Guide to the Selection

and Use of Hydraulic

Cements
Reported by ACI Committee 225

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American Concrete Institute
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ISBN: 978-1-945487-16-3

Guide to the Selection and Use of Hydraulic Cements

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 ACI 225R-16

Guide to the Selection and Use of Hydraulic Cements

Reported by ACI Committee 225

Jay E. Whitt, Chair Thomas J. Grisinger, Secretary

Gregory S. Barger Thomas M. Greene Kimberly E. Kurtis Nicholas J. Popoff

Claude Bedard Michael S. Hammer Mark R. Lukkarila Bryce P. Simons
Glen E. Bollin Geoffrey Hichborn Sr. Kirk L. McDonald Oscar Tavares
Michael M. Chehab R. Doug Hooton Leo M. Meyer, Jr. Paul D. Tennis
Marwan A. Daye Francis Innis Moncef L. Nehdi James I. Turici, Jr.
Jonathan E. Dongell Kenneth G. Kazanis James S. Pierce Stephen D. Wilcox
*The committee would like to acknowledge B. Blair and M. D. A. Thomas for their contributions in the development of this guide.

Cement is the most active component of concrete and usually has CONTENTS
the greatest unit cost; therefore, its selection and proper use is
imperative to attaining the desired balance of properties and cost CHAPTER 1 -INTRODUCTION AND SCOPE, p. 2
for a particular concrete mixture. Selection should include consid­ 1 . 1 -Introduction, p. 2
eration of the cement properties in relation to the required perfor­
1 .2-Scope, p. 2
mance of the concrete. This guide covers the influence of cement on
the properties of concrete, summarizing the composition and avail­
CHAPTER 2-NOTATION A N D DEFINITIONS, p. 3
ability of commercial hydraulic cements and the factors affecting
their performance in concrete. It includes a discussion of cement 2 . 1 -Notation, p. 3
types, a brief review of cement chemistry, the influences of chem­ 2.2-Definitions, p. 3
ical admixtures and supplementary cementitious materials, and
the ef
f ects of the environment on cement performance, and reviews CHAPTER 3-C E MENT TYPES, AVAILABILITY,
the sustainability aspects for the use and manufacture of port­ A N D SELECTION, p. 3
land cement. Cement storage, delivery, sampling, and testing of 3 . 1-Portland and blended hydraulic cements, p. 3
hydraulic cements for conformance to specifications are addressed. 3.2-Special-purpose, p. 4
Users will learn to recognize when a readily available, general­ 3.3-Research and development, p. 5
purpose cement will perform satisfactorily or when conditions
3 .4-Rational approach to selection, p. 5
require selection of a cement that meets additional requirements.

Keywords: admixture; blended cement; calcium-aluminate cement; cement CHAPTER 4-C E MENT CHEMISTRY, p. 8
storage; cement types; chemical analysis; hydraulic cement; pozzolan; 4 . 1-Portland cement, p. 8
physical properties; portland cement; slag cement; supplemental cementi­ 4.2-Blended hydraulic, p. 1 1
tious materials; sustainability.
4.3-Shrinkage-compensating expansive, p . 1 1
4.4-Calcium-aluminate, p. 1 1

CHAPTER 5-I N FLUENCE O F C H EMICAL

ACI Committee Reports, Guides, and Commentaries are
intended for guidance in planning, designing, executing, and
inspecting construction. This document is intended for the use
of individuals who are competent to evaluate the significance
and limitations of its content and recommendations and who
will accept responsibility for the application of the material it
contains. The American Concrete Institute disclaims any and
all responsibility for the stated principles. The Institute shall
not be liable for any loss or damage arising therefrom.
Reference to this document shall not be made in contract
documents. If items found in this document are desired by
the Architect/Engineer to be a part of the contract documents,
they shall be restated in mandatory language for incorporation
by the Architect/Engineer.
A D M IXTU RES, POZZOLANS, AND SLAG
C E M E NTS ON C E M ENTITIOUS SYSTEMS, p. 1 2
5 . 1-Air-entraining admixtures, p. 1 2
5.2-0ther chemical admixtures, p. 1 2
5 .3-Pozzolans, p . 1 4
ACI 225R- 16 supersedes ACI 225R-99 and was adopted and published September
2016.
Copyright © 20 16, American Concrete Institute.
All rights reserved including rights of reproduction and use in any form or by
any means, including the making of copies by any photo process, or by electronic
or mechanical device, printed, written, or oral, or recording for sound or visual
reproduction or for use in any knowledge or retrieval system or device, unless
permission in writing is obtained from the copyright proprietors.

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5.4-Slag cements, p. 1 5 APPENDIX A-CALCIUM-ALUMINATE CEM ENTS,

p. 34
CHAPTER 6-I N FLUENCE OF ENVIRO N M E NTAL A. 1-Manufacture and properties, p. 34
CON DITIONS ON THE HYDRATION OF C E M E NTS, A.2-lnfluences of admixtures and supplementary
p. 1 5 cementitious materials, p. 34
6 . 1 -Water requirements, p. 1 5 A.3-Influence of environment, p. 34
6.2-Temperature effects, p. 1 5 A.4-Heat of hydration, p. 34
6.3-Composition, p . 1 5 A.5-Setting characteristics, p. 34
A.6-Strength, p. 35
CHAPTER 7-I N FLUENCE O F C E M ENT ON A.7-Resistance to chemical attack, p . 35
CONC R ETE PROPERTIES, p. 1 5 A.8-Resistance to high temperatures, p. 36
7. 1-Thermal cracking, p. 1 5
7.2-Placeability, p . 1 7 C HAPTER 1 -I NTRODUCTION A N D SCOPE
7.3-Strength, p . 1 7
7.4-Volume stability, p . 1 8 1.1 -lntroduction
7.5-Elastic properties, p . 1 9 This guide assists specifiers and designers in choosing
7.6-Creep, p . 20 appropriate cement for specified concrete applications.
7.7-Permeability, p. 20 Although hydraulic cements are only one ingredient of a
7. 8-Corrosion of embedded steel, p. 20 concrete mixture, they are the active ingredient and, there­
7.9-Resistance to freezing and thawing, p. 2 1 fore, play a key role in the long-term viability of the struc­
7. 1 0-Resistance to chemical attack, p . 2 1 ture, floor, or pavement. Cement choice depends on many
7 . !!-Resistance to high temperatures, p . 2 1 variables, such as the service conditions for which the
7. 1 2-Cement-aggregate reactions, p . 2 1 concrete is designed, properties of other materials used in the
7. 1 3-Color, p . 23 mixture, or the performance characteristics of the concrete
required during or shortly after placement.
CHAPTER 8-C E MENT STORAG E AND DELIVERY, Cement paste is the binder in concrete or mortar that holds
p. 23 the fine aggregate, coarse aggregate, or other constituents
8. 1-Storage, p. 23 together in a hardened mass. The term "hydraulic" in this
8.2-Pack set (sticky cement), p. 24 guide refers to the basic mechanism by which the hardening
8.3-Delivery, p. 24 of the cement takes place-a chemical reaction between the
8.4-Contamination and handling, p. 24 cement and water. The term also differentiates hydraulic
8.5-Worker protection, p. 25 cement from binder systems that are based on other hardening
mechanisms, as hydraulic cements can harden underwater.
CHAPTER 9-SAMPLING AND TESTI NG OF Concrete properties depend on the quantities and quali­
HYDRAU LIC C E M E NTS FOR CONFORMANCE TO ties of its constituents. Because cement is the most active
SPECIFICATIONS, p. 25 component of concrete and usually has the greatest unit cost,
9 . !-Cement mill test report, p. 25 its selection and proper use are fundamental in obtaining the
9.2-Sealed silos, p. 25 most economical balance of properties desired for a partic­
9.3-Cement certification, p. 26 ular concrete mixture. Most cements will provide adequate
9.4-Quality management, p. 26 levels of strength and durability for general use. Some
provide higher levels of certain properties than are needed
CHAPTER 1 0-SUSTAINABI LITY ASPECTS OF in specific applications.
HYDRAU LIC C E M E NTS, p. 27
1 0. 1-Hydraulic cements, p. 27 1.2-Scope
1 0.2-Energy consumption, p. 27 This guide summarizes information about the composi­
1 0.3-Use of supplementary cementitious materials tion, availability, and factors affecting the performance of
(SCMs) as replacement for portland cement, p. 28 commercial hydraulic cements. It also provides information
1 0.4-Use of cement in concrete, p. 28 regarding:
1 0.5-Recycled raw materials as raw feed in the manufac- a) Cement selection, whether a cement is readily avail­
ture of portland cement, p. 28 able, and if conditions require a general-purpose cement or
1 0.6-Alternate fuels, p. 28 a special cement
1 0.7-Combustion emissions, p . 29 b) How the chemical and physical characteristics of a
1 0 . 8-Recent progress and strategy, p. 29 cement can affect certain properties of concrete
c) How interaction of cements with various additives,
CHAPTER 1 1 -REFERENCES, p. 29 admixtures, and mixture designs can affect concrete
Authored documents, p. 30 This guide only deals with hydraulic cements manufac­
tured under North American standards (ASTM International,
American Association of State Highway and Transportation

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Officials [AASHTO], and Canadian Standards Association Table 3 1 a-Characteristics of portland cements '
[CSA]). For information on other hydraulic cement standards, Optional
.

the user is directed to local specifications and building codes. Type Description characteristicst

I General use 1, 4
CHAPTER 2-NOTATION AND DEFINITIONS
General use; moderate
II 1, 4
sulfate resistance
2.1 -Notation
General use; moderate
Cement phases referred to throughout this guide follow II (MH) 1, 4
heat of hydration
the cement chemists' notations as follows:
III High-early-strength I, 2, 3
A Ah03
C CaO IV Low heat of hydration 4

C C02 v High sulfate resistance 4, 5

F Fe203 "For cements spec1fied m ASTM C 150/C 150M .
H H2 0 !Optional characteristics:
M MgO l. Air entraining (A)
S Si02 2. Moderate sulfate resistance: C,A maximum, 8 percent

s so3 3. High-sulfate resistance: C3A maximum, 5 percent

4. Low alkali: maximum of 0.60 percent alkalies, expressed as Na,O equivalent
tricalcium silicate: 3CaO·Si02 C3S =

5. Alternative limit of sulfate resistance is based on expansion tests of mortar bars

dicalcium silicate: 2CaO·Si02 = C2 S
tricalcium aluminate: 3CaO·Al203 C3A =

for Canada, in CSA-A300 1 . Blended cements are also speci­

tetracalcium aluminoferrite: 4CaO·Al2 03·Fe2 03 = C4AF
fied under the AASHTO M 240 requirements. For more on
Tricalcium silicate, Ca3Si05, in conventional notation
hydraulic cement specifications and selection, refer to 3 .4.
becomes 3CaO·Si02 in oxide notation, or C3 S in cement
Portland cements are manufactured by a process that
chemists' notation. Simple oxides, such as CaO or Si02 , are
begins by combining a source of lime such as limestone,
often written in full.
a source of silica and alumina such as clay, and a source
of iron oxide such as iron ore. The properly proportioned
2.2-Definitions
mixture of the raw materials is finely ground and then heated
ACI provides a comprehensive list of definitions through
to approximately 2700°F ( 1 480°C) for the reactions that
an online resource, "ACI Concrete Terminology," https ://
form cement phases to take place. The product of a cement
www. concrete. org/store/productdetail.aspx?ItemiD=CT 1 6.
kiln is portland cement clinker. After cooling, the clinker is
Equivalent alkali in hydraulic cement is the total of
ground with calcium sulfate (gypsum); processing additions;
sodium and potassium oxides as calculated from the chem­
and, in many cases, limestone to form a portland cement.
ical analysis, and using the formula: Na2 0eq = % Na2 0 +
Processing additions are organic or inorganic materials used
0.658%K20 (ASTM C2 1 9).
in the manufacture of cements that are added at the finish
mill. Their use is governed by ASTM C465 . Processing addi­
CHAPTER 3-C E M ENT TYPES, AVAILABILITY,
tion rates for portland cements are specified in ASTM C 1 50/
AND SELECTION
C 1 5 0M. The specific gravity of portland cement will vary
Selection of cement is an important consideration when
slightly depending on the amounts of limestone, gypsum,
proportioning mixtures for specific project requirements
and inorganic processing addition added to the clinker (for
and intended use. It is important that the specification for
further reference on inorganic process addition refer to
hydraulic cements be appropriate for the project and the
Taylor [2008]). Most of these additions are less dense than
hydraulic cements available in the area. Factors such as
clinker and tend to reduce the specific gravity of the port­
exposure conditions and desired properties can often require
land cement. When proportioning concrete mixtures, unless
specific cement types based on the chemistry or physical
an actual measurement of the specific gravity of the cement
properties. Specific cements may be available that are
has been made, 3 . 1 5 has been used for portland cements
designed for applications where performance requirements
(Kosmatka and Wilson 20 1 1 ). As the amount of processing
cannot be achieved with ordinary portland cement.
additions increase, the specific gravity value has been found
to decrease.
3.1 -Portland and blended hydraulic cements
Blended hydraulic cements are usually made by inter­
A majority of the cement used for concrete construction
grinding portland cement clinker with calcium sulfate
in the United States is either portland cement, manufactured
(gypsum); processing additions; and a quantity of a suitable
to meet the requirements of ASTM C 1 50/C 1 50M, blended
material such as slag cement, fly ash, limestone, silica fume,
hydraulic cement manufactured to meet the requirements
or raw or calcined natural pozzolans. They may also be made
of ASTM C595/C595M, or performance-based hydraulic
by blending the finely ground ingredients, or by a combina­
cement manufactured to meet the requirements of ASTM
tion of blending and intergrinding. The specific gravity of
C l l 57/C 1 1 57M. Tables 3 . 1 a and 3 . 1 b include basic charac­
a blended cement will vary with the type and amount of
teristics of these cements as listed in ASTM. Other portland
material(s) that is interground or interblended.
cement specifications can be found in AASHTO M 85 or,

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Ta bl e 3 1 b C h aractens
· res
1 of blended hydraulic and performance-based hydraulic cements
Blended ingredients range, percent by mass
ASTM C595/ Optional
.
C595M Type Name Pozzolan Slag cement Limestone characteristics

IP Portland-pozzolan cement I to 40 -
I, 2, 3 , 4, 5, 6

IS Portland blast furnace slag cement -

I to 95 I, 2, 3, 4, 6

IL Portland limestone cement - -

5 to 1 5 I, 4 , 5 , 6

IT Ternary blended cement! I to 40 I to 95 5 to 1 5 I, 2 , 3 , 4 , 5, 6

.
ASTM CII57/CII57M Type Name Optional characteristics

GU General use I, 6

HE High early strength I, 6

MS Moderate sulfate resistance I, 6

HS High sulfate resistance I, 6

MH Moderate heat of hydration I, 6

LH Low heat of hydration I, 6

Optional charactenst1cs that can be spec1fied for vanous cement types.
I. Air-entraining (A)
2. Moderate sulfate resistance (MS)
3. High sulfate resistance (HS)
4. Moderate heat of hydration (MH)
5. Low heat of hydration (LH)
6. Suitability for use with alkali-silica reactive aggregate
!Ternary blended cements include two of the ingredients (pozzolan, slag cement, or limestone) in the ranges noted, but not all three.

