are hazardous to work- Calcium chloride should be introduced into the con-
ers. Newer neutral-pH chloride-free proprietary com- crete mixture in solution form. The dihydrate and an-
pounds are penetrating the market slowly. hydrous solid forms should be dissolved in water prior
to use. Preparation of a standard solution from dry
calcium chloride requires that the user be aware of the
3.6-Wet- and dry-process shotcrete
Since the wet-process shotcrete mixture is mixed with percent calcium chloride printed on the container, In
water as in conventional concrete, the rapid-setting ac- dissolving the dry product, it should be added slowly to
celerator is added at the nozzle during shooting. Gen- the water, rather than the water to the calcium chloride
erally, the shotcrete mixture quickly stiffens and as a coating may form that is difficult to dissolve. The
reaches an initial set, with a final set occurring much concentration of the solution may be verified by check-
later than would occur with the dry process. However, ing the density, which should be approximately 1.28
the early stiffening imparted by the accelerator aids in g/ml (0.17 oz/gal.) at 73 F (23 C), for a 29 percent so-
vertical and overhead placement. lution. The correct density should be obtained from the
supplier.
Accelerated shotcrete is used for providing early rock
support in tunneling, applying thick sections in vertical All forms of calcium chloride should conform to
or overhead positions, sealing flowing water, and ap- ASTM D 98. Accelerating admixtures based on cal-
plying of shotcrete between tides. The rate of strength cium chloride should meet the requirements of ASTM
gain can be greatly accelerated using rapid accelerators C 494. The amount of water in the solution should be
in dry-process shotcrete. Strength in excess of 3000 psi deducted from the water required for the desired w/c.
(21 MPa) in 8 hr would be typical for a noncaustic ac- Batching systems are available and are recommended to
celerator and 2000 psi (14 MPa) with a conventional assure accurate and uniform addition of calcium chlo-
caustic accelerator. ride in liquid form.
Using dry-process shotcrete and a compatible cement 3.9-Proportions of concrete
and accelerator, an initial set of less than 1min and a The mix proportions for concrete containing an ac-
final set of less than 4 min can be attained. celerator generally are the same as for those without the
accelerator. The maximum recommended chloride-ion
3.7-Control of purchase dosage should not exceed those mentioned in the sec-
Accelerators should meet the requirements of ASTM tion of this chapter dealing with corrosion of metals.
C 494 for Type C or E. Calcium chloride also should
meet the requirements of ASTM D 98, solid or liquid. 3.10-Control of concrete
Performance tests should be made if adequate infor-
mation is not available to evaluate the effect of a par-
3.8-Batching and use ticular admixture on properties of job concrete using
The amount of accelerator needed to obtain the de- job materials with expected job temperatures and con-
sired acceleration of the time of setting and strength struction procedures. Since some accelerators contain
development depends on local conditions and specific substantial amounts of chlorides, the user should de-
materials used; for calcium chloride, generally 1 to 2 termine whether or not the admixture under considera-
percent of the dihydrate form (77 to 80 percent) based tion contains a significant amount of chlorides and, if
on the weight (mass) of cement, is added. so, the percent by weight (mass) of the cement that its
Practice in the industry has been to equate 1 lb of the use will introduce into the concrete. The in-service po-
dihydrate form to represent one percent of cement by tential for corrosion should then be evaluated accord-
weight (mass) (Calcium Chloride Institute 1959). Var- ingly.
ious researchers (Abrams 1924; Ramachandran 1976)
have studied the effects of calcium chloride on concrete CHAPTER 4-WATER-REDUCING AND SET-
using this dosage basis. For convenience and means of CONTROLLING ADMIXTURES
reference to various research data, this practice contin- 4.1 -General
ues and prevails. Certain organic compounds or mixtures of organic
It is recognized, however, that this practice does not and inorganic compounds are used as admixtures in
result in 1 percent anhydrous calcium chloride going both air-entrained and non-air-entrained concrete to
into the mixture (1 lb dihydrate x 77 percent minimum reduce the water requirement of the mixture for a given
assay/100 lb cement = 0.8 percent CaCl,). Multiples of slump or to modify the time of setting, or both. Re-
this one percent (1 lb) of dihydrate are then used de- duction in water demand may result in either a reduc-
pending on temperatures (see Table 3.1). tion in w/c for a given slump and cement content or an
In many locations, anhydrous (94 to 97 percent) solid increased slump for the same w/c and cement content.
forms or solutions of calcium chloride are more eco- When the w/c is reduced, the effect on the hardened
nomical. Table 3.1 lists the common dosage rates of concrete is increased compressive strength and reduc-
each form. The total chloride contributed to the mix- tion in permeability and, in combination with adequate
ture is shown in Table 3.1, and this includes chlorides air entrainment, improved resistance to freezing and
thawing. The gain in compressive strength is frequently 2. Modifications and derivatives of lignosulfonic
greater than is indicated by the decrease in w/c alone. acids and their salts
This may be due to improved efficiency of hydration of 3. Hydroxylated carboxylic acids and their salts
the cement. Such admixtures also may modify the time 4. Modifications and derivatives of hydroxylated
of setting of concrete or grouts. carboxylic acids and their salts
A common side effect of many water-reducing ad- 5. Salts of the sulfonated melamine polycondensa-
mixtures is a tendency to retard the time of setting of tion products
the concrete. Water-reducing admixtures that do not 6. Salts of the high molecular weight condensation
retard frequently are obtained by combining water-re- product of naphthalene sulfonic acid
ducing and retarding materials with accelerators to 7. Blends of naphthalene or melamine condensates
produce admixtures that still retain the water-reducing with other water-reducing or set-controlling materials,
property but are less retarding, nonretarding (some- or both
times called normal setting), or even somewhat accel- 8. Other materials, which include: (a) inorganic ma-
erating. The degree of effect depends upon the relative terials, such as zinc salts, borates, phosphates, chlo-
amounts of each ingredient used in the formulation. rides; (b) amines and their derivatives; (c) carbohy-
Such formulations may contain other materials to pro- drates, polysaccharides, and sugar acids; and (d) cer-
duce or modify certain other effects such as the inclu- tain polymeric compounds, such as cellulose-ethers,
sion of an air-entraining admixture to produce air-en- melamine derivatives, naphthalene derivatives, sili-
trained concrete, or an air-detraining admixture to re- cones, and sulfonated hydrocarbons.
duce or eliminate air-entrainment produced by certain These materials may be used singly or in combina-
ingredients in the formulation when air entrainment is tion with other organic or inorganic, active, or essen-
either not desired or the amount of air produced is ex- tially inert substances.
cessive.
High-range water-reducing admixtures, also referred 4.3-Application
to as superplasticizers, behave much like conventional Water-reducing admixtures are used to produce con-
water-reducing admixtures in that they reduce the in- crete of higher strength, obtain specified strength at
terparticle forces that exist between cement grains in the lower cement content, or increase the slump of a given
fresh paste, thereby increasing the paste fluidity. How- mixture without an increase in water content. They also
ever, they differ from conventional admixtures in that may improve the properties of concrete containing ag-
they do not affect the surface tension of water signifi- gregates that are harsh or poorly graded, or both, or
cantly; therefore, they can be used at higher dosages may be used in concrete that may be placed under dif-
without excessive air entrainment. ficult conditions. They are useful when placing con-
The specific effects of water-reducing and set-concrete by means of a pump or tremie.
trolling admixtures vary with different cements, addi- Set-retarding admixtures are used primarily to offset
tion sequence, changes in w/c, mixing temperature, the accelerating effect of high ambient temperature (hot
ambient temperature, and other job conditions. weather) and to keep concrete workable during the en-
tire placing period, thereby eliminating form-deflection
4.2-Classification and composition cracks (Schutz 1959). This method is particularly valu-
Water-reducing and set-controlling admixtures able to prevent cracking of concrete beams, bridge
should meet the applicable requirements of ASTM decks, or composite construction caused by form de-
C 494, .which classifies them into the following seven flections. Set retarders also are used to keep concrete
types: workable long enough so that succeeding lifts can be
1. Water-reducing placed without development of cold joints or discon-
2. Retarding tinuities in the structural unit. Their effects on rate of
3. Accelerating slump loss vary with the particular combinations of
4. Water-reducing and retarding materials used.
5. Water-reducing and accelerating High-range water-reducing admixtures can be used to
6. Water-reducing, high-range* reduce the water content of concrete. Concrete of a
7. Water-reducing, high-range, and retarding? very low w/c can be made to have high strength while
This ASTM specification gives detailed requirements maintaining a higher slump [over 3 in. (75 mm)] than
with respect to water requirement, time of setting, otherwise obtainable using a w/c as low as 0.28 by
strength (compressive and flexural), drying shrinkage, weight (mass). Water reduction up to 30 percent has
and resistance to freezing and thawing. been achieved. Moderate water reductions (10 to 15 per-
The materials that generally are available for use as cent) also have been obtained at somewhat higher
water-reducing and set-controlling admixtures fall into slumps (6 to 7 in).
one of eight general classes: With no reduction in water content, achievement of
1. Lignosulfonic acids and their salts flowing concrete with slumps in excess of 8 in. is typi-
cal (see Chapter 5). High-range water reducers also
have been employed to reduce cement content. Since
*Also covered by ASTM C 1017 as Type I.
t Also covered by ASTM C 1017 as Type I I. the w/c controls the strength of concrete, the cement
content may be reduced with a proportional reduction for bleeding, segregation, and possible set retardation.
of the water content for equivalent strength concretes. Therefore, trial mixtures should be conducted to deter-
mine the effects of redosing.