3.2.3 Expansive or shrinkage-compensating cements­

For specification purposes, portland and blended
These are designed to expand a small amount during the first
hydraulic cements are designated by type depending on their
few days of hydration to offset the effects of later drying
chemical composition and properties. The availability of a
shrinkage. Their purpose is to reduce cracking resulting
given type of cement may vary widely among geograph­
from volume decrease due to shrinkage or to cause stressing
ical regions. Commonly used descriptions of portland and
of reinforcing steel (ACI 223R). Those manufactured in the
blended cements are given in Tables 3 . 1 a and 3 . 1 b. The use
United States depend on the formation of a higher-than­
of blended cements is growing in response to the demand for
usual amount of ettringite during hydration of the cement
concrete requiring special properties, energy conservation,
to cause the expansion (ASTM C845/C845M). The expan­
and raw materials.
sive ingredient, an anhydrous calcium sulfoaluminate, can
be purchased separately. Magnesium or calcium oxide may
3 .2-Special-purpose
also be used as expansive agents.
In addition to portland and blended cements, other hydraulic
3.2.4 Rapid-hardening hydraulic cements-These are
cements are available for specialized uses (Table 3.2). Other
designed to give rapid strength gain during the first 24 hours
cement types are only touched upon, as their availability is
of hydration. Four categories of performance are specified in
limited in some regions.
ASTM C 1 600/C 1 600M with strength requirements from 1 .5
3.2.1 Masonry cements-These are used in masonry
to 24 hours. Rapid-hardening hydraulic cements can be used
mortars. They are specified in ASTM C91/C9 1 M and their
in the same application as portland and blended cements,
use is covered by ASTM C270 and ACI 530/530. 1 . Plastic
and usually include processing or functional additions. They
and mortar cements are also used in mortars and specified
are typically used for repair applications or where very rapid
in ASTM C 1 328/C l 328M and ASTM C l 329/C l 329M,
strength gain is needed.
respectively. In Canada, masonry and mortar cements are
3.2.5 Regulated-set cemen ts-Regulated-set cements are
specified in CSA-A3002.
similar in composition to portland cements, except that the
Certain portland cements can give the finished product
clinker from which they are made contains a small quan­
special colors, such as white or buff, which are used for
tity of fluorine. They are formulated to have unusually short
architectural purposes. White and buff cements are usually
setting times followed by development of a moderate early
furnished to meet ASTM C 1 50/C 1 50M specifications.
strength.
3.2.2 Modified portland cements Modified portland -

3.2.6 Well cements-Well cements are manufactured

cements as described in ASTM C90, which are sometimes
specifically for use in sealing spaces between well casings
referred to as block cements, are manufactured to meet the
and linings, and the surrounding geological formations.
needs of the concrete masonry unit manufacturing industry.
They are usually required to comply with API 1 OA. These

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Table 3.2-Miscellaneous or special-pu rpose cements

Type Description or purpose ASTM specification

White cement White architectural cement C I50/CI50M'

Buff cement Buff architectural cement C 1 50/C 1 50M'

Expansive cement, Type E-1t Expansive hydraulic cement C 845/C845M

For use where rapid setting and moderate early strength

Regulated-set cement None
development is needed

Rapid-hardening hydraulic cements For use where early strength development is needed C l 600/C l600M

Oil-well cements, Types A through H, J! Hydraulic cements used for oil-well casings and linings None

For use in mortar for masonry, brick and block construction,

Masonry cement, Types M, S, and N C 91/C 9IM
and stucco

Plastic cement For use in exterior stucco applications C I32 8/C I328M

Mortar cements Types M, S, and N For use in mortar for masonry, brick, and block construction C 1 32 9/C ! 32 9M

For use in refractory, high-early-strength, and moderately

Calcium-aluminate cement None
acid-resistant concretes

Block cement For use in making concrete masonry units C ll57/C l l 57M, C5 95/C5 95M, C l50/C l 50M

Magnesium phosphate cement Nonportland cement for use where rapid hardening is needed None
Although wh1te and buff cements are not listed specifically m ASTM C 150/CISOM, they could meet the reqwrements of ASTM C 150/C 150M as md1cated by the manufacturer.
1Thrce kinds are identified by letters K, M, and S.
!These are covered by American Petroleum Institute (API IOA).

cements specified in API 1 OA can also meet ASTM speci­
fications; for example, Class G well cements meeting API
l OA often meet the requirements of ASTM Cl50/Cl50M,
Type II or V. For very-high-temperature wells, less--reactive
cements are sometimes used, such as mixtures of dicalcium
silicate and finely ground silica.
3.2.7 Calcium-alumin ate cements-Calcium-aluminate
cements (Appendix A) are intended primarily for refractory
applications and are designated as being of! ow, intermediate,
or high purity. The purity level of the calcium-aluminate
cement is based on iron content in the low-purity cement
and free alumina content in the high-purity cement. Low­
purity calcium aluminate cements are also used for concretes
that are to be exposed to mild acids and certain industrial
wastes. Other possible applications are self-leveling floors,
and patching and repair when very high early strengths are
needed.
3.2.8 Plastic cements-Plastic cements (ASTM Cl328/
C l 328M) are formulated for use in mortars for stucco. They
are portland cements modified by small amounts of additives
that cause the mortars made from them to have flow proper­
ties that aid stucco applications.
3.2.9 Waterproof cements-These are portland cements
interground with stearic acid or other water repellents with
the objective of imparting water repellency to concrete
containing them.
3.2.10 Ultrafine cements-These are of fine particle size
with a 50 percent by mass distribution of the particles having
a mean diameter of less than 0.0002 in. (5 11m) and are
usually composed of blends of portland and slag cements.
These small-sized particle systems are required in geotech­
nical applications and repairing relatively large cracks and
other concrete applications where permeation grouting of
fine sands, underground strength, or water control in finely
fractured rock formations is needed.
3.2.11 Photocatalytic cements-These contain photo­
catalysts, often as engineered nanoparticles, which in the
presence of water, oxygen, and ultraviolet light, and visible
light, produce strong oxidizing agents. The net effect of the
surface-initiated reactions can impart new functionality to
cement-based materials, including self-cleaning, biocidal,
hydrophobicity, hydrophilicity, and smog-abatement func­
tionality (Giannantonio et a!. 2009; Husken et a!. 2009;
Bowering et a!. 2006; Kawakami et a!. 2007; Diamanti et
a!. 2008).
3.3-Research and development
Given the broad use of cement worldwide and the ever­
increasing demands for enhancements in properties and
performance, research and development has produced
continued innovations in cements. For example, over the
past decade, many innovations increasing the sustainability
of cement have been introduced (Chapter 1 0). Another key
area of innovation is the exploration of the potential for nano­
technology to improve cement and concrete performance.
Some research has explored the incorporation of nano­
sized materials (Sobolev et a!. 20 1 2). These nanoparticles
including, for example, nanotubes, can graft molecules onto
cement particles or cement phases to promote specific inter­
facial interactions and provide surface functionality. These
composites can have a range of novel properties, such as low
electrical resistivity, self-sensing capabilities, self-cleaning,
self-healing, high ductility, and self-control of cracks.
3.4-Rational approach to selection
The goal of the specifier is to provide specifications that
ensure that proper amounts and types of cement are used

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Table 3.4.1 a-Comparison of cement types and exposure cond itions (ASTM and AASHTO)
Exposure condition ASTM C I SO/CISOM or AASHTO M 85" ASTM C595/C595M or AASHTO M 240 ASTM Cll57/C 1157 M

General use I IL, IP, IS, IT GU

Moderate sulfate resistance II IP(MS), IS(MS), IT(MS) MS

Moderate heat of hydration II (MH) -

MH

High early strength Ill -

HE

Low heat of hydration IV IL (LH), IP(LH), IS(LH), IT(LH) LH

High sulfate resistance v IP(HS), IS(HS), IT (HS) HS

Cements specified m ASTM C 150/C 150M or AASHTO M 85 can be air entramed, m which case the Roman numeral designation IS followed by the letter A. Example Type IIA
indicates cement that meets the requirements for Type II, but in addition contains an air-entraining agent.

Table 3.4.1 b-Comparison of cement and blended cement types (CSA-A3001 )

Blended cement"
Exposure condition Portland cement Portland-limestone cement Using portland or portland-limestone cement

GUb-S, GUb-C, GUb-CI, GUb-F, GUb-N, GUb-SF, GULb-S,

General use GU GUL
GULb-C, GULb-CI, GULb-F, GULb-N, GULb-SF

Moderate sulfate resistance MS -

MSLb, MSb-S, MSb-C, MSb-CI, MSb-F, MSb-N, MSb-SF

MHb-S, MHb-C, MHb-CI, MHb-F, MHb-N, MHb-SF, MHLb-S,

Moderate heat of hydration MH MHL
MHLb-C, MHLb-CI, MHLb-F, MHLb-N, MHLb-SF

HEb-S, HEb-C, HEb-CI, HEb-F, HEb-N, HEb-SF, HELb-S,

High early strength HE HEL
HELb-C, HELb-CI, HELb-F, HELb-N, HELb-SF

LHb-S, LHb-C, LHb-CI, LHb-F, LHb-N, LHb-SF, LHLb-S,

Low heat of hydration LH LHL
LHLb-C, LHLb-CI, LHLb-F, LHLb-N, LHLb-SF

High sulfate resistance HS -

HSLb, HSb-S, HSb-C, HSb-CI, HSb-F, HSb-N, HSb-SF
Ternary blends are also allowed (refer to 4.2 for designatiOns).

to meet the structural and durability requirements of the
project. The cement choice for a particular concrete appli­
cation should be assessed through a combination of these
requirements related to the project. Imposing unnecessary
requirements is not only economically wasteful, but may
compromise other principal performance characteristics.
For example, moderate sulfate resistance may be specified
for certain structural elements that also require accelerated
strength gain in the production process. However, composi­
tional variations that impart sulfate resistance tend to reduce
the rate of strength gain, potentially requiring some form
of compromise. Nevertheless, some projects entail special
performance characteristics be implemented into the specifi­
cations. Another example, depending on the intended appli­
cation, is that it might be necessary to design for various
factors, including increased resistance to sulfate attack,
reduced heat evolution, or use with aggregates susceptible
to alkali-aggregate reaction (AAR). Failure to impose these
requirements may have serious consequences to the service
life of the structure.
It is for these reasons that the applications dictate the
type of cement specified. Yet, there are still specifications
that require cements with low alkali contents without inves­
tigating whether the actual aggregates being used in the
concrete are reactive, or they may also specify low C3A
contents without investigating the actual exposure to sulfate
conditions. Additional cement characteristics should only be
specified when it is known that they are necessary for long­
term durability of the structure.
3.4.1 U.S. and Canadian standards-There are multiple
standards for hydraulic cements for use in concrete in the
United States and Canada. The two primary specifying agen­
cies in the United States are ASTM International and the
American Association of State Highway and Transportation
Officials (AASHTO). Within ASTM and AASHTO, there
are separate standards: ASTM C l 50/C l 50M and AASHTO
M85, and ASTM C595/C595M and AASHTO M 240. Also,
ASTM has one standard-ASTM C l 1 57/C l l 57M-that
does not have an equivalent standard in AASHTO. Refer
to Tables 3 . l a and 3 . l b for characteristics of ASTM and
AASHTO portland and blended hydraulic cements.
In Canada, the Canadian Standard Association (CSA)
is the specifying agency for hydraulic cements, and
CSA-A3001 is the standard for cements, blended cements,
and supplementary cementitious materials. In CSA-A300 1 ,
portland cements are designated as Types GU (general use),
MS (moderate sulfate resistant), MH (moderate heat of
hydration), HE (high-early strength), LH (low heat of hydra­
tion), and HS (high sulfate resistance), and correspond in
intended use to ASTM C l 50/C l 50M cement Types I, II,
II(MH), III, IV, or V, respectively. CSA-A300 1 also covers
blended hydraulic cements that are designated GUb, MSb,
MHb, HEb, LHb, or HSb; portland-limestone cements
with up to 1 5 percent interground limestone designated as
GUL, MHL, HEL, or LHL; and portland-limestone blended
cements designated as GULb, MSLb, MHLb, HELb, LHLb,
or HSLb. Refer to Table 3 .4. l a and 3 .4. l b for comparisons
of the cement types.

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3.4.2 Supplementary cementitious materials-Supple­ Table 3.4.4-ACI 3 1 8 exposure categories for

mentary cementitious materials (SCMs) standards in the concrete (ACI 3 1 8- 1 4)
United States are ASTM C989/C989M and AASHTO M Exposure category Severity Class
302 ASTM C6 1 8 and AASHTO M 295 , ASTM C l 240 and Not applicable FO
AA �mTO M 307, and ASTM C l 697 (AASHTO does not
Moderate Fl
have an equivalent standard, but AASHTO M 32 1 may be Freezing and thawing (F)
referenced). In Canada, SCMs are included in CSA-A300 1 . Severe F2
3.4.3 General use cements-Using a general-purpose Very severe F3
cement that is locally available is advised as long as the
Not applicable so
special properties of the other cement types is not required.
Moderate Sl
General-purpose cements are described in ASTM C l 50/ Sulfate (S)
C 1 50M as Type I, II, or II(MH); in ASTM C595/C595M as Severe S2
Type IL, IP, IT, or IS(<70); and in ASTM C l l 57/C 1 1 57M Very severe S3
as Type GU. Obtaining a special cement type could result
Not applicable wo
in some improved performance characteristics, but could be
In contact with water (W) Required low
detrimental to others. For this reason, justification is gener­ WI
penneabi I ity
ally recommended before specifying a cement other than the
commonly available ASTM C l 50/C l 50M Type I or Type II Not applicable co
Corrosion protection
portland cement, or a corresponding blended cement. Moderate CI
reinforcement (C)
In ASTM C l 50/C l 50M, although the term "Type 1/II Severe C2
portland cement" is frequently used to describe some port­
land cements, it is not a standard ASTM designation. Type II
the cement types used with varying exposure conditions
II does, however, denote that the cement being represented
according to ASTM C l 50/C 1 50M, C595/C595M, ASTM
has a C3A content of 8 percent or less and meets all of the
C l l 57/C l l 57M, AASHTO M 85, and AASHTO M 240.
requirements of both ASTM C l 50/C l 50M Type I and Type
Note that Table 3 .4. l a excludes products that are generally
II. This is particularly helpful to the concrete producer who used in combination with portland cements. These include
has limited silo storage capacity, and for whom the ability slag cement, fly ash, silica fume, or blended SCM. ASTM
to inventory a single cement that meets both ASTM C l 50/ C595/C595M, covering blended cements, prescribes ingre­
C l 50M Type I and Type II specifications in one silo is a
dients and proportions, as well as some performance require­
convenience.
ments, whereas ASTM C 1 1 57/C !1 5 7M, with which blended
A technology that may reduce the environmental impact
cements can also be specified, is a performance specification
of cement production is the use of limestone as an ingre­ in which performance criteria alone govern the products and
dient in hydraulic cements in amounts up to 1 5 percent by
their acceptance.
mass. Environmental benefits may result from less energy For construction in Canada, the CSA-A30 0 1 specification
required for pyro-processing, a reduction in related green­
consist of standards for cements and cementitious materials,
house gases, and less raw materials used. This technology
including blended hydraulic cements. CSA-A300 1 specifi­
has been adopted by CSA-A300 1 and has been used for
cally covers portland, portland-limestone, and blended
several decades in Europe (Hooton et a!. 2007) and other
cement, as well as slag cement, pozzolans, and blended
countries. Cements using this technology in the United pozzolans. Table 3.4. 1 b compares the types of cement and
States are manufactured under ASTM C 1 1 57/C 1 1 57M,
blended cement types allowable in CSA-A300 1 for the
ASTM C595/C595M, and AASHTO M 240. ASTM C595/ different exposure conditions by specification. Table 3 .4. 1 b
C595M and AASHTO M 240 designate portland-limestone excludes the specifications for slag cement, fl y ash, silica
blended cements as Type IL. Similar strength gain and other
fume, or blended SCM products, which are generally used
properties can be achieved in optimized systems. For more
in combination with portland cement. Blended hydraulic
information, refer to Tennis et a!. (20 1 1 ) and Thomas and
cements under ASTM C595/C595M and CSA-A30 0 1 are
Hooton (20 1 0).
prescribed by ingredients, proportions, and performance
3.4.4 Cements used in various exposure conditions­
characteristics. ASTM C 1 1 57/C ! 1 57M is based on perfor­
Design requirements for concrete vary with the exposure
mance characteristics alone.
conditions. ACI 3 1 8- 1 4 Chapter 1 9 contains concrete speci­ 3.4.5 Summary-As seen from Tables 3.4. l a, 3 .4. l b, and
fications and hydraulic cement and SCM requirements for 3 .4.4, there is often more than one option for hydraulic
four exposure categories. These categories, as indicated in
binders for each exposure condition. A question might arise
Table 3 .4.4, are freezing-and-thawing exposures, sulfate regarding the propriety of a cementitious blend containing
exposures, water exposure, and corrosion protection of rein­
a particular SCM that is locally available instead of port­
forcement. Each category contains multiple levels of severity land cement only. When ACI-accepted concrete practices
that leads the designer toward the appropriate requirements are followed, slag cement, some fly ashes, and silica fume
for concrete and the choices available for hydraulic cements
hatched in concrete at the appropriate rates can impart advan­
and SCMs. Table 3.4.4 shows the exposure categories and tageous performance characteristics including improved
their different levels of severity. Table 3.4. l a compares

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Table 4.1 a-Common phases' in portland cements
Name (common name)
Tricalcium silicate (or alite)
Dicalcium silicate (or belite)
Tricalcium aluminate (or aluminate)
Tetracalcium aluminoferrite (or ferrite)
Calcium sulfate anhydrite (or anhydrite)
Calcium sulfate dehydrate (or gypsum)
Calcium sulfate hemihydrate (hemihydrate or bassanite)
Calcium carbonate (or limestone)
*Ideal composJtiOns; other elements are present m commercJal cements.
mitigation of alkali-silica reaction (ASR), more resistance to
sulfate attack, higher ultimate strengths, and lower permea­
bility. Many SCMs are recycled or processed by-products of
other industries, and using them improves sustainability of
the concrete mixture. Contrarily, the use of some SCMs can
perform differently than ordinary portland cement mixtures,
such as longer set times, lower early strengths, and more sensi­
tivity to cold weather temperatures in the field during place­
ment. Many of these aspects can be minimized or eliminated
through adjustment of the concrete mixture design propor­
tions and judicious use of chemical admixtures. Deciding on
the correct blend for a particular hydraulic cement depends
on the materials available in the local market and local expe­
rience with them. Input from local cement suppliers, concrete
labs, concrete producers, and contractors can be helpful when
deciding on mixture proportions.
In the United States and Canada, many producers of
concrete have multiple storage silos on site so that more
than one hydraulic cement can be used in concrete. In this
case, the concrete producer is able to batch multiple cements
as required by mixture design. Some concrete producers,
however, may only have one or two storage silos, limiting the
number of hydraulic cements specified. For producers who
are limited by silo space, blends manufactured and sold by
a local cement manufacturer might be available. Designers
and specifiers should be aware that some hydraulic cements
and SCMs, such as slag cement and Class C or Class F fly
ash, may not be available in some markets.
CHAPTER 4-C E M ENT C H E M I STRY
The principal constituents of cements, pozzolans, and slag
cements, or their hydration or reaction products, are phases
containing calcium, silicon, aluminum, iron, oxygen, sulfur,
and hydrogen. Chemical analyses of these materials usually
express the amounts of these elements present as percentages
of the oxides CaO, Si02, Al203 , Fe203 , S03 , and H20. The
oxides are, with few exceptions, not actually present as such,
but the elements are in the forms of more complex phases.
More complete descriptions of the chemistry of cements can
be found in Lea ( 1 998) and Taylor ( 1 997).
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Cement chemists' notation Oxide notation Conventional notation
cl s 3CaO·Si02 Ca3Si05
c, s 2CaO·Si02 Ca2Si04
C3A 3CaO·AI203 Ca3AI2Si06
C4AF 4CaO·AI203· Fe203 Ca4AI2Fe201o
css Ca0·S03 CaS04
C S H2 CaO · S03 ·2H,O CaS04·2H20
C S H 112 CaO•S03·112H20 CaSO.- 112H20
cc CaO·C02 CaC03
4.1 -Portland cement
The main phases present in portland cements are listed in
Table 4 . 1 a. The chemical phase or family of phases identi­
fied as tricalcium silicate (C3 S) exists in clinker in an impure
form known as alite. Alite is complex and may take on six or
seven crystal forms and contain sulfur, sodium, potassium,
iron, magnesium, and fluorine as trace elements. Dicalcium
silicate (C2S) exists as belite. Belite has at least five crystal
forms; the different forms of belite, unlike those of alite,
differ greatly in performance.
Both the tricalcium-aluminate phase(s), C3A, and the
ferrite phase, C4AF, also exist in several different crystal
forms with some variation in properties. The ferrite phase
can vary widely in composition. When the alumina to iron
oxide mass (Ah03/Fe203) ratio is less than 0.64, a ferrite
solid solution of C4AF and C2F is formed. The ferrites are
of less importance than C3A in cements because of slower
hydration of the latter.
The percentages of the phases in a portland cement,
such as those given in Table 4. 1 b, can be calculated from
an oxide analysis of the cement using certain simplifying
assumptions. Such calculated potential phase composi­
tions of a cement only approximate the percentages actually
present. The calculation procedure, which was developed by
Bogue ( 1 955), is given in ASTM C 1 50/C 1 50M. This proce­
dure assumes that chemical equilibrium is attained in the
burning zone of the kiln, where, in fact, equilibrium may
not be reached. X-ray diffraction analysis (ASTM C l 365)
provides a more accurate representation of phases present.
Small but significant quantities of other elements such as
sodium, potassium, magnesium, phosphorus, and titanium
are usually present in cements and may substitute for the
various principal elements or form other phases and solid
solutions. Bhatty ( 1 995) details the effects of over 50 trace
elements on the manufacture and performance of cement.
The manufacturing process can be controlled to vary the
relative proportions of the phases in cements and produce
cements with different characteristics. This is recognized in
ASTM C 1 50/C 1 50M. Typical phase compositions of some
commonly used ASTM types of portland cement are given
in Table 4 . 1 b. Typical strength, setting time, and fineness of
ASTM types of portland cement are provided in Table 4. 1 c.
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Table 4.1 b-Chemical and phase composition of portland cements in North America (Bhatty and Tennis 2008)
Chemical composition Potential phase composition
Cement Loss on Insoluble
type Value Si02 AlzOJ FezOJ CaO MgO so3 ignition Na20eq. residue c3s CzS C3A C4AF

Mean 20. 1 7 5.07 2.66 63.23 2.51 3.26 1 .52 0.70 0.29 56.9 14.8 8.9 8.2

Standard
0.66 0.54 0.44 1 .04 1 .02 0.62 0.48 0.26 0.11 4.57 3.71 1.8 1 1 .37
deviation

Type I Maximum 2 1 .8 6.1 3.6 65.2 4.5 4.4 2.7 1 .2 0.6 65 21 12 11

Minimum 19.0 3.9 2.0 6 1 .5 0.8 2.0 0.7 0.2 0.1 45 6 6 6

Number
51 51 51 51 51 51 50 51 41 51 48 51 48
of values

Mean 20.85 4.62 3.32 63.66 1 .98 2.91 1 .39 0.56 0.29 56.5 1 7.1 6.7 1 0.1

Standard
0.52 0.37 0.40 0.84 0.92 0.39 0.40 0.26 0. 1 1 3.93 3.48 0.88 1 .20
deviation

Type II Maximum 22.5 5.5 4.4 65.6 4.5 4.0 2.7 1 .2 0.6 68 25 8 13

Minimum 20.0 3.8 2.6 6 1 .3 0.6 2.1 0.5 0.2 0.1 48 8 4 8

Number
79 79 79 79 79 79 78 79 71 78 77 78 76
o f values

Mean 20.38 4.84 2.86 63.33 2.21 3.60 1 .51 0.61 0.30 56.2 1 6.2 7.8 8.8

Standard
0.70 0.64 0.59 0.93 0.93 0.55 0.41 0.27 0.13 4.13 3.91 2. 1 4 1 .80
deviation

Type III Maximum 22.1 7.3 4.2 64.9 4.3 4.9 2.9 1 .2 0.7 66 27 12 13

Minimum 18.6 3.4 1 .3 6 1 .6 0.8 2.6 0.7 0.1 0.1 48 8 2 4

Number
56 56 57 57 57 57 56 57 47 56 55 56 55
of values

Type V Mean 21.61 3.80 3.87 63.85 2. 1 8 2.34 1 .29 0.45 0.29 57.7 1 8 .4 3.5 11.8

Table 4.1 c-Physical characteristics of portland cements in North America (Bhatty and Tennis 2008)
Setting time
Fineness Fineness 45 11m
Compressive strength, MPa (psi) (Vicat), min
Cement (Blaine), (No. 325) sieve,
type Value 1 day 3 days 7 days 28 days Initial Final m2/kg % passing

Mean 15 . 8 (2290) 26.3 (38 10) 33 (4790) 41.3 (5990) 1 07 227 384 92.9

Standard deviation 2.82 (4 1 0) 2.4 (350) 2.48 (360) 3.55 (510) 1 7.7 46.2 1 9.3 4.25

Type I Maximum 21 (3050) 30.9 (4480) 40.9 (5930) 50.5 (7320) 1 66 429 431 99. 1

Minimum 8.7 (1260) 20.8 (3020) 28. 1 (4080) 34.8 (5050) 75 172 334 72.6

Number of values 41 50 50 49 48 31 51 51

Mean 14.9 (21 60) 25.2 (3650) 32.4 (4700) 42.9 (6220) 112 224 377 94.6

Standard deviation 2.57 (370) 2.62 (380) 2.86 (410) 3.64 (530) 1 9.8 38.7 20.0 2.62

Type II Maximum 22.5 (3260) 32.2 (4670) 39.1 (5670) 50.2 (7280) 1 85 411 461 98.7

Minimum 7.6 (1100) 1 5 .7 (2280) 2 1 .5 (3120) 30.8 (4470) 79 104 305 82.5

Number of values 72 78 78 78 75 62 77 77

Mean 25 (3630) 34.9 (5060) 4 1 .2 (5980) 49.3 (71 50) 91 185 556 98.5

Standard deviation 3.39 (490) 3.61 (520) 3 . 8 1 (550) 4.44 (640) 1 9.6 35.3 55.5 1.26

Type III Maximum 32.6 (4730) 42. 1 (6110) 48.7 (7060) 58 (84 1 0) 135 240 711 99.9

Minimum 16. 2 (2350) 26.3 (38 10) 32 (4640) 39.9 (5790) 55 78 387 95.0

Number of values 54 54 50 53 52 41 55 54

Mean 12. 8 ( 1 860) 23.3 (3380) 30.9 (4480) 43.6 (6320) 1 28 242 389 96.5

Standard deviation 1.83 (270) 3.23 (470) 4.2 (610) 4.66 (680) 25.7 39.1 42.5 2.05

Type V Maximum 15 .9 (2310) 27.6 (4000) 36.2 (5250) 50.2 (7280) 1 77 330 541 99.0

Minimum 7.4 (1070) 1 2.9 (1870) 17.5 (2540) 31.9 (4630) 85 177 312 91.7

Number of values 25 25 25 25 24 18 26 26

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Table 4.1.1 -Primary phases formed by reactions of portland cements with water'
Name (common name) Cement chemists' notation Oxide notation Conventional notation

Calcium silicate hydrate CSH 3.4Ca0·2Si02·8H20 C3.4Si,0,·8H,O

Calcium hydroxide CH CaO·H20 Ca(OH)2

Trisulfoaluminate hydrate (or ettrin-

C6AS 3H32 6CaO ·AI203·3S03·32H20 Ca6AI,S30,8· 32H,O
gite or AFt)

Monosulfoaluminate hydrate (or

c.As H , , 4Ca0·AIP3 · S03·12HP Ca.AI2S010·12H20
monosulfate or AFm)

Tetracalcium aluminate hydrate C4AH 13 4CaO·AI203 · 1 3H20 Ca4A1207·13H20

Calcium aluminoferrite hydrate C6(A,F)H12 6CaO·AI203· Fe203·12H20 Ca6A!,Fe207· 1 2H20

Water H H20 H20

"Major hydrated phases are shown in ideal compositions. Other phases also are present in hydrated cement pastes. Other elements are present in most phases and several phases
have a range of composition.