ASTM C 494 includes specifications for admixtures
4.4-Typical usage of the water-reducing and set-controlling types, It pro-
Expected performance of a given brand, class, or vides for evaluation of the admixture for specification
type of admixture may be projected from one or more compliance under controlled conditions such as tem-
of the following sources: perature, fixed cement content, slump, and air content
1. Results from jobs where the admixture has been using aggregates graded within stipulated limits. This
used under good field control, preferably using the standard requires certain minimum differences in water
same material and under conditions similar to those requirement and strength of the concrete, range in time
anticipated. of setting, and requirements in other properties such as
2. Laboratory tests made to evaluate the admixture. shrinkage and resistance to freezing and thawing.
3. Technical literature and information from the Most water-reducing admixtures perform consider-
manufacturer of the admixture. ably better than the minimum requirements of ASTM
The addition rate (dosage) of the admixture should C 494. Good quality water-reducing admixtures reduce
be determined from information provided by one or the water requirement of the concrete as much as 8 to
more of the sources just mentioned. Information 10 percent or more and substantially increase the
should be available on past performance of the pro- strength at the same cement content. High-range water
posed admixture substantiating the desired perfor- reducers may reduce the water requirement by more
mance. than 30 percent in some instances.
Various results can be expected with a given admix-
ture due to differences in dosage, cements, aggregates,
other materials, and weather conditions. Water-reduc- 4.5-Effects on fresh concrete
ing and set-controlling admixtures usually are found to 4.5.1 Water reduction-Water-reducing admixtures,
be more effective with respect to water reduction and ASTM C 494, Type A, reduce the water required for
strength increase when used with portland cements of the same slump concrete by at least 5 percent, and in
lower tricalcium aluminate (CA) and alkali content. some cases up to 12 percent. Concrete containing lig-
Differences in setting times also can be expected with nosulfonate or hydroxylated carboxylic acid salts gen-
different types and sources of cement as well as con- erally reduce the water content 5 to 10 percent for a
crete mixtures and ambient temperatures. given slump and cement content. High-range water re-
These admixtures generally are used to take advan- ducers must reduce the water requirement at least 12
tage of water reduction to increase the strength of con- percent but may reduce the water by more than 30 per-
crete. If it is desired to provide a given level of strength, cent at a given slump. They also can be used to signifi-
the cement content generally can be reduced, resulting cantly increase slump without increasing water content.
in cost savings. In mass concrete, low cement content is They also may be employed to achieve a combination
particularly desirable since it lowers the temperature of these two objectives- a slump increase with a water-
rise of the concrete. Water-reducing and set-controlling content reduction.
admixtures do not lower heat of hydration of concrete As the cement content of a concrete mixture in-
except as they permit a reduction in cement content. creases, the required dosage of a high-range water re-
The early temperature characteristics may be modified ducer, as a percentage by weight (mass) of cement, is
somewhat due to the modification of the setting prop- reduced. The effects of these admixtures also are de-
erties of the concrete. pendent on the calculated CA, C,S, and alkali con-
In the production of high-strength concrete [above tents of the cement. Concretes made with cements
6000 psi (41 MPa)], it has been found beneficial to in- meeting requirements for Type II and Type V cements
crease the dosage of the admixture. This usually pro- require lower admixture dosages than concretes con-
vides extra water reduction as well as, typically, a retaining Type I or Type III cements. In some cases, it
tarded time of setting and slower early strength gain. has been found that higher SO, content may be desir-
Concrete having slow early strength gain characteristics able when using high-range water reducers.
generally exhibits higher later strengths. 4.5.2 Time of setting-Lignosulfonates and hydrox-
Concretes containing high-range water reducers often ylated carboxylic acids retard times of setting by 1 to 3
have shown rapid slump loss. To overcome this, a sec- hr when used at temperatures of 65 to 100 F (18 to 38
ond dosage of high-range water reducer may be used to C). Sugar acids, carbohydrates, zinc salts, borates, and
restore the slump without any apparent ill effects. Gen- phosphates in unmodified form retard the setting of
erally, more than two dosages are less effective and portland cement in varying degrees. Most other mate-
concrete may lose its workability faster than with a sin- rials, including high-range water reducers, do not pro-
gle dosage. It has been found that redosage may result duce appreciable retardation.
in an increase or decrease in air content on the order of Accelerators may be incorporated in the formulation
1 to 2 percent for each redose. When redosages are to produce acceleration or decrease or eliminate retar-
used, the concrete may experience a greater potential dation. Retarders generally are not recommended for
controlling false set; water-reducing retarders have been 4.5.5 Bleeding-Admixtures affect bleeding capacity
known to contribute to premature stiffening. in varying degrees. For example, Class 3 admixtures
4.5.3 Air entrainment-Lignosulfonates are air-en- (see Section 4.2) tend to increase bleeding, while cer-
training agents to various degrees. The amount of air tain Class 4 admixtures, which are derivatives of the
entrainment generally is in the range of 2 to 6 percent, Class 3 admixtures, do not. Class 1 and 2 admixtures
although higher amounts have been reported. This air- reduce bleeding and segregation in freshly mixed con-
entrainment may consist of large unstable bubbles that crete, in part due to the air entrainment. Class 5
contribute little to resistance to freezing and thawing. through 7 admixtures, when used as high-range water
The air-entraining properties may be controlled by reducers, generally decrease bleeding, except when at a
modifying formulations. Materials in Classes 3 through very high slump.
8 (see Section 4.2) generally do not entrain air, but ma- 4.5.6 Heat of hydration and temperature
terials in all eight classes may affect the air-entraining rise-Within normal w/c ranges, adiabatic temperature
capability of both air-entraining cements and air-en- rise and heat of hydration are not reduced at equal ce-
training admixtures. ment contents with the use of set-controlling admix-
Materials in Classes 5, 6, and 7 (high-range water re- tures. Acceleration or retardation may alter the rate of
ducers) have an effect on air entrainment. The perfor- heat generation characteristics, which may change the
mance and effectiveness of an air-entraining admixture early rate of temperature rise under job conditions. If
is strongly dependent on the nature of the high-range the use of the admixture permits a reduction in cement
water-reducing admixtures with which it may be used. content, heat generated is proportionally reduced.
Certain air-entraining admixtures have been reported to 4.5.7 Raze of slump loss-Rate of slump loss may
be more effective with certain high-range water-reduc- not be reduced and often is increased. With the low w/c
ing admixtures in the production of adequate air en- attainable with high-range water reducers, the concrete
trainment. may show a greater-than-normal rate of slump loss.
Since the key factor in producing frost-resistant con- Because of this, high-range water reducers often are
crete is the air-void system-that is, the total volume of added at the jobsite. Working time can be extended
air, spacing factor, voids per inch, and specific sur- with the careful use of an ASTM C 494, Type B re-
face-these factors should be quantified to achieve the tarding admixture or a Type D water-reducing and re-
desired durability and that reliance is not placed wholly tarding admixture. The working time depends on many
on the air content of the freshly mixed concrete. There- factors, including the high-range water-reducer dosage,
fore, different combinations of air-entraining admix- the use of other chemical admixtures, cement charac-
tures and high-range water-reducing admixtures should teristics, concrete temperature, slump, and the age of
be evaluated to achieve concrete that is resistant to the concrete when the high-range water reducer is in-
freezing and thawing, with determination of air-void traduced.
content and parameters of the air-void system in hard- 4.5.8 Finishing-The finishing characteristics of con-
ened concrete specimens being a desirable addition to crete containing Class 3 and 4 admixtures generally are
the test program. improved.
It is prudent to include testing for resistance to freez- At reduced water contents achieved with high-range
ing and thawing in the evaluation, as in some instances water reducers, finishing may become more difficult
spacing factors may exceed generally accepted limits due to the decrease in bleeding, and surfaces may have
[i.e., 0.20 mm (0.008 in.)] yet concrete may still be frost a tendency to crust and promote plastic-shrinkage
resistant when subjected to freezing and thawing. cracking. The surface may be kept from drying by fog-
4.5.4 Workability-When otherwise comparable ging, use of evaporation retarder, or other procedures
concretes with and without a water-reducing admixture (see ACI 308). This should be done with caution so that
having the same slump and air content are compared, the durability of the surface is not affected adversely.
differences in workability are difficult to detect since
there is no standard test for workability. However, 4.6-Effects on hardened concrete
concrete containing a water-reducing admixture gener- 4.6.1 Strength-Reduction in w/c causes an increase
ally is less likely to segregate. When vibrated, some in strength. There is a further increase in strength due
workers detect better flowability for the concrete con- to the use of a water-reducing admixture, apart from
taining the admixture. that due to reduction of w/c, due to modification of
Concretes proportioned for high strength using high- the hydration reaction and microstructure. Unless used
range water reducers usually have a sufficiently high at unusually high rates, retarding admixtures generally
cement content to supply the fines required. Repropor- will produce an increase in strength at 24 hr. The re-
tioning such concrete can be accomplished by making tarding types may decrease the very early strength while
up the volume of water reduced by increasing the vol- the normal setting and accelerating types increase the
ume of coarse and fine aggregate equally. If trial mix- very early strength.
tures are sticky, the volume of coarse aggregate should Later strength may be increased 20 percent or more
be increased and that of the fine aggregate reduced. at the same cement content. Cement contents, thus, can
This usually results in a mixture that is easier to place be reduced without lowering 28-day strengths. When
and finish. high-range water reducers are used to decrease the w / c
28-day compressive strength may be increased by 25 gether, they should be added to the batch separately so
percent or more. Increases in flexural strength of con- that they will be adequately diluted before coming in
crete containing a water-reducing admixture usually are contact with each other. The manufacturer of the ad-
attained, but they are not proportionally as great as in- mixtures should recommend proper procedures.
creases in compressive strength.
4.6.2 Shrinkage and creep-Information on the ef- 4.8-Proportioning
fects of these admixtures on shrinkage and creep is A concrete mixture may need reproportioning when
conflicting. Long-term shrinkage may be less, depend- an admixture is used if the water content, cement con-
ing on the degree to which the water content of the tent, or air content is changed. By definition, for ex-
concrete is reduced. Creep will be reduced proportional ample, the water requirement of a concrete mixture for
to the increase in the strength of the concrete. The de- given consistency is reduced 5 percent or more with the
gree to which the use of an admixture, in given dos- introduction of a water-reducing admixture. Proce-
ages, affects shrinkage and creep may be different if dures for proportioning and adjusting concrete mix-
cements of different compositions are used in the con- tures are covered by ACI 211.1.
crete. One fundamental rule to remember is that when a
4.6.3 Durability-The effect of these admixtures on concrete mixture that is considered satisfactory in
resistance to freezing and thawing, including deicer workability and finishing qualities is modified to incor-
scaling, is small since resistance to freezing and thaw- porate a chemical admixture, the ratio of volumetric
ing is almost wholly a function of the air-void system proportions of mortar to coarse aggregate should re-
in the hardened concrete. An improvement may result main the same. Changes in water content, cement con-
from a decrease in w/c and increased strength. tent, and air content are compensated for by corre-
Some high-range water reducers cause bubble-spac- sponding changes in the content of fine aggregate, all
ing factor& higher than typically deemed necessary to on a solid or absolute volume basis, so that the volume
produce concrete that will survive freezing and thawing of mortar remains the same.
if critically saturated. A spacing factor of 0.008 in. Most chemical admixtures of the water-reducing type
(0.20 mm) or less generally is needed to insure resis- are water solutions. The water they contain becomes a
tance to freezing and thawing. Concrete made with part of the mixing water in the concrete and usually is
some high-range water reducers having spacing factors considered in the calculation of w/c ratio. The propor-
of 0.010 in. (0.25 mm) or higher was found upon test- tiona1 volume of the solids included in the admixture is
ing to be highly resistant to freezing and thawing. This so small in relation to the size of the batch that it can
may be a function of increased strength and density and be neglected.
reduced permeability, which allowed the concrete to re-
main less than critically saturated in the presence of 4.9-Quality control
water while being tested. It sometimes is necessary or desirable to determine
A small increase in resistance to freezing and thaw- that an admixture is the same as that previously tested,
ing and to aggressive waters and soils results from wa- or that successive lots or shipments are the same. Tests
ter reduction. This is due largely to decreased permea- that can be used to identify admixtures include solids
bility and increased strength. content, density, infrared spectrophotometry for or-
.
ganic materials, chloride content, pH, and others.
4.7-Preparation and batching Guidelines for determination of uniformity (variability)
Water-reducing and set-controlling admixtures of chemical admixtures are given in ASTM C 494.
should be batched and dispensed as liquids. When sup- Job inspectors may be instructed to sample deliveries
plied as solids, they should be mixed to a suitable so- of the admixture as part of the job quality control.
lution concentration following the manufacturers rec- Density can be determined on the job by a hydrometer
ommended practices. or volumetric flask as mentioned previously.
The density of admixtures mixed on the job, or those Admixture users should become familiar with ad-
applied as solutions, should be determined and com- mixtures appearances and odors. This knowledge has
pared with the manufacturers standards. Determina- sometimes prevented errors and mixups.
tion of density can be made easily and quickly with a
hydrometer or volumetric flask. The determinations 4.10-Precautions
should be made at a standard temperature and re- If adequate information is not available, tests should
corded for future reference as part of the job quality be made to evaluate the effect of the admixture on the
control program. Storage tanks for solutions should be properties of concrete made with job materials under
plainly identified and the solutions should be protected the anticipated ambient conditions and construction
from contamination, dilution, evaporation, and freez- procedures. Tests of water-reducing admixtures and set-
ing. controlling admixtures should indicate their effect on
Two or more admixtures of different types, such as a the following properties of concrete, insofar as they are
water-reducing and an air-entraining admixture, may pertinent to the job: (1) water requirement, (2) air con-
not be compatible when mixed together. Unless it is tent, (3) slump, (4) bleeding and possible loss of air
known that admixtures can be satisfactorily mixed to- from the fresh concrete, (5) time of setting, (6) corn-
pressive and flexural strength, (7) resistance to freezing ticles and causes a repulsion among them. The concrete
and thawing, (8) drying shrinkage, and (9) setting char- loses slump at a more rapid rate than the same concrete
acteristics. without the plasticizing admixture.
When admixtures are evaluated in laboratory trial
batches prior to job use, the series of mixtures should
be planned to provide necessary information. They The admixtures that are used to achieve flowing con-
need not follow ASTM C 494 procedures, although crete should meet the requirements of ASTM C 1017,
these may be a helpful guide. The trial mixtures should Type 1 (plasticizing) or Type 2 (plasticizing and retard-
be made with the same materials, particularly cement, ing). Commonly used materials are:
that will be used on the job and as close to job condi- 1. Sulfonated napthalene condensates, Types 1or 2
tions as possible. Temperature is particularly important 2. Sulfonated melamine condensates, Types 1or 2
to time of setting and early strength development. 3. Modified lignosulfonates
Trial mixtures can be made at midrange slump and 4. A combination of these types plus a water-reduc-
air contents expected or specified for the job. The ce- ing admixture, Type A; or water-reducing retarding
ment content or w/c ratio should be that required for admixture, Type D; or water-reducing accelerating ad-
the specified design strength and durability require- mixture, Type E
ments for the job. Trial mixtures also can be made with 5. High dosages of a water-reducing admixture, Type
a range of cement contents or w/c or other properties A, plus a water-reducing accelerating admixture, Type
to bracket the job requirements. E
Air content and time of setting of job concrete can This latter combination requires higher water con-
differ considerably from laboratory concrete with the tents than are required when using a high-range water-
same materials and mixture proportions. All parties reducing admixture (superplasticizer).
should be alert to this possibility at the start of a job
and be ready to make adjustments in the addition rates 5.3-Evaluation and selection
of materials (particularly air-entraining admixtures) to A decision to produce and use flowing concrete
achieve the specified properties of the concrete at the should include selecting the type of admixture to use.
project site. Factors to be considered in the choice of admixture(s)
Admixtures of all classes may be available in either include type of construction; restriction imposed on the
powder or liquid form. Since relatively small quantities chloride-ion content, time interval from introduction of
are used, it is important that suitable and accurately cement and water into the mixer; availability of accu-
adjusted dispensing equipment be employed. Refer to rate admixture dispensing equipment at the plant, job-
Chapter 1 for information on dispensing admixtures. site, or both; and ambient temperature.
If the decision is made to add the plasticizing admix-
CHAPTER 5-ADMIXTURES FOR FLOWING ture at the jobsite, an accurate means of introducing
CONCRETE the admixture into the concrete mixer must be assured.
5.1 -General Truck mixers should be equipped with admixture tanks
ASTM C 1017 defines flowing concrete as concrete designed to introduce the admixture into the concrete
that is characterized as having a slump greater than 7 V2 mixer so that it can be distributed evenly throughout
in. (190 mm) while maintaining a cohesive nature. . . the batch, and adequate mixing speed and revolutions
Flowing concrete can be placed so as to be self-leveling should be maintained. The concrete plant must be
yet remaining cohesive without excessive bleeding, seg- equipped to accurately measure the admixture into the
regation, or abnormal retardation. truck-mounted tanks.
Since production of flowing concrete by addition of Admixtures must be handled and measured properly.
water only would result in concrete of extremely low An admixture batching system must include a means of
quality, flowing concrete must be obtained through the visual verification of the dosage.
use of a plasticizing admixture, either normal (Type 1)
or retarding (Type 2). These materials used as plasticiz- 5.4-Application
ing admixtures for production of flowing concrete gen- Flowing concrete commonly is used in areas requir-
erally are identical to those used as high-range water- ing maximum volume placement (slabs, mats, pave-
reducing admixtures (superplasticizers) and conform to ments) in congested locations where the member is un-
ASTM C 494, Types F and G (see Chapter 4). usually shaped or a great amount of reinforcement is
As an example, concrete could be delivered to the present. Proper consolidation of high-strength concrete
jobsite at an initial slump of 2 to 3 in. (50 to 75 mm) for columns is difficult. Flowing concrete can be used
and the plasticizing admixture then could be added to in areas of limited access or where the maximum hori-
increase the slump to 8 in. or more, or the plasticizing zontal movement of the concrete is desirable.
admixture could be added at the plant to achieve this Flowing concrete is useful for pumping because it re-
slump level. duces pumping pressure and increases both the rate and
The plasticizing admixture, either a conventional wa- distance that the concrete can be pumped. Such con-
ter-reducing admixture or a high-range water-reducing crete is useful for projects requiring rapid form cycling
admixture, is adsorbed onto the hydrating cement par- with a maximum volume of concrete required per day,
2 MANUAL OF CONCRETE PRACTICE
coupled with a low w/c to achieve the early strengths slump, and air content, using aggregates graded within
required for stripping or tensioning. A short time cycle stipulated limits. This standard requires certain mini-
often can be used on such projects. mum differences in strength of concrete, range of times
of setting, and requirements regarding other aspects of
5.5-Performance criteria performance such as shrinkage and resistance to freez-
Expected performance of a given brand, class, or ing and thawing.
type of admixture may be estimated from one or more It is preferable to keep the cement content constant,
of the following sources: (a) results from jobs where the allowing the significant slump increase to assist in
admixture has been used under good technical control, placement. When admixtures are evaluated in labora-
preferably using the same concreting materials and un- tory trial mixtures prior to job use, the series of mix-
der conditions similar to those anticipated; (b) labora- tures should be planned to provide the necessary infor-
tory tests made to evaluate the admixture; and (c) tech- mation. Assuming specification compliance has been
nical literature and information from the manufacturer established, the tests need not follow ASTM C 1017
of the admixture. procedures such as slump, air content, and cement
The dosage required to increase the slump to flowing content; however, consistency of procedures should be
consistency varies depending upon the cement, the ini- maintained.