4.1.1 Reactions of portland cement with water-When

portland cement and water are mixed, a series of chemical
z
reactions begin that result in slump loss, setting, hardening,
evolution of the heat of hydration, and strength develop­
g
...
cc
ment. The overall process is referred to as cement hydra­ II:
tion because it involves formation of water-containing ...
z
hydrated phases. The primary phases that form are listed in w
()
Table 4. 1 . 1 . The gypsum, or other form of calcium sulfate, z
0 Total alkalis
that is usually interground with the cement clinker is used () (Na++ K+)
to prevent flash setting and control the setting and early
hardening process primarily by regulating the early hydra­
tion reactions of the C3A (Tang 1 992). It is thought to func­ 3 10 7 28
tion, in part, by dissolving rapidly and causing a protective ......___, ..._._.....,

coating of ettringite to form on the C3A surfaces. A side MINIS- DAYS

effect of gypsum is accelerating the hydration of the sili­

Fig. 4. 1 . 1a-Diagram illustrating changes with time of
cates. Information on the relative differences in hydration
concentrations of ions in solution in the pore water of a
rates of hydraulic cementitious materials and mixtures can
portland cement paste (adaptedfrom Mindess et al. [2003]).
be obtained by using isothermal calorimetry to track the heat
evolution (for example, ASTM C 1 679 or C 1 702).
The ions or water-soluble compounds dissolved in the
water are believed to affect the behavior of cements and their
interactions with other concrete materials such as aggre­
gates and admixtures. Figure 4. 1 . 1 a is a representation of
how the quantities of some of the significant ions in solu­
tion might change with time. Figure 4. 1 . 1 b (Soroka 1 980)
indicates how the quantities of important cement reaction
phases might change with time. It also indicates that a reduc­ C S H ( Long fibres)
tion in the volume of the originally water-filled pores takes
place as the reactions proceed. The actual rates of reactions
and nature and amounts of the phases formed depend on the
specific compositions and fineness of the cements; they also
depend on temperature, nature, and quantities of admixtures 0 5
present (Helmuth et a!. 1 995).
Age: Minutes Hours Days
ASTM C 1 50/C 1 50M establishes default maximum S03
contents ranging from 2.3 percent for Type V to 4.5 percent
Fig. 4. 1 . 1 b-Diagram illustrating formation of portland
for Type III. The S03 content for Type I cements typically
cement reaction products and reduction with time of the
ranges from 2.0 to 4.4 percent (Bhatty and Tennis 2008).
volume ofpore space in a portland cement paste (adapted
Generally, the maximum permissible amount of S03 is a
from Locher et al. [1976]).
function of the C3A content and the fineness. The S03 not
consumed in the first few days might combine with unre­ the expansion in water at 1 4 days (ASTM C 1 038/C 1 038M)
acted C3A at later ages to produce ettringite, resulting in is not excessive for ASTM C 1 50/C 1 5 0M, ASTM C595/
destructive long-term expansion. Sulfate content exceeding C595M, and ASTM C 1 1 57/C 1 1 5 7M cements.
the default maximum is permitted if tests demonstrate that

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The S03 present in cement comes principally from one
or more forms of calcium sulfate added during grinding,
but significant amounts may also come from the clinker if
high-sulfur fuel is used in the clinker burning process. The
combustion of sulfur compounds in the fuel often forms
sulfites and sulfates that are less effective than the inter­
ground gypsum in controlling the setting. The amount of
so3 added is established by the cement producer primarily
to optimize strength and time of set. The S03 content will
also influence among other properties, drying shrinkage, and
slump loss in concrete.
4.2-Biended hyd raulic
The overall chemistry of blended hydraulic cements
is similar to that of portland cements. They contain port­
land cement blended with such materials as slag cements,
fly ashes, silica fumes, limestone, raw or calcined natural
pozzolans, or combinations of two of these, if producing
a ternary blend. Chemical requirements, physical require­
ments, or both, of the slag cements, pozzolans, or limestone
to be used in blended hydraulic cement are described in
ASTM C595/C595M. Detwiler et a!. ( 1 996) discusses the
use of these materials in blended hydraulic cement.
4.2.1 Blast-furnace slags Blast-furnace slags are
- cement, but allowance for this can be made in the manu­
by-products of the manufacture of iron. The molten slag
leaves the blast furnace as a liquid. There are primarily
two methods of rapidly cooling the molten slag: 1 ) water
granulation, which involves quenching with water; and
2) pelletization, which includes a combination of both air
and water spray. These methods form glassy nodules that
can be ground to form a cementitious powder called slag
cement. If the molten slag is cooled slowly, it forms a much
less reactive crystalline product called air-cooled slag that
is frequently crushed and used as aggregate. For additional
information, refer to ACI 233R.
4.2.2 Fly ashes-Fly ashes are the finely-divided residues
from the combustion of powdered coal. Large quantities are
obtained from coal-burning power plants. Fly ashes contain
small, spherical particles of glassy material with pozzolanic
properties. In addition, crystalline components are also
present. For additional information, refer to ACI 232.2R.
4.2.3 Limestone-Limestone is a rock consisting mainly
of calcium carbonate that can be finely ground and used as
an ingredient in portland and blended cements. Limestone
can contribute beneficially to the performance of cements
through physical effect, such as improved particle size distri­
bution, acting as nucleation sites for cementitious hydrates,
and by providing a minor amount of chemical reaction.
Cements with up to approximately 1 5 percent limestone
can generally be produced to have comparable strength and
performance characteristics to portland and other blended
cements. For additional information, refer to Tennis et a!.
(20 1 1 ).
4.2.4 Natural pozzolans-Natural pozzolans are naturally
occurring siliceous, or siliceous and aluminous, minerals.
Though they are usually not cementitious by themselves,
pozzolans in finely divided form will react with the calcium
hydroxide produced by cement hydration to form the same
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11
compounds as are formed by the hydration of portland
cements. Most natural materials require heat treatment,
grinding, or both, to make them useful as pozzolans. They
include materials such as opaline cherts and shales, volcanic
ashes, other noncrystalline materials such as diatomaceous
earths, calcined clays (Hooton et a!. 1 997), and sometimes
metastable crystalline materials such as tridymite. For addi­
tional information, refer to ACI 232 . 1 R.
4.2.5 Silica fum e-Silica fume is a finely divided silica­
bearing residue of the silicon metal manufacturing process
that possesses pozzolanic properties. This material is added
as a separate ingredient to concrete mixtures or as a compo­
nent in blended cement to produce a cementitious system for
concrete. Silica fume is often used in conjunction with fly
ash or slag in concrete mixtures. For additional information,
refer to ACI 234R.
4.2.6 Reactions ofblended hydraulic cements with water­
The blended ingredients all react with water, or with water
and calcium hydroxide, to form the maj or phases of calcium
silicate hydrates and calcium aluminate hydrates, similar
to those produced by the reactions of portland cement with
water. The rates of reaction of the materials blended with
the portland cement tend to be lower than those of portland
facture of the cement and curing of the concrete to ensure
suitable performance in concrete, including strength devel­
opment. Specially activated, blended hydraulic cements are
available to provide very early high strength.
4.3-Shrinkage-compensating expansive
Shrinkage-compensating expansive cements are designed
to expand a small amount during the first few days of
hydration. The amount of expansion is intended to approxi­
mately offset the amount of drying shrinkage anticipated
in the concrete. The expansion is brought about by incor­
porating specific compounds such as calcium sulfoalumi-
nate, calcium aluminate, calcium sulfate (C4A3 S , CA, and
C S ), or other phases that, in the presence of water, react
to produce a larger quantity of ettringite than is normally
produced by portland cements. The production of the ettrin­
gite in the hardened concrete causes the concrete to expand.
This expansive reaction occurs during the first few days and
is essentially complete after 7 days. ASTM C845/C845M,
which describes the three cements of this type, limits the
increase in expansion between 7 and 28 days to 1 5 percent
of the 7 -day expansion.
To achieve the proper performance of shrinkage-compen­
sating expansive cements, the inclusion of the appropriate
amounts of reinforcing steel in the concrete is necessary. For
maximum expansion, additional moisture beyond that added
as mixing water should be supplied during curing of the
concrete to ensure that the desired amount of ettringite will
be produced. The use of shrinkage-compensating expansive
cements is described in detail in ACI 223R.
4.4-Calcium-al u m i nate
Calcium-aluminate cements are primarily used for high
heat refractory applications. Other uses include moderate
cCiC'iJ
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12 GUIDE TO TH E SELECTION A N D U S E O F HYDRAULIC CEMENTS (ACI 225R-16)
acid-resistant applications, high-early-strength and quick­
setting mixtures, and as part of the expansive component in
some shrinkage-compensating cements. They are produced
by pulverizing a solidified melt or clinker that consists
predominantly of hydraulic calcium aluminates formed from
proportioned mixtures of aluminous and calcareous mate­
rials. These cements are typically designed to gain strength
much faster than ordinary portland cements and predomi­
nately consist of calcium aluminate that can produce large
amounts of heat during the first 24 hours. The cement
phase ratios (CA or CA2) are proportioned according to the
intended application performance characteristics (Lea 1 998;
Robson 1 962).
Potential users of calcium-aluminate cements should be
aware that conversion of the hydration products from meta­
stable hexagonal hydrates (CAH10) to stable cubic hydrates
(C3AH6) of lower volume can reduce strength (Robson
1 962). Primary causes of the conversion from metastable
to stable hydrates, with resulting loss of strength, are high
water-cement ratios (w/c), high curing and ambient tempera­
tures, and high ambient humidity. Conversion can be delayed
by keeping the concrete cool and dry and by using a low
w/c, but it will eventually occur. Therefore, concrete struc­
tures using this cement should be designed for converted
strengths. In most refractory applications, strength is not a
major concern and, therefore, conversion is not normally
a major factor. The conversion of hydrates can increase
permeability and result in acceleration of the corrosion of
embedded steel in structures (Odler 2000). These cements
are discussed further in Appendix A and ACI SP-57 (Amer­
ican Concrete Institute 1 978).
CHAPTER 5-I N FLUENCE OF C H E M I CAL
ADM IXTU R ES, POZZOLANS, AND SLAG
C E M ENTS ON C E M E NTITIOUS SYSTEMS
Chemical admixtures, pozzolans, and slag cements have
become essential parts of concrete technology. The effects of
admixtures on the performance of concrete are usually intri­
cately linked to the particular cement-admixture combina­
tions used. Although they may not be fully understood, it is
helpful to recognize the types of effects that may result from
changes in cement composition. This chapter is intended to
provide a brief introduction to this subject.
ACI 2 1 2.3R contains extensive information on admix­
tures and their use. Slag cement, silica fume, raw and
calcined natural pozzolan, and fly ash are discussed in ACI
233R, 234R, 232. 1 R, and 232.2R, respectively. The primary
purpose of this discussion is to highlight those characteris­
tics of chemical admixtures, slag cements, and pozzolans
that influence cement performance. Only air-entraining,
accelerating, retarding, and water-reducing chemical admix­
tures are discussed.
Pozzolans and slag cements are finely divided inorganic
materials that can be added to concrete to enhance its perfor­
mance and possibly reduce the overall cost. Specifications
for fly ash and natural pozzolans are given in ASTM C6 1 8.
Slag cement specifications are given in ASTM C989/C989M
and silica fume specifications are given in ASTM C 1 240.
(ciCiJ American Concrete Institute- Copyrighted© Material- www.concrete.org
Canadian specifications for slag cement and pozzolans
are included in CSA-A3000. Pozzolans and slag cements
can improve the workability and flow properties of fresh
concrete, reduce shrinkage, and improve the strength and
other properties of hardened concrete. Some can diminish
the likelihood of sulfate attack and alkali-aggregate reaction
(AAR) expansion. Additional guidance is given on natural
pozzolans in ACI 232 . 1 R, fly ash in ACI 232.2R, silica fume
in ACI 234R, and slag cement in ACI 233R.
5 . 1 -A i r-entra i n ing admixtu res
Air-entraining admixtures are surface-active agents that
form stable air bubbles with diameters less than 0.04 in.
( 1 mm) in concrete during mixing (Klieger 1 994; Mielenz
et a!. 1 95 8a,b,c,d). The generally available admixtures are
formulated to provide these small-sized bubbles rather than
undesirable larger ones. A discussion of factors affecting the
performance of air-entraining agents in concrete is given in
ACI 2 1 2.3R, Whiting and Stark ( 1 983), and Whiting and
Nagi ( 1 998).
Serious problems sometimes occur in obtaining consistent
high-quality air-void systems in concrete under field condi­
tions. Both the volume and characteristics of air voids are
influenced by many factors, including water-cementitious
materials ratio (w/cm); aggregate grading; other admixtures;
temperature; and, to some extent, the particular cement used.
The ability to entrain air in concrete or mortar for a given
admixture dosage is also affected by the slump or fluidity
of the mixture; concrete temperature; and some properties
of the aggregate such as texture, angularity, and grading.
During the many years of successful use of air entrainment,
specific influences of cements have not received as much
attention as those of other factors. Recent trends toward
concrete with lower w/cm, smaller coarse aggregate, and
increased use of pozzolans and chemical admixtures are
bringing about renewed study of air entrainment, including
the influence of cement. Increasing the amount of cement
or other finely divided material in concrete decreases the
amount of air entrained by a given amount of admixture.
Two characteristics of portland cement are known to
influence air entrainment: 1 ) an increase in cement fineness;
or 2) a decrease in cement alkali content, which generally
increases the amount of admixture required for a given air
content.
Blended hydraulic cements may require a greater quan­
tity of air-entraining admixture than portland cements to
produce a given air content. Further, if fly ash is used in a
blended cement, there may be an increased tendency for
loss of air during mixing, transit, and placement than when
portland or blended cements that do not contain fly ash are
used. For additional information, refer to ACI 2 1 2.3R on air­
entraining admixtures and ACI 232.2R on fly ash.
5.2-0ther chemical admixtures
ASTM C494/C494M defines the types of chemical
admixtures and classifies them according to their effects on
portland-cement concrete, as shown in Table 5.2.
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16) 13