tial slump, w/c, temperature, time of addition, and The trial mixtures should be made with the same ma-
concrete mix proportions. The dosage required to in- terials, particularly cement, that will be used on the job,
crease slump from 1 to 8 in. may be 50 percent higher and simulate the job conditions as closely as possible.
than that required if the starting slump is 3 in. The Temperature is particularly important to times of set-
proposed flowing concrete mixture should be used ini- ting and early strength development. Trial mixtures can
tially in noncritical work so that proportions and pro- be made with a starting slump and air content in the
cedures can be verified before the mixture is used in the specified range. The dosage of the plasticizing admix-
areas requiring flowing concrete. The proportions of ture can be varied to achieve various slump increases.
the various concrete ingredients can be adjusted and the If allowed, the starting slumps also may be varied. The
dosage or the type of admixture varied to achieve an specified w/c should be maintained in each case, and a
acceptable initial slump, rate of slump loss, and setting range of slump can be reviewed. In this manner, the
characteristics. optimum mixture proportions can be selected and the
Results may vary with a given admixture due to dif- required results achieved.
ferences in cement, aggregates, other material, and Air content and time of setting of job concrete can
weather conditions from day to day. The use of admix- differ considerably from laboratory concrete with the
tures to increase slump from the 2 to 3 in. range may same materials and mixture proportions. Therefore,
also allow a cement reduction with a resultant cost sav- adjustment of the proposed mixture on the jobsite prior
ing. Since very little concrete is placed at that low to its use in the required locations usually is beneficial.
slump level, the additional water required to raise the
slump of conventional concrete from 2 to 3 in. to 5 to 5.6-Proportioning of concrete
6 in. would have to be matched with an increase in the A concrete mixture usually needs reproportioning
cement content if the strength and, consequently, the when a plasticizing admixture is added to achieve flow-
w/c is kept constant. ing concrete. Procedures for proportioning and adjust-
Flowing concrete is desirable for use in mass place- ing concrete mixtures are covered in 211.1. The
ments. The cement content may be kept low, which will fine aggregate-coarse aggregate ratio may require ad-
minimize heat development, and the lower water con- justment to assure that sufficient fines are present to
tent will reduce shrinkage. The plasticizing admixture allow a flowable consistency to be achieved without ex-
does not lower the temperature rise in concrete except cessive bleeding or segregation. It also may be neces-
as a result of reducing cement content. The early tem- sary to increase the cement content or add other fine
perature-rise characteristics also may be modified with materials such as pozzolan or slag.
the use of the retarding version of the plasticizing ad- Since 0.5 gal. or larger volume of plasticizing admix-
mixture (Type 2) or in combination with a conven- ture is customarily used per yd (m) of concrete to pro-
tional water-reducing retarding admixture (Type D). duce flowing concrete, the water in the admixture must
Concrete intended to have a compressive strength be accounted for in calculating w/c and the effect on
higher than 6000 psi (41 MPa) may be produced as mixture volume.
flowing concrete; since a low w/c is required, reducing
the mixing water is the best approach. Flowing con- 5.7-Effect on fresh concrete
crete, being easier to consolidate, also contributes to 5.7.1 Times of selling-ASTM C 1017 Type 1 ad-
proper bond between reinforcing steel and concrete in mixtures do not have much effect on times of setting.
areas where reinforcement is congested. Therefore, flowing concrete with a water content that
ASTM C 1017 is the specification for admixtures for would give a 2 to 4 in. slump if an admixture were not
flowing concrete. It provides for evaluation of the ad- used will set as quickly as if the admixture had not been
mixture for specification compliance under controlled used. Type 2 admixtures can reduce slump loss signifi-
conditions of temperature, fixed cement content, cantly and retard the initial times of setting of the con-
crete. At concrete temperatures below 60 F (15 C), the the w/c is lower than that of conventional concrete of
time of setting of concrete containing the Type 1 ad- Similar cement content at a 5-in. (127-mm) slump, and
mixture may be increased. strength improvement therefore is realized. Flowing
5.7.2 Workability and finishing-When concrete concrete with no water reduction, as compared to con-
mixtures are properly proportioned, flowing concrete is ventional concrete, often shows strength increases,
extremely workable without bleeding and segregation. When concrete strengths above 6000 psi (41 MPa) at 28
The fine-to-coarse aggregate ratio often has to be ad- days are desired, a high-range water-reducing admix-
justed by an increase in fine aggregate content to pre- ture often is added to achieve a low w/c. It then may
vent segregation at high slump. Flowing concrete be added again in the field as a plasticizing admixture
should be vibrated to achieve proper consolidation. to increase the slump in order to obtain the flowing
The characteristics of flowing concrete at the time it concrete required for the placing conditions.
is being machine floated or troweled will be similar to When flowing concrete is used, the flexural strength
those of conventional concrete with the same ingredi- is not changed significantly from that of the initial
ents. Properly proportioned flowing concrete should concrete of the same w/c at a lower slump.
not exhibit objectionable bleeding even at high slump. 5.8.3 Drying shrinkage and creep-When low-slump
Proper timing is imperative in the finishing operation. concrete and flowing concrete are compared, the drying
If a concrete is over-sanded or the air content is too shrinkage will be approximately the same if the water
high, or both, the surface of the concrete tends to dry contents are virtually identical. If, in conjunction with
before it sets. This condition may cause the concrete to producing flowing concrete, the water content of the
feel rubbery or jelly-like and cause finishing problems mixture at equal cement content is lowered, then the
by its stickiness and rolling. The problem of excessive drying shrinkage may be reduced. There seems to be
air entrainment in concrete used in floor slabs is partic- little change in the creep characteristics of concrete with
ularly apparent when the initial machine-finishing op- the use of these admixtures when comparisons are made
erations begin. on the basis of equal w/c concretes.
5.7.3 Bleeding and segregation-Properly propor- 5.8.4 Air entrainment-Higher dosages of air-en-
tioned concrete mixtures should not bleed excessively or training admixture usually are required for flowing
segregate. The upper slump limit of cohesive yet flow- concrete to maintain proper air content as compared to
able concrete varies and it can be determined from test- conventional concrete. As with any air-entrained con-
ing the mixture prior to its use. Segregation and bleed- crete, the air content in the field must be checked so
ing may be reduced by increasing the fine-to-coarse ag- that the air-entraining admixture dosage can be modi-
gregate ratio, or by the addition of other fine materials. fied as required to keep the air content in the specified
5.7.4 Rate of slump loss- The rate of slump loss may range.
be altered by many factors such as concrete tempera- 5.8.5 Resistance to freezing and thawing-Flowing
ture, type and amount of cement, water content, time concrete exhibits degrees of resistance to freezing and
of admixture addition, and amount of admixture em- thawing similar to conventional concrete with a similar
ployed. Therefore, an acceptable rate of slump loss can w/c and air-void system. The air-void structure may
be achieved by monitoring these conditions and by have larger spacing factors and a decrease in the num-
changing the initial time of setting characteristics of the ber of voids per inch compared to the control concrete;
concrete. however, satisfactory resistance to freezing and thaw-
5.7.5 Additional dosages-Additional dosages of ing has been achieved in most cases. Lucas (1981) indi-
plasticizing admixture should be used when delays oc- cated that concrete made with a high-range water-re-
cur and the required slump has not been maintained. ducing admixture (superplasticizer) has a smaller ten-
Two additional dosages have been used with success; dency to absorb chloride than do untreated concretes of
more dosages generally are less effective. In general, the the same w/c.
compressive strength level is maintained or increased 5.8.6 Permeability-Flowing concrete has resistance
and the air content decreased. Therefore, if air entrain- to chloride penetration similar to, if not slightly greater
ment is of concern, it must be checked after the con- than, that of conventional concrete with the same w/c.
crete has been redosed and returned to its intended When the admixture is used to reduce the w/c, the re-
slump. sistance of the concrete to chloride penetration is even
5.8-Effect on hardened concrete greater. Flowing concrete tends to be of lower permea-
5.8.1 Heat of hydration and temperature rise-Heat bility because of better consolidation, reduced bleed-
of hydration is not reduced if the cement content is not ing, and increased cement hydration.
reduced. If the use of flowing concrete involves the use Low permeability results from low w/c concrete
of a lower cement content, the heat evolved will be re- when it is properly placed and cured. Flowing concrete
duced. If the rate of hydration is not changed, the tem- with a low w/c can be placed and consolidated easily.
perature rise will not be changed if the cement content This allows concrete with a w/c below 0.40 to be placed
is not reduced. easily; therefore, the resultant concrete, if properly
5.8.2 Strength-Since concrete that is intended to be cured, can be of extremely low permeability and have
flowing often is batched with a water content that good resistance to the penetration of aggressive solu-
would result in a slump of 2 to 4 in. (51 to 102 mm), tions.
5.8.7 Bond-Flowing concrete can improve bond abnormally slow or the temperature is high, or both,
strength to reinforcing steel when compared to similar the USC of a Type 2 admixture may be desirable.
concrete with a 100-mm (4-in.) slump (Collepardi and Changes in cement composition or in aggregate
Corradi 1979) conventional and flowing concrete. Brett- grading, or both, can cause significant variations in the
man, Darwin, and Donahey (1986) found that in reinforced flowing concrete characteristics. Therefore, these
concrete beams bond strength of concrete of equal w4c was changes should be minimized.
decreased as the slump was increased and was decreased the
longer the concrete remained unhardened. Proper vibration
is required for both concretes. Proper consolidation around CHAPTER 6-MISCELLANEOUS ADMIXTURES
the reinforcing is more easily achieved with flowing con- 6.1 -Gas-forming admixtures
crete. 6.1.1 Introduction-The gas-void content of con-
crete can be increased by the use of admixtures that
generate or liberate gas bubbles in the fresh mixture
5.9-Quality assurance during and immediately following placement and prior
It is desirable and sometimes necessary to determine to setting of the cement paste. Such materials are added
that an admixture is the same as that previously tested to the concrete mixture to counteract settlement and
or that successive lots or shipments are the same. Tests bleeding, thus causing the concrete to retain more
that can be used to identify admixtures include solids nearly the volume at which it was cast. They are not
content, density, infrared spectrophotometry for or- used for producing resistance to freezing and thawing;
ganic materials, chloride content, pH, and others. Ad- any such effect is incidental. Air-entraining admixtures
mixture manufacturers can recommend which tests are are discussed in Chapter 2.
most suitable for their admixtures and the results that 6.1.2 Materials-Admixtures that produce these ef-
should be expected. Guidelines for determining uni- fects are hydrogen peroxide, which generates oxygen;
formity of chemical admixtures are given in ASTM metallic aluminum (Menzel 1943; Shideler 1942), which
c 1017. generates hydrogen; and certain forms of activated car-
bon from which adsorbed air is liberated.
5.10-Control of concrete Only aluminum powder is used extensively for gas
5.10.1 Concrete mixture proportioning-Concrete formation. An unpolished powder usually is preferred,
should be proportioned with flowing characteristics in although polished powder may be used when a slower
mind; therefore, sufficient fines must be present in the reaction is desired. The rate and duration of gas evolu-
mixture to allow the desired slump to be achieved with- tion of the cement (particularly alkali content), temper-
out excessive bleeding and segregation. Trial batches ature, w/c, and fineness and particle shape of the
usually are prepared to confirm concrete characteris- aluminum powder.
tics. The mixture is adjusted in the field to verify flow- The effectiveness of the treatment is controlled by the
ing characteristics. duration of mixing, handling, and placing operations
Necessary adjustments can be made to assure the user relative to the speed of gas generation. The addition
of the optimum mixture with regard to slump, work- rate may vary from 0.006 to 0.02 percent by weight
ability, rate of slump loss, and setting characteristics. (mass) of cement under normal conditions, although
Verification of early strengths can be accomplished if larger quantities may be used to produce low-strength
required. The rate of slump loss should be noted and cellular concrete. Approximately twice as much alumi-
adjusted as required. The mixture proportions also num powder is required at 40 F (4 C) as at 70 F (21 C)
should conform to the procedures indicated in ACI to produce the same amount of expansion.
211.1 or ACI 211.2. Flowing concrete should be placed Because of the very small quantities of aluminum
in accordance with ACI 304 and consolidated in ac- powder generally used [a few grams per 100 lb (45 kg)
cordance with ACI 309. of cement], and because aluminum powder has a ten-
5.10.2 Field control-Flowing concrete control re- dency to float on the mixing water, it generally is pre-
quires checking the initial slump or water content prior mixed with fine sand, cement, or pozzolan, or incor-
to the addition of the admixture to assure that the wa- porated in commercially available admixtures having
ter content and the w/c are as required. After the plas- water-reducing set-retarding effects.
ticizing admixture is added and thoroughly mixed into In cold weather, it may be necessary to speed up the
the batch, the resulting slump should be in the speci- rate of gas generation by the addition of such caustic
fied range. For air-entrained concrete, the air content materials as sodium hydroxide, hydrated lime, or tri-
also must be checked at the point of discharge into the sodium phosphate. This may be done to insure suffi-
forms. cient gas generation before the mixture has set and
Rate of slump loss, initial setting characteristics, and hardened.
both early and final strength results may require mix- 6.1.3 Effectiveness- The release of gas, when prop-
ture adjustments. Slump loss and setting characteristics erly controlled, causes a slight expansion of freshly
may be adjusted by changes in the plasticizing admix- mixed concrete. When such expansion is restrained,
ture dosage or by concurrent use of accelerating or re- there will be an increase in bond to horizontal reinforc-
tarding admixtures. When the concrete placement is ing steel without excessive reduction in compressive
strength. Too much gas-producing material may pro- 6.3.2 Materials-The most common admixture for
duce large voids, seriously weakening the matrix. To a this purpose is a combination of finely divided or gran-
considerable extent, the effect on compressive strength ulated iron and chemicals to promote oxidation of the
depends on the degree to which the tendency of the iron. Expansion is greatest when the mixture is exposed
mixture to expand is restrained; therefore, it is impor- alternately to wetting and drying. Expansive cements
tant that confining forms be tight and adequately are used on large projects where a predetermined uni-
closed. Gas-forming agents will not overcome shrink- form degree of expansion is required (Klein and Trox-
age after hardening caused by drying or carbonation. ell 1958). Materials are available (calcium sulfoalumi-
nates) that can be added to portland cements to
6.2-Grouting admixtures produce useful amounts of expansion. These materials
6.2.1 Introduction-Many of the admixtures used for are part of the cementitious component and, therefore,
specific purposes in concrete are used as grouting ad- not admixtures. For additional information regarding
mixtures to impart special properties to the grout. Oil- these cements refer to ACI 223.
well cementing grouts encounter high temperatures and 6.3.3 Effect of expansion on concrete-The con-
pressures with considerable pumping distances in- trolled expansion produced by these admixtures may be
volved. Grout for preplaced-aggregate concrete re- of about the same magnitude as the drying shrinkage
quires extreme fluidity and nonsettling of the heavier expected at later ages or it may be slightly greater. For
particles. Nonshrink grout requires a material that will a given application, the extent of expansion and the
not exhibit a reduction from its volume at placement. time interval during which it takes place are very im-
Installation of tile subjects bonding and joint-filling portant and must be under control for the most satis-
grout to very fast drying or loss of water through ab- factory results.
sorption by the substrate and the tile. A wide variety of For unrestrained concrete, the expansion must not
special purpose admixtures are used to obtain the spe- take place before the concrete gains sufficient tensile
cial properties required. strength, or else the concrete will be disrupted. For re-
6.2.2 Materials-For oil-well cementing grouts, restrained applications, the concrete must be strong
tarders, as described in Chapter 4, are useful in delay- enough to withstand the compressive stresses devel-
ing setting time. Bentonite clays may be used to reduce oped. It is reported that restraint in only one direction
slurry density, and materials such as barite and iron fil- (Klein, Karby, and Polivka 1961) creates some degree
ings may be used to increase the density (Hansen 1954). of compression in the other two orthogonal directions.
Tile grouts and certain other grouts use materials such
as gels, clays, pregelatinized starch, and methyl cellu- 6.4-Bonding admixtures
lose to prevent the rapid loss of water. 6.4.1 Introduction-Admixtures specifically formu-
Grout fluidifiers for preplaced-aggregate concrete lated for use in portland cement mixtures to enhance
grouts usually contain water-reducing admixtures along bonding properties generally consist of an organic
with admixtures to prevent settlement of heavy constit- polymer emulsion commonly known as latex (Goeke
uents of the grout. Nonshrink grouts may contain gas- 1958; Ohama 1984). In general, latex forms a film
forming or expansion-producing admixtures, or both. throughout the concrete.
Special grout applications may require such admix- 6.4.2 Materials-A wide variety of types of latex is
tures as accelerators and air-entraining materials as de- used in paints, paper coatings, textile backing, etc. La-
scribed in other sections. Tests should be conducted to tex for use as a concrete admixture is formulated to be
determine the compatibility of admixtures with the ce- compatible with the alkaline nature of the portland ce-
ment to be used. ment paste and the various ions present. An unstable
6.2.3 Effect-Retarders may be used to keep a grout emulsion will coagulate in the mixture, rendering it un-
fluid at temperatures up to 400 F (204 C) and pressures suitable for use.
as high as 18,000 psi (124 MPa) for 1 hr or more. 6.4.3 Function- When used as admixtures in the
Grouting is a highly specialized field, usually requiring quantities normally recommended by the manufactur-
material properties not necessary for ordinary concret- ers (5 to 20 percent by weight [mass] of the cement),
ing operations. The admixture manufacturers sugges- different latexes may affect the unhardened mixture
tions on addition rates should be followed; however, differently. For example, a film-forming latex may feel
tests must be performed on the grout to determine if tacky in contact with air.
the properties of the grout meet the project require- Water still is necessary to hydrate the portland ce-
ments. ment of the cement-polymer system. The polymer com-
ponent becomes effective only when the emulsion is
6.3-Expansion-producing admixtures broken through a drying out process. The polymer
6.3.1 Introduction-Admixtures that expand during emulsion carries a portion of the mixing water into the
the hydration period of the concrete or react with other mixture, the water being released to the cement during
constituents of the concrete to cause expansion are used the hydration process.
to minimize the effects of drying shrinkage. They are At the same time, this release of water sets the emul-
used both in restrained and unrestrained concrete sion. Hence, after an initial 24 hr of moist curing to
placement. eliminate chances of cracking, additional moist curing
is not necessary and actually is undesirable since the 1. Water-soluble synthetic and natural organic poly-
emulsion will not have an opportunity to dry and de- mers that increase the viscosity of water-cellulose de-
velop the desired strength. The only exception to this is rivatives (methyl, ethyl, hydroxyethyl, and other cellu-
when a very low w/c is used (less than 0.3 by weight lose gums); polyethylene oxides; acrylic polymers;
[mass]). polyacrylamides; carboxyvinyl polymers; natural wa-
Upon drying or setting, the polymer particles coa- ter-soluble gums; starches; and polyvinyl alcohol,
lesce into a film, adhering to the cement particles and 2. Organic flocculants -carboxyl-containing styrene
to the aggregate, thus improving the bond between the copolymers, other synthetic polyelectrolytes, and natu-
various phases. The polymer also fills microvoids and ral water-soluble gums.
bridges microcracks that develop during the shrinkage 3. Emulsions of various organic materials-paraffin,
associated with curing (Isenburg et al. 1971). This sec- coal tar, asphalt, and acrylic and other polymers.
ondary bonding action preserves some of the potential 4. High-surface-area inorganic materials-bentonites
strength normally lost due to microcracking. and organic-modified bentonites and silica fume.