The most commonly used types are A, C, D, and E. Of Table 5.2-Types and effects of chem i cal
these, Types A or E admixtures are generally made by the admixtures
addition of an accelerator to a basic water-reducing and Type Description
retarding material similar to a Type D admixture. Type G A Water-reducing
admixtures are generally made by the addition of a retarder
B Retarding
to a Type F admixture.
The behavior of chemical admixtures with cements other c Accelerating
than portland cements is difficult to predict. With blended D Water-reducing and retarding
cements, the behavior is determined primarily by the amount
E Water-reducing and accelerating
of portland cement present. Variations in the effectiveness of
F High-range water-reducing
chemical admixtures frequently make it necessary to make
trial mixtures simulating job materials, conditions, and G High-range water-reducing and retarding
procedures. Field experience with specific combinations is s Specific performance admixture
also valuable. A general discussion of the effects of admix­ _
tures with shrinkage-compensating expansive cements is
The amount and form of S03 in a cement affect the
given in ACI 223R.
amount of a specific admixture required at the concrete
5.2.1 Accelerators-Calcium chloride is the most widely
temperature in use. Meyer and Perenchio ( 1 979) concluded
used inorganic accelerator. Chlorides can increase the
that the addition of a chemical admixture, which may alter
corrosion of steel (ACI 222R). Chapter 1 9 of ACI 3 1 8- 1 4
the rates of the reactions in the presence of water, can upset
provides additional information on the limits and rest�ic­
the balance between the soluble sulfate and the C3A in a
tions on chloride content of concrete. Several nonchlonde
portland cement. This may result in rapid loss of slump or
accelerators are commercially available for all applica­
extended setting time.
tions in which the chloride content of the concrete should
To some extent, each cement-admixture combination is
be limited. Some examples are calcium formate, calcium
unique. The temperature and mixing time have a large effect
nitrate, calcium nitrite, sodium thiocyanate, and combina­
on the early hydration reactions, and the specific results with
tions thereof. Organic compounds, such as triethanolamine,
different combinations are difficult to predict. The effects
are used in proprietary admixtures to offset retardation, but
previously outlined, however, are the most significant
are not normally sold separately as accelerators.
effects of cement composition on the response of admix­
Calcium chloride does react, to some extent, with the
tures. Because the effects cannot be predicted with confi­
aluminate compounds in portland cements but, at the levels
dence, admixtures should be evaluated with job materials
required to give significant acceleration, a considerable
using temperatures, delivery times, and placing conditions
portion remains soluble and uncombined so that the potential
_ expected on the job.
for chloride-assisted corrosion of steel reinforcement remams.
5.2.3 High-range water-reducing admixtures-Most high­
5.2.2 Water-reducing retarders-ACT 2 1 2.3R lists a
range water-reducing admixtures are typically dispersing
variety of materials that are marketed, singly or in combi­
surfactants. These chemicals adsorb onto the surface of
nation, as water-reducing retarders. The composition of the
cement particles and repel other cement particles that also
cementitious material in concrete can have a significant
have dispersant molecules adsorbed onto their surfaces.
influence on the behavior of all chemical admixtures. As
These admixtures permit considerably larger water reduc­
much as these admixtures affect the early stages of hydra­
tions than Types A, D, and E, and can be used to produce
tion, and are at least partly removed from solution by the
very low w/c concretes at conventional slumps, or flowing
early reactions, the cement phases that react most rapidly
concretes at conventional w/c. Concretes containing these
have a large influence on their action. The early-reacting
admixtures, particularly those with low slump and low w/c,
compounds include C3A and the alkali and calcium sulfates.
may lose slump and stiffen rapidly. The performance char­
For more information, refer to ACI 2 1 2 .3R, Klieger ( 1 994),
acteristics of high-range water-reducing admixtures, such as
Mather ( 1 994), and Cain ( 1 994).
retention of slump, rate of setting, and strength gain, seem to
The quantity of admixture required to produce the desired
be related to the same cement properties as those mentioned
results increases with an increase in the C3A, the alkali
under water-reducing retarders, though not always in the
content, and the fineness of the cement (Ramachandran
same way as those that influence conventional water­
1 995). The alkali content of the cement, the amount and
reducing admixtures. Properties of cement that can regulate
form of so3 in the cement, the temperature, and the compo­
the rate at which the early hydration reactions occur include
sition and amount of admixture affect the performance of
sulfate content, C3A content, alkali content, and fineness.
the cement-admixture combination (Helmuth et a!. 1 995).
The practice of delaying the addition of a high-range
In general, the cement has less effect on the reduction in
water-reducing admixture allows for the early cement grain
mixing water than on the setting and strength gain of the
surface hydration to occur and the surfactant to adsorb onto
cement-admixture combination. C3A and alkali contents and
the top surface of the hydration products without being
the fineness vary not only among cements from different
chemically absorbed, trapped, or hindered by the hydration
sources, but also, to a lesser degree, among samples of
products, and kept from performing the dispersing func-
cement from the same source.

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14 G U I D E TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
tion (Ramachandran 1 995). The effect of temperature is
also significant with high-range water reducers and gener­
ally similar to the effects observed with conventional water
reducers. For further information on admixtures for flowing
concrete, refer to ACI 2 1 2.3R and ASTM C l 0 1 7/C l 0 1 7M.
5.2.4 Type S: Specific performance admixtures-Type S
admixtures are admixtures that provide a desired perfor­
mance characteristic other than reducing water, changing
the time of setting, or both, without adversely affecting the
fresh, hardened, or durability properties of the concrete.
Specific performance characteristics include, but are not
limited to, shrinkage reduction, mitigation of alkali-silica
reaction, and viscosity modification (ASTM C494/C494M).
This does not include admixtures that are used primarily in
the manufacture of dry-cast concrete products.
5.3 - Pozzolans
-
5.3.1 Fly ashes Fly ashes are pozzolanic materials.
Those with relatively high calcium contents are typically
more reactive than those with lower calcium contents. Also,
fly ashes with higher alkali contents are more reactive than
those with lower alkali contents. Because the main elements
in fly ashes are the same as those present in portland cements,
fly ashes are generally compatible with portland cements.
The percentage will depend on the properties of the fly ash
and cement and the desired properties of the concrete.
When improved sulfate resistance is desired, the sulfate
resistance of the combination of cement and fly ash should
be tested before use. ASTM C l 0 1 2/C l 0 1 2M is an appro­
priate test method and ASTM C6 1 8 specifies the acceptable
expansion limits. The alumina in the fly ash as well as the
C3A in the cement both contribute to susceptibility to sulfate
deterioration. The minimum quantity of fly ash required for
sulfate resistance is variable, but it is generally accepted that
the addition rate used should be that which has been demon­
strated to provide adequate sulfate resistance.
Some fly ashes are helpful in reducing the disruptive
effects of the AARs of some siliceous aggregates. Mortar
bar expansion tests in accordance with ASTM C227, ASTM
C l 567, or concrete tests such as ASTM C l 293 should be
made with the appropriate combinations offly ash, the poten­
tially reactive aggregates, and the cement under consider­
ation to determine whether the expansion due to the AAR is
adequately reduced.
Possible problems with fly ash include irregular perfor­
mance, particularly with regard to air entrainment, lower
early strength, longer setting time, and the need for longer
curing of the concrete. The lack of uniformity in response
to air-entraining admixtures results from variations in the
quantity of carbon in the ash and possibly other organic resi­
dues from the fuel. These problems can be largely alleviated
by using uniform, high-quality fly ash. ACI 232.2R provides
additional information on the use of fly ash in concrete.
-
5.3.2 Natural pozzo lans Naturai pozzolans can be
incorporated in a concrete mixture to provide additional
cementing value because of their reactions in the presence of
cement and water. To increase their reactivity, natural pozzo­
lans often need to be activated by heating for a short time
(ciCiJ American Concrete Institute- Copyrighted© Material- www.concrete.org
at temperatures between 900 and 1 800°F (500 and 1 000°C)
and by grinding. The main constituents of pozzolans are
compounds of calcium, silicon, aluminum, iron, and oxygen.
Benefits from the use of natural pozzolans in concrete can be
increased strength at late ages, modified color, improved dura­
bility in sulfate environments, and inhibition of AAR. Disad­
vantages can be lower early strength, longer curing time,
increased water requirement, and the problems of handling an
additional material. As with fly ash, if sulfate resistance and
reduction of expansion due to alkali-silica reaction (ASR) are
desired, tests should be made with project-specific materials.
For more information, refer to ACI 232 . 1 R.
-
5.3.3 Calcined clay Clay is a naturally occurring raw
material composed essentially of alumino-silicate minerals.
Examples are known as kaolinite, dicite, halloysite, and illite.
The purity of these naturally occurring deposits can vary
from 98 percent pure mineral types, to mixtures of multiple
mineral types. Because clays are, by definition, very fine­
grained materials, they are easily quarried and stockpiled.
Stockpiles of kaolinitic clay compacted fines often weather
and dry and return to the uncompacted state and, therefore,
require little or no additional deagglomeration.
The calcining of clay is known as dehydroxylation and
is performed by removing bound water. This is typically
performed in rotary kilns or flash calciners where the clays
are heated to a temperature adequate to decompose the
clay's crystal structure and render it amorphous. For kaolin­
itic clays, this temperature is usually approximately I 022
to 1 3 82°F (550 to 750°C). Other clay types may require
different thermal activation temperatures to optimize the
material's pozzolanic reactivity. This process is easily moni­
tored by X-ray diffraction.
Depending on the purity of the clay material, calcined clay
may result in one or more phases present. These phases may
be amorphous, crystalline, or both. Calcined clays have been
used as manufactured pozzolans in concrete for many years.
In the Midwest United States, calcined kaolinitic clays have
been documented as containing a mixture of approximately
85 to 90 percent metakaolin, 5 to 1 0 percent quartz, and
residual mixed clays of illite and montmorillonite or smec­
tite (Barger et al. 1 997). Kaolinite is a higher-purity calcined
clay with greater than 95 percent metakaolin.
-
5.3.4 Silica fume Silica fume is extremely reactive with
portland cements. As a pozzolan in concrete, it is often used
to reduce permeability and increase strength. Typically,
silica fume consists of extremely fine spherical particles of
amorphous silicon dioxide. Because of its high surface area,
the amount used is generally less than approximately 1 0
percent by mass of cement. Silica fume has also been used
to increase strength in calcium-aluminate cement systems.
Usually, high-range water reducers are used with silica fume
to maintain mixing water requirements at acceptably low
levels to control drying shrinkage and improve workability.
Because of its reactivity, silica fume can generally replace
three to four times its mass of portland cement and main­
tain equal compressive strength. For additional information,
refer to ACI 234R.
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
5.4-Siag cements
Slag cements are used either as a separate cementitious
material introduced to the concrete batch, or as an ingre­
dient in blended hydraulic cements. Slag cements have been
used throughout the world for many years in the concrete
industry. The main constituents of slag cements are oxides of
calcium, magnesium, silicon, and aluminum. A range of 25
to 7 5 percent of slag cement in the total cementitious content
is commonly used.
In most cases, slag cement is used in tandem with portland
cement, but can also be used in mixtures with combinations
of portland cement and fly ash, silica fume, or natural pozzo­
lans. The amount of portland cement required varies with
each application. The performance of a given slag cement
depends on characteristics of the cementitious system in
which it is used. Improved strength performance was found
with cements that have higher contents of alkali and C3A
and higher fineness (Schroder and Vinkeloe 1 969; Detwiler
et a!. 1 996). Other factors influencing reactivity are chem­
ical composition, glass fraction, fineness, and temperature
during the early phases of hydration. Refer to ACI 233R,
ASTM C989/C989M, and CSA-A30 0 1 for additional infor­
mation on the use of slag cement in concrete.
CHAPTER 6-I N FLUENCE OF ENVIRONM E NTAL
CONDITIONS ON THE HYDRATION O F C E M E NTS
The hydration of cement in concrete is affected by the
environmental conditions to which the concrete is exposed,
particularly during curing. Curing is the process of main­
taining a satisfactory moisture content and a favorable
temperature in concrete during its early ages so that the
desired properties are developed. Curing methods and
materials are discussed in ACI 308R. The degree to which
temperature and relative humidity affect the behavior of the
cement mixture depends on the chemical and physical char­
acteristics of the cement. These effects are reviewed briefly
to provide background for the more extensive discussion of
factors affecting concrete performance given in Chapter 7.
6.1 -Water req u i rements
Hydraulic cements require water for hydration. The quan­
tity of mixing water required to completely hydrate portland
cement is a w/c of approximately 0.4 by mass, of which
approximately 0.2 is chemically combined and 0.2 fills the
gel pores; the chemically combined water cannot form gel
unless other water is available to fill the gel pores (Philleo
1 986). Loss of water from concrete by evaporation, absorp­
tion, or both, may reduce the quantity of water available for
hydration. Excessive loss of water during the early stages of
hydration may result in premature termination of hydration.
6.2-Temperature effects
The rate of reaction between cement and water can be
dramatically affected by temperature. Although hydra­
tion of most cements proceeds very slowly below approxi­
mately 40°F (4 °C), the rate will increase with the tempera­
ture. Typically, the rate of reaction as a function of the total
extent of reaction doubles for each 1 8°F ( 1 0°C) increase in
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15
temperature and, conversely, is halved for each 1 8°F ( 1 0°C)
decrease. According to ACI 305R, placement temperatures
in excess of95°F (35°C) can reduce long-term strength gain.
Lower temperatures produce higher ultimate strengths, but
the rate of strength development is reduced. For a discussion
of steam curing, refer to Kosmatka and Wilson (20 1 1 ). Other
references concerning high-temperature curing include
Hanson ( 1 963) and Bush et a!. ( 1 963).
6.3-Composition
Fineness and chemical composition are the major char­
acteristics of cement that influence its rate of reaction and
strength development in concrete. Generally, the finer the
portland cement, the higher its rate of reaction and early
strength gain. Tables 4. 1 b and 4. 1 c show typical differ­
ences in fineness and composition between Type III cements
and other portland cements. At standard laboratory testing
temperatures of 73°F (23°C) and below, blended hydraulic
cements may gain strength slower than portland cements of
the same fineness and may require longer curing.
The hydration of hydraulic cements is an exothermic reac­
tion and can alter the effects of temperature-induced retarda­
tion when these hydration reactions are accelerated. Thus,
the higher the rate ofreaction of the cement, the more rapidly
heat is produced. In thick sections of concrete, a condition
can exist under which temperature-related cracking can
occur. Surface cracks can develop from a steep temperature
gradient between the exposed surface and interior concrete.
Information on mass concreting and guidance on estimating
the effects of heat generation and volume changes on the
behavior of thick structures is given in ACI 207 .2R.
CHAPTER 7-I NFLUENCE OF CEM ENT ON
CONCRETE PROPERTIES
Cement is characterized on the basis of its effects on the
performance of concrete and on its chemical composition. For
some performance-related properties, such as strength and
volume stability, comparatively rapid and reliable test proce­
dures are available. For other properties involving aspects
of long-term durability, the time required for testing and
the difficulties of duplicating specific environmental factors
seem to require characterization of the cement by composi­
tion. Therefore, proper selection of cement to provide specific
properties or to meet special service requirements can only be
made if the influence of cement upon individual properties of
concrete is understood (Transportation Research Board 1 999).
7.1-Thermal cracking
Heat is liberated as cement hydrates, and the amount and
rate of heat liberation are functions of the composition and
fineness of the cement (Lea 1 998). In general, the rate of
heat liberation parallels the rate of strength increase. In most
concrete construction, the heat evolved is quickly dissipated
and is oflittle concern. In structures such as large abutments,
massive foundations, and dams, however, precautions may
have to be taken to limit the temperature rise. If they are
not taken, thermal expansion may be so great that cracking
will occur later, either as the exterior of the mass cools and
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16 GUIDE TO TH E SELECTION A N D U S E O F HYDRAULIC CEMENTS (ACI 225R-16)