Greater strength and durability are associated with 5. Finely divided inorganic materials that supplement
the lower w/c of latex mixtures. The polymer particles cement in cement paste-fly ash and various raw or
act as a water replacement, resulting in more fluidity calcined pozzolanic materials, hydrated lime, and nat-
than in mixtures without latex, but having a similar w/c ural or precipitated calcium carbonates and various
ratio. rock dusts.
The compressive strength of moist-cured grouts, This list does not include all of the materials listed in
mortars, and concrete made with these materials may McCutcheons Functional Materials (McCutcheon Di-
be greater or less than that of mixtures of the same ce- vision 1975). Classifications may be misleading since
ment content without the admixture, depending on the the performance of a given admixture can change
admixture used (Grenley 1967). However, the increase drastically with change of dosage rates, cement com-
in bond, tensile, and flexural strengths far outweigh the position, mixing temperature and time, and other fac-
possible disadvantage of slight compressive-strength re- tors. An example is provided by the polyethylene ox-
duction. Latex-modified concrete has better abrasion ides. When used in small amounts of 0.01 to 0.05
resistance, better resistance to freezing and thawing, percent of cement weight (mass), they improve pumpa-
and reduced permeability. bility. Larger amounts produce thickening that may or
6.4.4 Limitations-Surfactants present in latex emul- may not disappear upon prolonged mixing.
sions can entrap air and may require that a foam-sup- Other examples are provided by synthetic polyelec-
pressing agent be used. Dosage rates for air-entraining trolytes, which act as flocculants or thickeners depend-
agents will be affected. Some types of polymers will ing upon dosage levels. It would appear to be highly
soften in the presence of water; therefore, these types undesirable to induce flocculation and increase bleed-
should not be used in concrete that will be in contact ing in pumped concrete. Nevertheless, these admixtures
with water during service. The ultimate result obtained are considered effective in pumped concrete because
with a bonding admixture is only as good as the sur- they lower bleeding capacity or total bleeding despite
face to which the mixture is applied. The surface must causing increases in initial rates of bleeding.
be clean, sound, and free from such foreign matter as Other problems with the listing given previously oc-
paint, grease, and dust. cur with the natural gums (algins, tragacanth, arabic).
They can function as thickeners or flocculants depend-
6.5-Pumping aids ing upon dosage levels and other factors. These agents
6.5.1 Introduction-Pumping aids for concrete are and some of the synthetic materials also can have dis-
admixtures with the sole function of improving con- persing or water-reducing effects. Gum arabic is a
crete pumpability. They normally will not be used in powerful water reducer for calcium-sulfate plasters, but
concrete that is not pumped or in concrete that can be in portland cement pastes, it can produce a gluelike
pumped readily. stickiness.
The primary purpose of using admixtures to enhance Factors to consider in the use of emulsions (paraf-
pumpability of concrete is to overcome difficulties that fins, polymers) are whether they function in the desired
cannot be overcome by changes in the concrete mixture way in cement paste by remaining stable or by breaking
proportions. As in the use of many ingredients in con- of the emulsion. Both types of paraffin emulsion are
crete, the objective is economic. considered to be useful in Australian concrete technol-
6.5.2 Materials-Many pumping aids are thickeners ogy*
that increase the cohesiveness of concrete. The Stan- The listing given previously does not include such air-
dards Association of Australia* identified five cate- entraining agents or surface-active agents widely used in
gories of thickening admixtures for concrete and mor- concrete as hydroxylated carboxylic acid derivatives,
tar as follows: lignosulfonates and their derivatives, formaldehyde-
condensed naphthalene sulfonates, melamine poly-
mers, and other set-retarding or water-reducing admix-
* " I n f o r m a t i o n on Thickening Admixtures for Use in Concrete and Mor- tures, The omission here is deliberate because a
tar, " Draft for Comment, Miscellaneous Publication No. DR 73146, Stan-
dards Association of Australia, Committee BD/33, Oct. 1973, unpublished.
substantial proportion of concrete that is to be pumped
in North America will be specified as air-entrained Table 6.6.2 - Colors produced by various
concrete, and probably also will contain a water-reduc- pigments
ing or set-retarding admixture. Therefore, such admix-
tures may be considered to be normal constituents of Black iron oxide
Grays to black
concrete. Mineral black
Evaluation of and experience with these admixtures Carbon black
are well known. In this chapter, these types of admix- Blue Ultramarine blue
tures are not considered specifically as pumping aids. Bright red to deep red Red iron oxide
Brown Brown iron oxide
They will be present in many cases in combination with Raw and burnt umber
other agents introduced for the specific purpose of im- Ivory, cream, or buff Yellow iron oxide
proving pumpability. In such cases, evaluation of ef- Green Chromium oxide
fects of such combinations on pumpability and other Phthalocyanine green
properties of concrete will be required to determine White Titanium dioxide
whether or not adverse interactions occur between ad-
mixtures. pigment generally have little or no effect on the physi-
6.5.3 Effects on concrete-A side effect of a con- cal properties of the fresh or hardened concrete. Larger
crete pumpability-enhancing admixture is any effect it quantities may increase the water requirement of the
may have on fresh concrete other than that on pumpa- mixture to such an extent that the strength and other
bility, and any effect that changes the characteristics of properties, such as abrasion resistance, may be ad-
the hardened concrete. Since the main effect of a water vcrscly affected.
thickener is to increase viscosity, substantial thickening The addition of an unmodified carbon black will in-
can increase water requirements with the usual conse- crease considerably the amount of air-entraining ad-
quences of reduced strength. By using a suitable dis- mixture needed to provide resistance of the concrete to
persant in combination with a thickening agent, no in- freezing and thawing (Taylor 1948). However, most
crease in water may be required. At certain dosage carbon blacks available for coloring concrete do con-
levels, some thickeners act as dispersants of solid par- tain air-entraining materials in sufficient quantity to
ticles. Many of the thickening agents cause entrainment offset the inhibiting effect of the carbon black.
of air. To control air content, a defoamer (for exam- Brilliant concrete colors are not possible with either
ple, tributyl phosphate) may be needed, especially when natural or synthetic pigments due to their low allow-
higher concentrations of pumping aid are used in mor- able addition rates and the masking effects of the ce-
tars and concretes. ment and aggregates. Stronger colors can be obtained
Many of the synthetic and natural organic thickening if white rather than grey cement is used. If bright colors
agents retard the setting of portland cement pastes. For are required, a surface coating should be specified in
dosages of methyl or hydroxyethyl cellulose of 0.1 per- lieu of pigment admixtures.
cent or more by weight (mass) of portland cement, re-
6.7-Flocculating admixtures
tardation may be substantial. In any case, the particu- Synthetic polyelectrolytes, such as vinyl acetate-mal-
lar concrete system in which a pumpability-enhancing eic anhydride copolymer, have been used as flocculat-
admixture is incorporated must be evaluated in terms of ing admixtures. Published reports (Bruere and Mc-
side effects upon the fresh and hardened concrete in Gowan 1958; Vivian 1962) indicate that these materials
addition to assessing the effectiveness of the admixture increase the bleeding rate, decrease the bleeding capac-
in performing its intended function. ity, reduce flow, increase cohesiveness, and increase
early strength. Although the mechanism of this action
6.6-Coloring admixtures is not understood fully, it is believed that these com-
6.6.1 Introduction-Pigments specifically prepared pounds, containing highly charged groups in their
for use in concrete and mortar are available both as chains, are adsorbed on cement particles, linking them
natural and synthetic materials. They are formulated to together. The net result is equivalent to an increase in
produce adequate color without materially affecting the interparticle attraction, which increases the tendency of
desirable physical properties of the mixture. They are the paste to behave as one large floc.
covered by ASTM C 979.
6.6.2 Materials-The pigments listed in Table 6.6.2 6.8-Fungicidal, germicidal, and insecticidal
may be used to obtain a variety of colors. admixtures
6.6.3 Effects on concrete properties-The addition 6.8.1 Introduction- Certain materials have been
rate of any pigment to concrete normally should not suggested as admixtures for concrete or mortar to im-
exceed 10 percent by weight (mass) of the cement (Wil- part fungicidal, germicidal, and insecticidal properties.
son 1927); however, some pigments, such as carbon The primary purpose of these materials is to inhibit and
black, should be used at lesser quantities. Natural pig- control the growth of bacteria and fungus on concrete
ments usually are not ground as finely as, and often are floors and walls or joints. They may not always be
not as pure as, synthetic materials and generally do not completely effective.
produce as intense a color per unit of addition. Except 6.8.2 Materials-The materials that have been found
for carbon black, additions of less than 6 percent of to be most effective are: polyhalogenated phenols (Le-
vowitz 1952), dieldrin emulsion (Gay and Wetherly 2. Butyl stearate reportedly performs better than
1959), and copper compounds (Robinson and Austin soap as a water repellent. It does not entrain air and
195 1; and Young and Talbot 1945). has a negligible effect on strength. It is added as an
6.8.3 Effectiveness-Addition rates vary from 0.1 to emulsion with the stearate being 1 percent by weight
10 percent by weight (mass) of the cement, depending (mass) of the cement.
on the concentration and composition of the chemical. 3. Among petroleum products are mineral oils, as-
The higher rates, above 3 percent, may have an adverse phalt emulsions, and certain cutback asphalts. Heavy
effect on the strength of the concrete. The effectiveness mineral oil is effective as a water repellent for concrete
of these materials, particularly the copper compounds, and in reducing its permeability. The petroleum prod-
is reported to be of a temporary nature. This probably uct must be a fluid and have a viscosity approximately
will vary with the type of wear and cleaning methods equal to SAE60, with no fatty or vegetable oils.
employed. 4. In addition, there is a group of miscellaneous ma-
terials sometimes advertised as dampproofing agents.