contracts before the interior does so, or as the entire struc­
ture cools, and cracks due to the restraint are imposed.
Information on estimating the temperature of concrete over
time due to hydration is given in ACI 207.2R, and guidance
on thermal cracking is given in ACI 224R. Information on
concrete for mass structures is given in Portland Cement
Association ( 1 987) and Bamforth ( 1 984).
The principal phases in portland cements hydrate at
different rates. They also yield considerably different
amounts of heat per unit mass hydrated (Table 7. 1 a). Gener­
ally speaking, tricalcium aluminate (C3A) releases most of
its heat in the first day, tricalcium silicate (C3 S) in the first
week, and dicalcium silicate (C2 S) and calcium aluminofer­
rite (C4AF) hydrate more slowly.
The data shown in Table 7 . 1 a are the heats evolved in the
complete hydration of a unit mass of each of the pure phases.
Although useful in indicating the orders of magnitude of the
Table 7.1 a-Heats of complete hydration of pure
cement compounds
Compound Heat of hydration, kJ/kg (cal/g)
c3s 502 (120)
c2s 259 (62)
C3A 865 (207)
C.AF 4 1 8 (100)
CaO (free lime) 1166 (279)
total contributions of the individual phases to the heats of
complete hydration, the data in Table 7. l a cannot be used
for calculating heats of hydration of commercial portland
cements for the following reasons:
a. The phases mixed together in a cement may hydrate at
different rates from phases hydrating alone; unless the rates
are known, the contribution of each phase at a given time
will not be known.
b. The phases in commercial cements contain elements
other than those indicated by the simple formulas and their
reactivity is affected by crystal size and morphology.
c. Various parameters involved in the manufacturing of
clinker, including temperature, residence time, and cooling
rate, affect the formation of the clinker phases; thus, the
potential Bogue phase composition may differ from actual
phase composition.
Fineness of cement is a prime factor affecting the rate of
heat liberation, particularly at early ages. Data for modem
cements are given in Table 7. l b. Fineness is also a major
contributor to the differences between the characteristics for
Type III and Type I cements. In all cases, including Type III,
cements continue to hydrate even beyond the age of 1 year.
The rate of strength gain during hydration is related to the
rate of heat liberation for each of the five types of cement.
ASTM C 1 50/C 1 50M recognizes the heat of hydration as
a potentially critical characteristic for some applications.
This specification contains composition and fineness limits
for Type II(MH) (moderate heat of hydration) and Type IV

Table 7.1 b-ASTM C 1 86 heat of hydration for selected portland cements, cal/g (Portland Cement
Association 1 997)
Type II (moderate
Type I cement Type II cement heat) cement Type III cement Type IV cement Type V cement

No. 7-day 28-day No. 7-day 28-day No. 7-day No. 7-day 28-day No. 7-day 28-day No. 7-day

I 82.0 -
16 77.7 10 1 .4 32 67.6 36 88.0 99.0 38 60.0 -
41 81.5

2 85.6 -
17 82.6 88.8 33 65.0 37 89.0 95.0 39 57.3 -
42 66.5

3 81.6 -
18 88.7 89.4 34 54.3 40 49.7 65.5 43 79.3

4 80.2 -
19 88.0 -
35 64.7 44 80.4

5 78.4 -
20 73.6 -
45 76.1

6 88.3 90.2 21 88.5 -

46 61.4

7 88.2 106. 1 22 77.1 89.7

8 87.7 93.5 23 87.3 -

9 88.9 97.7 24 8 1 .9 100.3

10 76.4 91.7 25 88.3 99.4

II 84.4 91.7 26 86.5 96.8

12 84.4 98.5 27 79.5 -

13 83.5 -
28 79.4 -

14 79.5 -
29 80.0 -

15 83.0 -
30 80.0 -

- - -
31 77.6 -

Avg. 83.5 95.6 Avg. 82.3 95 . 1 Avg. 62.9 Avg. 88.5 97.0 Avg. 55.7 NM Avg. 74.2

Max. 88.9 106. 1 Max. 88.7 10 1 .4 Max. 67.6 Max. NM NM Max. 60.0 NM Max. 81.5

Min. 76.4 90.2 Min. 73.6 88.8 Min. 54.3 Min. NM NM Min. 49.7 NM Min. 61.4

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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
(low heat of hydration) cements and optional limits for heat
of hydration based on physical testing by ASTM C 1 702 or
ASTM C 1 86. Options for cements with low or moderate
heat of hydration are also provided in ASTM C595/C595M
and ASTM C l l 57/C 1 1 57M.
It is often assumed that blended cements have lower heats
of hydration than portland cements. However, depending on
the ingredients, they may have lower or roughly equal heats
of hydration. In a structure, the temperature-induced effects of
expansion or contraction depend on the mass of the member
and its age. In general, the heat of hydration of shrinkage­
compensating expansive cements, as stated in ACI 223R, is
within the range of variation of the heat of hydration of the
particular portland cements used in their manufacture.
7.2-Placeability
Several characteristics of cement may influence the place­
ability of the concrete in which the cement is used. The
influence of the cement on placeability can be beneficial or
detrimental.
7.2.1 Cement fineness Fineness of cement influences the
- Flash set is another phenomena associated with slump
placeability, workability, and water demand of a concrete
mixture in much the same way as the amount of cement
used in the concrete. The overall importance of cement fine­
ness, however, is only modest compared to the effect of the
amount of cement used.
In concrete, other constituents such as entrained air,
mineral and chemical admixtures, and the fine materials and
clays in aggregates also affect workability, plasticity, and
mixing-water requirements.
7.2.2 Cement-setting characteristics-The setting or stiff­
ening characteristics of cement are transferred directly to
the concrete mixture. A tendency for the mixture to stiffen
prematurely or to rapidly lose slump directly affects place­
ability, consolidation, and finishability. The normal setting
or stiffening characteristics will determine the time available
for placement, consolidation, and finishing. Rich mixtures
frequently set slightly sooner than lean mixtures.
The temperature of the concrete has a significant effect on
its rate of hardening. The temperature of the cement itself
has very little influence on the temperature of the concrete
and, consequently, on its hardening rate. Often, a rapid loss
of slump or reduction in hardening time is considered to be
caused by the use of hot cement. As cement clinker is ground
into finished cement, energy, in the form of heat, is imparted
to the finished ground cement. Dependent on the efficiency
of the cooling system, the cement temperatures may range
from a low of 90°F (32°C) to a high of 1 70°F (77°C). After
the cement is put into the storage silo, it takes a considerable
amount of time for the heat to dissipate. The thermal accel­
eration of the cement hydration, however, is controlled by
the overall concrete temperature. ACI 305R gives a formula
for estimating the effect of cement temperature on the
temperature of freshly mixed concrete. When the tempera­
ture of each of the individual components is known, it is esti­
mated in ACI 305R that a 2°F ( 1 .2°C) change in aggregate
temperature equates to 1 °F (0.6°C) change in a normally
proportioned concrete mixture as does a 9°F (5°C) cement
American Concrete Institute- Copyrighted© Material- www.concrete.org
17
temperature change. While cement temperature does affect
the concrete temperature, other components should not be
overlooked for their influence on the concrete temperature.
Distinguishing between normal slump loss of concrete
with time and a false-setting cement is important. Normal
slump loss is gradual and more or less proportional to time
until there is no slump. Ordinary slump loss cannot be
restored by remixing. With a severe false set, all slump may
be lost in 5 or 1 0 minutes, but remixing will restore nearly all
of the original slump. This phenomenon is the result of the
use of some of the mixing water to rehydrate the dehydrated
calcium sulfate phases present. A mild or moderate case of
false set may result in only a high rate of slump loss shortly
after mixing. False set is less affected by the temperature of
the concrete than slump loss, which is more rapid in warmer
weather. In some cases, false set and excessive slump loss
occur together and the problems tend to merge. In stationary
plant mixers operating with mixing times less than 1 minute,
increasing the mixing time will frequently alleviate false set
and the associated early slump loss.
loss, but is typically more severe and not recoverable.
Flash set is a result of the mixing water being chemically
combined by the C3A or free lime component of cement or
fly ash in the cementitious system. This water, however, is
not released and therefore slump is not recovered. The rate
of the sulfate solubility in the system is the key to reducing
flash set when it is associated with the C3A phase. Increasing
the calcium sulfate content, or increasing of the solubility
rate of the existing calcium sulfate present during the manu­
facture of the cement, helps to eliminate this phenomenon.
Concrete containing water-reducing or retarding admix­
tures may exhibit faster slump loss than similar concretes
without the admixtures. This effect is especially pronounced
and common with high-range water-reducing admixtures.
Certain admixtures can cause significant changes in setting
time (Hersey 1975).
As discussed in ACI 223R, shrinkage-compensating
expansive cements may show somewhat greater slump loss
than portland cements in hot weather.
7.3-Strength
A number of researchers have studied the possibility of
predicting the compressive strength potential of portland
cements from the chemical composition expressed either as
potential phases or oxides and physical characteristics such
as fineness (Alexander 1 972; Blaine et a!. 1 968; Gonnerman
1 934; Gonnerman and Lerch 1 95 1 ; Popovics 1 976).
7.3.1 Cement composition-C3S, C 2 S, and C3A are the
principal strength-producing phases in portland cement
(Lea 1 998 ; Taylor 1 964). The proportions of these can be
varied in the manufacturing process and can change both
the early-strength characteristics and the long-term strength.
The following paragraphs describe these effects for curing
temperatures between 35 and 1 90°F (2 and 90°C).
Increasing the proportion of C3S increases strength at
ages from 1 0 to 20 hours through 28 days. The percentage
of C3 S in portland cements typically ranges from 5 6 to 58
Licensed to: Florida Suncoast Chapter
18 G U I D E TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)