6.9-Dampproofing admixtures All of these are usually detrimental to concrete
6.9.1 Introduction-The term dampproofing im- strength, and none are truly dampproofers. These in-
plies prevention of water penetration of dry concrete or clude barium sulfate and calcium and magnesium sili-
stoppage of water transmission through unsaturated cates, finely divided silica and naphthalene, colloidal
concrete. However, admixtures have not been found to silica and fluosilicate, petroleum jelly and lime, cellu-
produce such effects and the term has come to mean a lose materials and wax, silica and aluminum, coal tar
reduction in rate of penetration of water into dry con- cut with benzene, and sodium silicate.
crete or in rate of transmission of water through unsat- 6.9.3 Effectiveness-Dampproofing admixtures may
urated concrete. aid in shedding or repelling water from the surface of
When some concrete dams, retaining walls, tanks, the concrete. Some dampproofing admixtures also may
and other structures show evidence of leakage, it usu- aid in reducing the ability of rain to penetrate the sur-
ally is the result of faulty production and placement of face of the concrete or reducing the wicking or wetting
concrete. When properly proportioned concrete mix- properties of concrete. These admixtures, by reducing
tures are used and placed with high-quality workman- penetration of the visible pores, may retard penetration
ship under qualified inspection, the concrete in a struc- of rain into concrete block made of nonplastic mix-
ture should be virtually impermeable, although leakage tures. Test data show that they also reduce the rate of
still may occur through cracks. Dampproofing admix- penetration of moisture into the micropores of dry
tures cannot be expected to be as reliable or effective as concrete, but there is no indication that there are com-
applying a moisture-barrier system to the concrete. parable effects on the transmission of moisture through
Dampproofing may reduce the rate of penetration of unsaturated concrete, except when the concrete con-
aggressive chemicals found in water; however, it will tains paste with relatively high porosity.
not stop them. Dampproofing admixtures also may A paste of high porosity results from low cement
reduce the penetration of water into concrete, thus de- content and correspondingly high w/c, lack of curing,
laying the effects of damage caused by freezing and or from both factors. If the concrete has a sufficiently
thawing by reducing the amount or rate of moisture low porosity, such as that obtained by producing a
entering the concrete. well-cured paste having w/c not over 0.6 by weight
An admixture described as a dampproofer may have (mass), dampproofing agents give no appreciable im-
a secondary effect on the properties of fresh concrete provement.
not directly indicated by the name. For example, it may The Building Research Advisory Board (1958) re-
promote entrainment of air; thus, it may more prop- ported that in the opinion of the majority of 61 observ-
erly be considered an air-entraining admixture. ers, dampproofing admixtures are not . . . effective or
This section deals with those effects directly implied acceptable in controlling moisture migration through
by the word dampproofing on the properties of slabs-on-ground.
hardened concrete. A special advisory committee to the Building Re-
6.9.2 Materials-Admixtures for dampproofing are search Advisory Board reached the following conclu-
used to render the concrete hydrophobic and therefore sion on the basis of data from tests of moisture trans-
capable of repelling water that is not under hydrostatic mission through unsaturated concrete slabs: The
pressure. Committee does not find adequate data to demonstrate
Admixtures for dampproofing include soaps, butyl the effectiveness of any admixture to reduce the trans-
stearate, and certain petroleum products (Dunagan and mission of moisture through concrete slabs-on-ground
Ernst 1934; Uppal and Bahadur 1958). in a manner sufficient to replace either a vapor barrier
1. The soaps are composed of salts of fatty acids, or granular base, or both, under conditions where such
usually calcium or ammonium stearate or oleate. The protection would be needed.
soap content usually is 20 percent or less, the remain-
der being calcium chloride or lime. Total soap added 6.10-Permeability-reducing admixtures
should not exceed 0.2 percent by weight (mass) of con- Permeability refers to the rate at which water is
crete. Soaps cause entrainment of air during mixing. transmitted through a saturated specimen of concrete
under an externally maintained hydraulic gradient. Ad- admixtures are based on the use of 0.2 percent by
mixtures of the kinds discussed in the previous section weight (mass) of concrete. Some laboratories have re-
do not reduce the permeability of saturated concrete. ported on the use of calcium chloride with the barium
However, mineral powders (essentially fly ash, raw or salts to counteract strength loss.
calcined natural pozzolans, and silica fume), properly Air entrainment, regardless of the admixture used,
proportioned, reduce the permeability of mixtures in has been shown to lower the expansion slightly,
which the cement content of the paste is relatively low. 6.11.3 Effectiveness-Limited laboratory data on the
This is due to the production of additional cementi- use of chemical admixtures to reduce expansion result-
tious material, primarily calcium silicate hydrates and ing from the alkali-silica reaction are available; there-
calcium aluminum silicate hydrates, which form by the fore, no recommended practices are presented. Any
combination of lime from the cement and silica and user of these materials should test them thoroughly be-
other components in the mineral powder. fore proceeding to field use.
The reduction of total water content by means of a
water-reducing admixture should reduce the total po- 6.12-Corrosion-inhibiting admixture
rosity slightly, hut there are no adequate data to dem- 6.12.1 Introduction-Many investigators have stud-
onstrate that permeability is reduced materially. How- ied the corrosion of iron and steel with particular ref-
ever, decreased permeability with the use of high-range erence to protective coatings. It has been found that
water reducers at equivalent w/c has been reported. concrete furnishes ample protection to the steel embed-
Polymer-emulsion admixtures have been used to re- ded in it, although a limited number of cases have been
duce permeability of concrete overlays for bridge decks reported in which infiltrating or percolating waters find
and parking decks. The polymer particles coalesce into a way through the concrete, removing or carbonating
a continuous film, which reduces permeability by seal- the calcium hydroxide (Cushman 1909; Cushman and
ing air voids and blocking microcracks (Isenburg et al. Gardener 1910). Reports indicate that the use of small
1971; Whiting 1981).* quantities of bentonite in the mixing water reduces cor-
Accelerating admixtures such as calcium chloride in- rosion by reducing the permeability of the concrete.
crease the rate of hydration (see Section 3.2.2), thereby The major contributor to corrosion of reinforcing
reducing the length of time required for a concrete steel is the presence of chlorides in the concrete. The
mixture to attain a given fraction of its ultimate degree chlorides may come from circumstances such as expo-
of impermeability (see Section 3.2.1). However, any sure of the concrete to saline or brackish waters, expo-
advantage attained this way is likely to be temporary sure to saline soils from which chlorides can reach the
since, if conditions are such that water is being trans- steel by diffusion through the concrete, by entrance of
mitted through the concrete, they also are conducive to deicer solutions through cracks or pores in the con-
continued hydration of cement. crete, or use of calcium chlorides as an admixture con-
stituent (see Chapter 3).
6.11 -Chemical admixtures to reduce alkali- Corrosion caused by the inclusion or infiltration of
aggregate expansion chlorides in concrete is difficult to control once it has
6.11.1 Introduction-The use of pozzolans to reduce started. Numerous chemicals have been evaluated as
expansion caused by alkali-aggregate reaction has been potential corrosion-inhibiting admixtures for concrete
studied widely and reported (Stanton 1950). As early as (Verbeck 1975; Clear and Hay 1973; Griffin 1975).
1950, reports began to appear on admixtures other than These include chromates, phosphates, hypophosphor-
pozzolans to reduce expansion caused by alkali-aggre- ites, alkalies, nitrites, and fluorides. Recently, calcium
gate reaction. Since that time there has been little new nitrite has been reported as an effective corrosion in-
information added in the form of meaningful research hibitor (Rosenberg et al. 1977). Studies of this material
of field practice (see ACI Committee 212s 1963 re- are continuing (Virmani, Clear, and Pasko 1983).
port). 6.12.2 Materials-The use of sodium benzoate at a
6.11.2 Materials-Soluble salts of lithium, barium, rate of 2 percent in the mixing water or a 10 percent
and certain air-entraining and some water-reducing set- benzoate-cement slurry painted on reinforcement, or
retarding admixtures have been reported to produce re- both, have been described as effective (Lewis, Mason,
duction in expansion of laboratory mortar specimens. and Brereton 1956). Analysis showed that the sodium
Outstanding reductions have been obtained in such benzoate remained in the concrete after five years ex-
specimens using 1 percent additions of the lithium salts posure. It also accelerates compressive strength devel-
and 2 to 7 percent additions by weight (mass) of ce- opment.
ment of certain barium salts. The lithium salts are very Calcium lignosulfonate reduces the tendency for cor-
expensive. rosion of steel in concrete containing calcium chloride
Salts of proteinaceous materials and water-reducing (Kondo, Takeda, and Hideshima 1959).
set-retarding materials have shown moderate reduc- Sodium nitrite has been investigated by Moskvin and
tions in expansion. Data on the protein air-entraining Alekseyev (1958) as an inhibitor of corrosion of steel in
autoclaved products. These authors suggest that the
*Also, Grenley, Dallas G., Michalyshin, J., and Molodovan, D., Mar. 1983,
Effect of Certain Concrete Admixtures on the Chloride Permeability of high alkalinity, which normally is present in concrete
Concrete, Dow Chemical Company, Inc., presented at the Annual Meeting of
the American Concrete Institute, Los Angeles. and which serves to passivate the steel, may be reduced
212.3 MANUAL OF CONCRETE PRACTICE
and Brereton 1956). Analysis showed that the sodium 212.2R Guide for Use of Admixtures in
benzoate remained in the concrete after five years ex- Concrete
posure. It also accelerates compressive strength devel- 222R Corrosion of Metals in Concrete
opment. 223 Standard Practice for Use of Shrinkage-
Calcium lignosulfonate reduces the tendency for cor- Compensating Concrete
rosion of steel in concrete containing calcium chloride 304R Guide for Measuring, Mixing, Trans-
(Kondo, Takeda, and Hideshima 1959). porting, and Placing Concrete
Sodium nitrite has been investigated by Moskvin and 306R Cold Weather Concreting
Alekseyev (1958) as an inhibitor of corrosion of steel in 308 Standard Practice for Curing Concrete
autoclaved products. These authors suggest that the 309R Guide for Consolidation of Concrete
high alkalinity, which normally is present in concrete 311.1R Manual of Concrete Inspection (SP-2)
and which serves to passivate the steel, may be reduced 311.4R Guide for Concrete Inspection
considerably by autoclave treatment, especially when 318 Building Code Requirements for
siliceous admixtures are present. Two to 3 percent so- Reinforced Concrete
dium nitrite by weight (mass) of cement was found to 506R Guide to Shotcrete
be an efficient inhibitor under these conditions. 523.lR Guide for Cast-in-Place Low Density
Sarapin (1958) found by storage tests that 2 percent Concrete
sodium nitrite was effective in preventing corrosion of 548R Polymers in Concrete
steel in concrete containing calcium chloride under cer-
tain conditions of storage. Low-solubility salts such as
certain phosphates or fluosilicates and fluoaluminates
are beneficial, according to limited reports. Dosage
should be limited to 1 percent by weight (mass) of ce-
ment. ASTM
6.12.3 Effect-Warnings have been sounded against
the use of inhibitors, For example, the South African C 94 Standard Specification for Ready-Mixed
National Building Research Institute (1957) made the Concrete
following statement, Integral additives: although cer- C 114 Standard Methods for Chemical Analysis
tain inert and reactive materials have shown promise, of Hydraulic Cement
their use cannot be recommended at this stage, as in- C 125 Terminology Relating to Concrete and
sufficient evidence of their effectiveness or possible di- Concrete Aggregates
seffects from the inhibitor addition might reasonably be C 138 Standard Test Method for Unit Weight,
expected, if the steel surface is clean and chlorides ab- Yield, and Air Content (Gravimetric) of
sent; but under such conditions, there is unlikely to be Concrete
serious trouble without added inhibitor. C 150 Standard Specification for Portland
Cement
C 173 Standard Test Method for Air Content
of Freshly Mixed Concrete by the
Volumetric Method
C 231 Standard Test Method for Air Content
of Freshly Mixed Concrete by the
Pressure Method
CHAPTER 7-REFERENCES C 233 Standard Test M e t h o d f o r Air-
Entraining Admixtures for Concrete
C 260 StandardSpecificationforAir-Entraining
7.1-Recommended references Admixtures for Concrete
C 457 Standard Practice for Microscopical
The documents of the various standards- Determination of Air Void Content and
producing organizations referred to in this document Parameters of the Air Void System in
follow with their serial designation. Hardened Concrete
C 494 Standard Specification for Chemical Ad-
American Concrete Institute mixtures for Concrete
C 595 Standard Specification for Blended
116R Cement and Concrete Terminology Hydraulic Cements
201.2R Guide to Durable Concrete C 666 Standard Test Method for Resistance of
211.2 Standard Practice for Selecting Concrete to Rapid Freezing and
Proportions for Normal, Heavyweight, Thawing
and Mass Concrete C 979 Standard Specification for Pigments, for
212.1R Admixtures for Concrete Integrally Colored Concrete
C 1017 Standard Specification for Chemical Ad- trolytes as Concrete Admixtures, Australian Journal of Applied
mixtures for Use in Producing Flowing Science (Melbourne), V. 9, No. 2, pp. 127-140.
Bruere, G. M.; Newbegin, J. D.; and Wilson, L. M., 1971, "Lab-
Concrete oratory Investigation of the Drying Shrinkage of Concrete Contain-
D 98 Standard Specification for Calcium ing Various Types of Chemical Admixtures, Technical Paper No. 1,
Chloride Division of Applied Mineralogy, Commonwealth Scientific and ln-
dustrial Research Organization, East Melbourne, 26 pp.
Building Research Advisory Board, July 1958, Effectiveness of
Concrete Admixtures in Controlling the Transmission of Moisture
Through Slabs-on-Ground, Publication No. 596, National Re-
search Council, Washington, D.C.
Calcium Chloride Institute, 1959, Calcium Chloride in Concrete,
3rd Edition, pp. 40-41.
Clear, K. C., and Hay, R. E., 1973, Time-to-Corrosion of Rein-
forcing Steel in Concrete Slabs, V. 1: Effect of Mix Design and Con-
struction Parameters, Report No. FHWA-RD-73-32, Federal High-
way Administration, Washington, D.C., 103 pp.
Collepardi, M., and Corradi, M., 1979, Influence of Naphtha-
lene-Sulfonated Polymer Based Superplasticizers on the Strength of
Ordinary and Lightweight Concrete, ACI SP 62-16.
Collepardi, M.; Marcialis, A.; and Solinas, V., 1973, The Influ-
ence of CaCl, on the Properties of Cement Paste, Il Cemenro, V.
70, pp. 83-92.
These publications may be obtained from the follow- Cordon, William A., 1966, Freezing and Thawing of Concrete,
ing organizations: Mechanisms and Control, ACI Monograph No. 3, American Con-
crete Institute/Iowa State University Press, Detroit, 99 pp.
American Concrete Institute Cordon, William, A., et al., June 1946, Entrained Air in Con-
P. 0. Box 19150 crete: A Symposium, ACI JOURNAL, Proceedings V. 42, No. 6, pp.
Detroit, MI 48219-0150 601-699, and Discussion, pp. 700-1-700-12.
Cushman, A. S., 1909, Preservation of Iron and Steel, Engi-
ASTM neering (London), V. 87, p. 742.
1916 Race Street Cushman, A. S., and Gardener, H. A., 1910, Corrosion and Pres-
Philadelphia, PA 19103 ervation of Iron and Steel, McGraw-Hill Book Co., New York, p. 11.
Djabarov, N. D., Feb. 1970, Oxalic Acid as an Additive to Ce-
ment, Zement-Ku/k-Gips (Wiesbaden), V. 23, No. 2, pp. 88-90. (in
7.2-Cited references German)
Abrams, Duff A., 1924, Calcium Chloride as an Admixture in Dodson, V. H.; Farkas, E.; and Rosenberg, A. M., Oct. 1965,
Concrete, Proceedings, ASTM, V. 24, Part 2, pp. 781-834. Non-Corrosive Accelerator for Setting of Cement, U. S. Patent
Adams, R. F., and Kennedy. J. C., Dec. 1950, Effect of Batch No. 3,210,207.
Size and Different Mixers on the Properties of Air-Entrained Con- Dunagan, W. M., and Ernst, G. C., 1934, Study of the Permea-
crete, Laboratory Report No. C-532, U. S. Bureau of Reclamation, bility of a Few Integrally Water-Proofed Concretes, Proceedings,
Denver. ASTM, V. 34, Part 1, pp. 383-392.
Angstadt, R. L., and Hurley, F. R., July 18, 1967, Spodumene Duriex, M., and Lezy, R., 1956, New Possibilities for Ensuring
as an Accelerator for Hardening Portland Cement, U. S. Patent No. the Rapid Hardening of Cements, Mortars, and Concretes, An-
3.331.695. na/es, Institute Technique du Batiment et des Travaux Publics (Paris),
Arber, M. G., and Vivian, H. E., 1961, Inhibition of the Corro- No. 9, p. 138.
sion of Steel Imbedded in Mortars, Australian Journal of Applied Edwards, G. C., and Angstadt, R. L., 1966, Effect of Some Sol-
Science (Melbourne), V. 12, No. 12, pp. 339-347. uble Inorganic Admixtures on the Early Hydration of Portland Ce-
Bash, S. M., and Rakimbaev, Sh. M., June 1969, Quick-Setting ment, Journal of Applied Chemistry and Biotechnology (Oxford),
Cement Mortars Containing Organic Additives, Beton i Zhelezobe- V. 16, No. 5, pp. 166-168.
ton (Moscow), V. 15, No. 7, pp. 44-45. (in Russian) Farmer, H. G., Jan. 1945, Air-Entraining Portland Cement in
Baslazs, B. Y.; Kelmen, J.; and Kilian, J., 1959, New Method for Concrete Block, Rock Products, V., 48, p. 209.
Accelerating the Hardening of Concrete, Epitoanyag (Budapest), V. Feret, L., and Venuat, N., 1957, Effect on Shrinkage and Swell-
10, No. 9, pp. 326-331. ing of Mixing Different Cements to Obtain Rapid Set, Revue des
Bensted, J., 1978, Effect of Accelerator Additives on the Early Materiaux de Construction (Paris), No. 496, pp. l-10.
Hydration of Portland Cement, Il Cemenro (Rome), V. 75, pp. 13- Foster, Bruce, 1966, Chemical Admixtures, Significance of Tests
19. and Properties of Concrete and Concrete-Making Materials, STP-
Berger, R. L.; Kung, J. H.; and Young, J. F., 1967, Influence of 169A, ASTM, Philadelphia, pp. 556-665, 571.
Calcium Chloride in the Drying Shrinkage of Alite Paste, ASTM Gay, F. J., and Wetherly, A. H., Sept. 1959 (Mar. 1960), Ter-
Journal of Testing and Evaluation, V. 4, No. 1, pp. 85-93. mite Proofing of Concrete,* Constructional Review (Sydney), V. 32,
Blanks, R. F., and Cordon, W. A., Feb. 1949, Practices, Expe- NO. 9, pp. 26-28. Also, Summary, ACI JOURNAL, Proceedings V. 56,
riences, and Tests with Air-Entraining Agents in Making Durable No. 9, p. 904.
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(Bombay), V. 32, p. 55. proved in accordance with ACI balloting procedures.
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What is the purpose of this report?

What are the main types of chemical admixtures discussed in the report?

ACI 212.

Members of the committee voting on the 1991 revisions:

William F. Perenchio Joseph P. Fleming

CONTENTS Chapter 4-Water-reducing and set-controlling

will jeopardize conformance of concrete with a specifi- 1.10-Preparation and batching

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