percent (Bhatty and Tennis 2008). In the case of Type IV 7000

cements, however, C3S can be as low as 20 percent and C2S .. «<
Q. 6000 40 II.
can be as high as 55 percent. Type IV cements are now rarely :IE
£ %
produced. 1- 5000
" 1-
"
C2S contributes slightly to strength at ages as early as 1 z 30 z
w
w
or 2 days and significantly to 28-day strength with a major a: 4000 a:
1-
1-
effect of increasing later-age strengths. Most portland 1/) 1/)
w 3000 20 w
cements contain 1 0 to 35 percent C2 S. Increasing propor­ > >
tions of c2s with proportional decreases in c3s content, 0 iii
1/) 2000 1/)
however, generally reduces 28-day strength and increases w w
a: 10 a:
II. II.
strength at ages of 45 to 60 days through 5 years and more. :IE 1 00 0 :IE
The long-term strength contributions of C2S are dependent 0 0
0 0
on extended availability of moisture. Hydration stops when 0 0
7 14 28 90 1 80 1 2 3
the internal relative humidity falls below approximately 80
percent, and the later-age strength benefits of C2S may not 1.. DAYS YEARS --I
be obtained. Thick sections of concrete tend to retain mois­ Fig. 7. 3. 1-Rates of strength development for concretes
ture and benefit from the long-term strength contributions of made with various types of ASTM C150/C150M portland
C2S, thin sections such as slabs or pavements may be more cement and subjected to continuous moist curing (U.S.
susceptible to premature drying. Bureau of Reclamation 1981).
C3A contributes principally to strength at 24 hours or less.
The C3A itself hydrates quickly. At the same time, its hydra­ The strength gain characteristics of shrinkage-compen­
tion generates heat, which has a modest effect in acceler­ sating expansive-cement concrete are comparable with those
ating the hydration of the C3 S and C2S. The C3A content of of Type I portland-cement concretes.
portland cements ranges from 0 to 1 7 percent. 7.3.2 Fineness-Typical high-early-strength cements
C4AF makes a smaller contribution to the strength ofportland have Blaine fineness values greater than 500 m2/kg. The
cement; it facilitates burning of the cement clinker and forma­ higher fineness increases the strengths of portland cement
tion of the strength-producing silicates. Typical C4AF contents at early ages and up to approximately 28 days. The effect
for different portland cements range from approximately 5 to is most pronounced at 1 0 to 20 hours and diminishes as the
20 percent. Strength development curves for concrete made age increases. At 2 to 3 months, under proper moist-curing
with various cement types are shown in Fig. 7.3. 1 . conditions, the high-fineness cements provide strengths
Some minor components of portland cement also affect approximately equal to those of normal-fineness, general-use
strength. In particular, the quantity of calcium sulfate is cements with fineness values of 350 m2/kg. At ages greater
normally chosen to optimize strength and other properties than 2 to 3 months, the strengths of normal-fineness cements
under the most common conditions of curing and use. become greater than the strengths of high-fineness cements
The loss on ignition of a cement is generally an indicator if moist curing is continued so that hydration may proceed.
of the amount of water, carbon dioxide, or both, that are If the cement content is held constant, very high fineness
chemically combined with the cement. Strengths tend to may increase the water requirement to such an extent that the
decrease with increasing ignition loss. Combined water in early strength benefits are partially offset by the higher w/c
a cement may have come from clinker that has been stored required for workability and placement. This can typically
outside. The presence of combined water produces a spurious be addressed with adjustments to the mixture proportioning.
increase (Blanks and Kennedy 1 95 5) in the indicated air The strength characteristics of portland cements are also
permeability fineness (Blaine method, ASTM C204), and affected by the heating and cooling rate conditions in the kiln,
to maintain the same actual fineness, the cement should be the incorporation of trace elements into the crystal structure,
ground to a significantly higher fineness. and the particle size distribution. For these reasons, there
Small amounts of sodium and potassium from the fuel, are moderate differences in cements of apparently similar
raw materials, or both, are normally present in portland composition and fineness.
cements. The effects of these on strength are not well under­ When compared at constant w/c by mass and comparable
stood. Some tests have indicated that potassium causes small fineness, the strengths of portland cements are usually higher
increases in strength in the first few days but has little effect than the strengths of blended cements at ages of 7 days or
on later-age strength. Yet, other tests indicate sodium seems less, and lower at ages of28 days or more. Blended cements
to have little effect on strength in the first few days, but are frequently ground finer than portland cements to make
causes a moderate decrease in strength at ages greater than 1 their early strengths more comparable with those of portland
month (Lea 1 998). cements (Neville 1959).
Magnesium oxide is usually present in portland cements
because of its unavoidable occurrence in the raw materials. In 7.4-Volume stabil ity
the proportions usually present, it has little effect on strength. Concrete is subject to changes in volume both during the
ASTM C 1 50/C 1 50M limits magnesium oxide to a maximum setting and initial hardening process and after it has gained
of 6.0 percent to avoid the possibility of unsoundness. significant strength (Kosmatka and Wilson 20 1 1 ). Freshly

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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
mixed concrete is subject to volume changes from tempera­
ture and moisture changes, including absorption, bleeding,
hydration reactions, and drying. Bleeding is the segregation
of water at the surface of concrete or under aggregate parti­
cles and horizontal reinforcing bars due to the settlement of
solid ingredients. The amount of bleeding is greatly influ­
enced by the slump, w!cm, grading, amount of fines in aggre­
gates, and other variables relating to the proportioning of the
concrete. Cement properties that tend to decrease bleeding
include increased fineness (particularly increased amounts
of the smallest sizes present at the cement), increased alkali
content, and increased C3A content (Neville 1 963 ; Kosmatka
1 994).
The normal cement hydration reactions occurring during
setting and hardening tend to produce small changes in the
volume of the hydrating paste. Because the volume of hydra­
tion products is less than the volume of water and cement
that react to form them, there is a net decrease in volume that
is referred to as chemical shrinkage. After initial set, hydra­
tion reactions continue, resulting in slight bulk shrinkage
and, if the water content is low enough, voids in the micro­
structure through self-desiccation. Autogenous shrinkage
is chemical shrinkage that occurs after initial set, exclu­
sive of the voids formed. Figure 7.4 provides a schematic
diagram showing the relationships between the various
volume changes. Except in the case of expansive cements
or concretes with low w!cm (less than approximately 0.30),
these volume changes have not been shown to be of signifi­
cance to concrete performance. Concretes made with high
cement contents, low w/cm, and high-fineness cements tend
to exhibit higher chemical shrinkage. There is evidence that
use of portland-limestone cements can have lower autog­
enous shrinkage (Bucher et al. 2008) despite their higher
fineness, possibly due to a broader particle size distribution,
refinement of the pore structure, or both. Other significant
concrete factors to also consider may include aggregate
type, gradation, and SCM content and type.
Cements that contain significantly larger-than-normal
quantities of free lime (calcium oxide) or periclase (magne­
sium oxide) could have a potential for detrimental expansion
due to the hydration of these phases. Cements that exhibit
such detrimental expansion are said to be unsound. Unsound­
ness is very rare in present-day commercial cements because
a tendency to unsoundness can be detected readily by the
autoclave expansion test, ASTM C 1 5 1 /C 1 5 1 M, which is
carried out routinely in the testing of cements.
Cements can have significant effects on the drying
shrinkage of concrete. The effects are minimized if the
cement is maintained at an optimum sulfate content (Alex­
ander 1 972; Hobbs 1 977; Lerch 1 946; Mardulier et al.
1 967). In tests of a large number of cements, there was no
clear separation in shrinkage potential of different types
of cement. Shrinkages of different cements ranged from
approximately 25 percent less than the median value to 40
or 50 percent above the median. Cements with S03 contents
0.5 percent less than optimum could have drying shrinkages
increased by 1 0 to 24 percent (Alexander 1 972). Optimum
sulfate content increases with concrete temperature and may
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19
Chemical
shrinkage
(absolute
volume
reduction)
Unhydrated
cement
and
water
Paste Paste at Paste after Paste after
as cast initial set final set final set
Fig. 7. 4-Chemical shrinkage and autogenous shrinkage
volume changes offresh and hardened paste. Not to scale
(Kosmatka and Wilson 2011).
increase when certain water-reducing admixtures are used
(Verbeck 1 966); expansions, however, may increase with
curing temperatures above 1 5 8°F (70°C) (Taylor 1 997). An
increase of 1 .0 percent by mass in sulfate content results
in an increase of approximately 73 ft2/lb ( 1 5 m2/kg) in air­
permeability fineness (ASTM C204). This air-permeability
fineness increase occurs due to the easier grindability of the
calcium sulfate source as compared to that of clinker during
the cement manufacturing process. Calcium sulfate gener­
ates more surface area. The sulfate phase or phases in a
cement may also affect the optimum sulfate content. Sulfate
present in the clinker as alkali sulfate-for example, sodium
sulfate (Na2 S04), potassium sulfate (K2 S04), or aphthitalite
([Na, KhS04)-behaves somewhat differently from sulfate
present as interground gypsum or other forms of calcium
sulfate (Taylor 1 997).
7.5-Eiastic properties
The modulus of elasticity of concrete is a function of the
modulus of elasticity of the concrete components and the
volume concentrations of each. Several equations have been
proposed to express the relationship. The relationship has
been detailed by Hansen ( 1 960), Counto ( 1 964), and Popo­
vics ( 1 980).
Hydrated portland cement has a nearly constant modulus
of elasticity regardless of cement composition. Thus, the
modulus of elasticity of cement paste is a function of the
degree of filling of the space available to the hydration
product. The greater the degree of filling, the higher the
modulus. The degree of filling increases as the w/c decreases
and the degree of hydration increases. For the practical range
of w/c and for the ages for which the information is normally
desired, the modulus of elasticity of cement paste is between
1 and 2 x 1 06 psi (7 and 14 GPa). Because these values
are below those of most normalweight aggregates and the
volume concentration of aggregate is usually three to four
times that of cement paste, aggregate is usually the prin­
cipal determinant of modulus of elasticity of concrete. The
minor effect of cement is to increase the modulus of elas­
ticity of concrete as w/cm decreases and degree of hydration
cCiC'iJ
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20 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)

increases, and to reduce the modulus as the volume concen­

tration of cement paste increases. 1 00

7.6-Creep
80
Creep is the time-dependent deformation due to sustained .!!!
E
load. The constituent of concrete that creeps is the hydrated M

cement paste. The property of cement paste that most affects 6 60

creep is its porosity. Cement pastes of lower porosity and �
lower w/cm impart lower creep to the concrete. There is :0
"' 40
Q)
virtually no direct effect of cement composition except that E
cements with gypsum contents significantly below optimum Qi
a..
may demonstrate increased creep (Neville 1 959). For more 20
information on the definitive relationship between w/c and
creep, refer to Neville and Meyers ( 1 964) and ACI 209R.
0
0% 1 0% 20% 30% 40%
7. 7-Permeabil ity Capillary porosity, %
The permeability of concrete depends on the permeability
of the paste, as well as that of the aggregate and the rela­ Fig. 7. 7a-Relationship between coefficient ofpermeability
tive proportions of each. It also depends greatly on placing, and capillary porosity for portland-cement pastes (Powers
finishing, and curing procedures, particularly consolida­ 1 958).
tion (Grube 1 985). Permeability of concrete to liquid water
or water vapor is not a simple function of its porosity, but 140
depends also on the size, distribution, and continuity of the
pores in both the cement paste and the aggregates. There are 1 20
two kinds of pores in cement paste. Gel pores are inherent
.!!!
in the structure of C-S-H and constitute approximately 28 E 1 00
percent of its volume. These pores are between 6.0 x 1 0-8 ;!:
6
and 1 2 x 1 0-8 in. ( 1 .5 and 3.0 nm) in diameter and contribute 80
relatively little to permeability. Capillary pores are the spaces �
:0
remaining after cement particles react and can range from "' 60
Q)
0 to 40 percent of the paste volume, depending on the w!c E
Qi
a.. 40
and extent of hydration. These are larger than gel pores­
approximate diameters of 0.000004 in. ( 1 11m), irregularly
20
distributed throughout the cement paste-and are generally
responsible for its permeability. For a given w/c, Powers et
0
al. ( 1 954) found that cement phase composition and fineness 0.2 0.3 0.4 0.5 0.6 0.7 0.8
of cement have relatively little impact on total porosity and water:cement ratio
permeability of concrete, although coarse cements tended
to produce pastes with higher porosities than finer cements. Fig. 7. 7b-Relationship between coefficient ofpermeability
There is also some evidence that the permeability of port­ and w/c for mature portland-cement pastes (Powers et al.
land-cement pastes increases with the curing temperature 1 954).
(Bakker 1 983 ; Roy and Goto 1 9 8 1 ).
or calcined natural pozzolan, fly ash, or slag cement have
As hydration progresses, permeability decreases. The
increased resistance to the movement of water and pene­
flow of water through concrete is fundamentally similar to
tration of ions than comparable paste and concrete made
flow through any porous medium. Powers ( 1 958) presented
with portland cement (Hooton 1 986; McGrath and Hooton
a relationship between permeability and capillary porosity
1 997; Garboczi and Bentz 1 992; Martys and Ferraris 1 996;
of cement paste, as shown in Fig. 7.7a. For pastes hydrated
Halamickova et al. 1 995 ; Thomas 20 1 3a,b).
to the same degree, the permeability decreases as the w/c
decreases. This is shown in Fig. 7.7b, which presents data
7.8-Corrosion of embedded steel
obtained by Powers et al. ( 1 954) for pastes with 93 percent
For portland cements, the cement type has only a minor
of the cement hydrated.
effect on the level of protection of the steel. Cements with
Air entrainment might be expected to increase the perme­
high alkali contents have shown superior performance in
ability of concrete. However, because air entrainment
chloride environments. According to Verbeck ( 1 968), the
improves workability, reduces the mixing water required,
higher the C3A content, the greater the amount of chloride
and reduces bleeding, the overall effect of air entrainment
ion that can be precipitated as calcium chloroaluminate,
will usually be reduced permeability. There is evidence
and thus be rendered innocuous, relative to steel corro­
from laboratory experiments that paste and concrete made
sion. For this reason, Type V cements with their low C3A
with blended hydraulic cement containing silica fume, raw

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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEM ENTS (ACI 225R-16)
contents make concretes that are less resistant to chloride­
induced steel corrosion (Rasheeduzzafar et a!. 1 992). There
is substantial evidence that, when compared with portland
cements only, blended cements with appropriate quantities
of pozzolans or slag cements have reduced permeabilities
to chlorides (Bakker 1 983; Short and Page 1 982; Smolczyk
1 984). Dense concrete of low permeability with adequate
cover and low chloride levels should be used to provide
protection against corrosion. Use of epoxy-coated reinforce­
ment or corrosion-inhibiting admixtures may be needed to
enhance corrosion protection. For severe exposure condi­
tions, refer to ACI 222R and ACI 20 1 .2R.
7.9-Resistance to freezing and thawing
As discussed in ACI 20 1 .2R, the vulnerability of concrete
to be damaged by freezing and thawing depends on whether
it becomes critically saturated with water. This, in turn, is
a function of the pore structure of the paste and exposure
to conditions that provide sufficient access to moisture.
The content and composition of the cement or cementi­
tious materials used in a concrete mixture will influence the
rate of hydration that, in turn, will affect the strength and
permeability of the concrete at the time freezing and thawing
occurs.
7.1 0-Resistance to chemical attack
Portland cement-based concretes are generally resistant to
chemicals whose pH is higher than approximately 6. There
are, however, notable exceptions and qualifying conditions.
ACI 20 1 .2R summarizes factors leading to increasing or
decreasing the rate of deterioration. Sulfate attack (Table
7. 1 0) is of special importance because of the widespread
occurrence of sulfate in soils, seawater, groundwater, and
chemical process effluents. Due to the tendency of high­
C3A portland cements to be susceptible to sulfate attack, the
lower-C3A portland cements (ASTM C 1 5 0/C 1 50M Types II
and V) are often required for concretes to be used in sulfate
environments (Tuthill 1 936). Moderate-sulfate-resistant and
high-sulfate-resistant blended cements use the chemical and
physical properties induced by pozzolans and slag cements
to help resist sulfate attack.
In addition, high-C3A cements, when combined with suffi­
cient replacements of pozzolans or slag cements, can also
provide moderate- or high-sulfate-resistant cementitious
systems. ACI 3 1 8 permits use of such combinations of mate­
rials, provided they meet the expansion limits when tested
by ASTM C l 0 1 2/C l 0 1 2M.
The proper use of a sulfate-resistant cement or a combina­
tion of cementitious materials with demonstrated equivalent
performance, along with a low w/cm, proper mixture propor­
tioning, and good placing and curing practices, provide an
effective means to sulfate resistance in a concrete system
(Stark 2002). Guidance on selecting cementitious materials
and w/cm with respect to various sulfate exposures is provided
in ACI 20 1 .2R. More detailed information about the response
and protection of concretes to the various types of chemical
attack is available in Detwiler and Taylor (2005), Kerkhoff
(200 1 ), Panarese (2005), ACI 20 1 .2R, and ACI 5 1 5.2R.
American Concrete Institute- Copyrighted© Material- www.concrete.org
21
Table 7.1 0-Cements for use i n concretes exposed
to sulfates in soil or water
ASTM C150/ ASTM C595/ ASTM C1157/
CI SOM C595M C1157M
IP(MS)
Moderate sulfate
II, II(MH) IS(<70)(MS) MS
exposure
IT(MS)
IP(HS)
High sulfate
v IS(<70)(HS) HS
exposure
IT(HS)
Calcium-aluminate cement may be required where
concrete is to be used in a particularly aggressive environ­
ment in the pH range from 3.5 to 6, as calcium-aluminate
cement concretes (Appendix A) resist a number of agents
that attack portland-cement concretes.
7. 1 1 -Resistance to high tem peratures
If properly cured and dried, normal portland-cement
concretes can withstand temperatures up to 2 1 2°F ( 1 00°C)
with little loss of strength. They can also withstand tempera­
tures up to approximately 570°F (300°C) for several hours
with only a slow loss of strength due to partial dehydration
and alteration of the calcium silicate hydrate. If resistance
to higher temperatures is needed, the properties of both
the cement and the aggregate should be considered. Port­
land cements are being used in applications to temperatures
as high as 2000°F ( 1 1 00°C) with high-temperature-stable
aggregates in noncyclic (repeated heating and cooling) oper­
ations. For the most demanding applications, high-purity
calcium-aluminate cements (Appendix A) are combined
with selected refractory aggregates to produce refractory
concretes suitable for use at temperatures up to 3400°F
( 1 870°C). ACI SP-57 (American Concrete Institute 1 978)
and Lankard ( 1 982) provide more information on refractory
concretes using hydraulic-cement binders. For determining
the fire endurance of concrete structures, refer to ACI 2 1 6. 1 .
A decrease in strength and toughness of ordinary concrete
may occur during the fire, as well as during and after cooling
of the structure. Caution is required regarding the residual
strength of concrete in structures that have been exposed to
incidental fire.
7. 1 2-Cement-aggregate reactions
In dense concrete, the hydration of cement develops
strong adhesion bonding to the surfaces of aggregate parti­
cles. Where the pore fluid touches siliceous aggregate parti­
cles, calcium alkali-silica hydrates may form as the bonding
material. Limestone particles may develop strong bonding
by crystal growth on other crystals, resulting in similar struc­
tural orientation between the calcium hydroxide and the
limestone. These bond reactions constitute the reasons why
concrete can be made to be a monolithic material.
The term "alkali-aggregate reaction" (AAR) is used for
alkali-silica reaction (ASR) and alkali-carbonate reaction
(ACR). These reactions with aggregate particles can cause
fracturing and sometimes expansions or warping of field
concrete, as well as of test specimens of concrete or mortar.
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22 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
Table 7. 1 2 . 1 -Some reactive substances found in aggregates
Reactive substance Chemical composition
Opal Si02·nH20
Chalcedony Si02·H20 and air
Quartz Si02
Cristobalite Si02
Tridymite Si02
Glass from acid to intermediate
Siliceous, with smaller proportions of Ah03,
rocks, and their cryptocrystalline
Fe203, alkaline earths, and alkalies
devitrifcation products
Siliceous, with smaller proportions of alkalies,
Synthetic" siliceous glasses
alumina, with or without other substances
Some reactive rocks
Opalinechert, chalcedonic chert, quartzosechert, opalinelimestones and dolomites, cherty carbonate rocks; rhyolites, dacites, andesites, and their tuffs;
opalineshales; phyllites and metamorphic subgraywackes containing strained quartz, argillites, quartzites, schists, granite gneiss, sandstones, and shales.
SynthetiC glass IS found m aggregates downstream from c1t1es and towns.
Aggregate constituents readily decomposed by oxidation
in the presence of water include a number of unstable sulfides
of iron often associated with coal, lignite, and black shale.
Their presence in aggregates may cause severe acid attack
on concrete, and also expansive reactions due to formation
of excessive amounts of calcium sulfoaluminate, commonly
referred to as ettringite. Aggregate constituents or contami­
nants that hydrate include anhydrite, periclase, quicklime,
and portland-cement clinker. In sand and coarse-aggregate
size ranges, some of these reactions may cause expansions
to occur.
7.12.1 Alkali-silica reactions-The most predominant
cement-aggregate reactions, from the standpoint of poten­
tial for damage to mortar or concrete in service, are those
with alkalies. Of these, the best-known and longest-studied
is ASR. This reaction results from the presence of pore fluids
with pH values of 1 3 or higher in the pores of the concrete.
Beyond 1 day, the pore solution of concrete is dominated
by sodium and potassium hydroxides. The concentration of
these alkali hydroxides and, hence, the pH of the pore solu­
tion, generally increase as the alkali content of the cement
and the cement content of the concrete increase. Greater
concentration in the alkalinity (pH) of the pore solution
increases the solubility of reactive silica that may be present
in some aggregates. The high pH renders the siliceous
aggregate particles more soluble by the alkali-hydroxide.
The product of the ASR may be a hydrous calcium-alkali­
silica gel that is expansive only to a limited degree, or a
hydrous alkali-silica gel that may imbibe water and expand
much more and disrupt concrete. This is dependent on the
hydroxyl-ion concentration, the presence and proportion
of reactive aggregate particles and their physical charac­
teristics, the w/c, and the cement in the concrete. Elevated
temperatures, as in summer seasons and hot climates, will
further suppress the calcium hydroxide solubility.
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Physical character
Amorphous by light microscopy; includes a wide range of discolored
cristolbalite-tridymite stacking; micromorphology usually spherical
when known (precious opal is made up of spherical bodies with
ordered domains)
Microcrystalline to cryptocrystalline, often fibrous
a) Microcrystalline to cryptocrystalline
b) Crystalline but intensely strained or fractured and inclusion-filled,
or both
Crystalline
Crystalline
Glass or cryptocrystalline materials as the matrix of volcanic rocks or
fragments in the tuffs
Glass
The use of cements with an equivalent alkali content of
not more than 0.60 percent have been shown to control
many known reactive aggregates. However, using only
cements with alkali contents not more than 0.60 percent may
not always effectively control expansion due to ASR. ACI
20 1 .2R, ASTM C 1 778, and AASHTO PP65 provide guid­
ance on methods for determining aggregate reactivity and
the selection of appropriate measures to minimize the risk of
damaging expansion in concrete when alkali-silica reactive
aggregates are used. Finer-sized siliceous particles found
in pozzolans and slag cements consume calcium hydroxide
and concurrently sequester alkali-hydroxides. This results in
a less permeable concrete matrix and helps prevent delete­
rious reactions with aggregate particles.
Table 7. 1 2 . 1 provides information on reactive substances
found in aggregates. It indicates that aggregate containing
opal, chalcedony, quartz, cristobalite, tridymite, and some
natural and synthetic sources of glass may be reactive. It
does not say whether the reaction will occur as a harmless
modification or cause damage in days, months, or 1 to 50
years after a structure is built. Low-silica aggregate, such
as most basalts and diabases; limestones without siliceous
inclusions; and quartz sand are usually not reactive.
Although opal is not a common constituent of aggregates,
it has been used extensively in research on ASR. The first
extensively studied case of ASR involved an aggregate
called siliceous magnesium limestone that contained opal
as its alkali-reactive ingredient. Small opaline shale grains,
common in some aggregates in the Midwest United States,
create small popouts on finished flatwork in 24 hours. When
all of the reactive aggregates that have affected structures
are considered, more behave quite differently from opal than
behave like it. The original period of investigation of ASR,
from 1 940 to approximately 1 960, focused on many exam­
ples of rapidly reacting aggregates, mostly from the Western
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
United States, and led to the tentative conclusion that rapid
reaction will usually take place if the aggregate is reactive
and the alkali content of the cement is high enough. Further
information can be found in Famy and Kerkhoff (2007) and
ASTM C 1 778.
Since that time, more and more structures containing
aggregates with fairly low rates of expansive reactivity have
been found that were not recognized as having problems
involving ASRs until the structures were over 30 years old.
These reactive rock types include certain granite gneisses,
schists, phyllites, quartzites, argillites, and greywackes,
all of which contain microcrystalline and strained quartz
(Dolar-Mantuani 1983 ; Buck 1 983 ; ACI 22 1 . 1 R). For more
on alkali-reactive aggregates, refer to ACI 221 . 1 R.
7.12.2 A lkali-carbonate rock reactions-The second cate­
gory of potentially damaging AARs is the alkali-carbonate
rock reaction. Preventive measures such as use of blended
cements or low-alkali cements for ASR are not effective
in mitigating ACR. Alkali-carbonate-reactive aggregates
should be avoided for use in concrete. Refer to ACI 22 1 . 1 R
for further information. The phenomenon is generally asso­
ciated with rocks that are not approaching pure calcium
carbonate or pure dolomite; rather, they consist of crystals
of the mineral dolomite in a fine-grained matrix of clay and
calcite. These rocks may react by decomposition of dolo­
mite to form magnesium hydroxide and calcium carbonate.
ASTM C586 can be used to identify carbonate rocks capable
of expansive reaction with alkalies. Such tests should be used
to supplement data from field service, petrographic exami­
nation, and tests of aggregate in concrete. ASTM C 1 1 05 and
CSA-A23.2-27A- 14A have been developed to test aggregate
in concrete.
7.1 3-Color
The most critical aspect of concrete color is usually its
uniformity. However, the exact color of a concrete is some­
times important to an architect or owner for its contribution
to the esthetic value of a structure (Gage 1 970). Variations
in the color of concrete due to the cement can be minimized
by purchasing the cement from a single plant and strictly
adhering to uniform quality-control procedures for propor­
tioning, mixing, placing, forming, and curing the concrete.
The color of a concrete depends on, among other factors,
the cement and other materials used. Cement color reflects
chemical composition and processing conditions. Usually,
cement colors vary from white to shades of gray and
brown. Color differences are often discernible between
cements manufactured from different plants. The influence
on concrete color from the variation in the color of cement
from a single plant is typically outweighed by concrete
finishing and curing practices, w/cm, and use of supplemen­
tary cementitious materials (SCMs).
White cements contain very little iron or other transition
metals-for example, chromium, manganese, and vana­
dium; each transition metal makes its own contribution to
cement color. For example, experimental cements made with
unusually large quantities of chromium, but with no other
transition metal present, are green. The common gray and
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23
brownish colors of commercial cements are primarily due
to the iron compounds in them, although small quantities of
other transition metals also have an effect on them. Concretes
made using slag cement can initially appear to have a dark
green color, but this fades as the surface oxidatizes and typi­
cally becomes whiter than a portland-cement concrete. This
is discussed in ACI 233R. Pigments are sometimes added to
produce colored cements (ASTM C979/C979M).
The contribution of cement color to the color of the
concrete depends on the pigments, fly ash, sand, or other
fine particles present. Variations in color and grading of all
fine particles can have an effect on concrete color unifor­
mity. Other factors that could cause variations in concrete
color are mixture constituents and proportions, moisture
movement, curing conditions, presence of efflorescence, and
surface carbonation. For more information on these topics,
refer to ACI 302 . 1 R and ACI 308R.
7.13.4 Effiorescence-Efflorescence is a deposit some­
times seen on surfaces of concrete or masonry. On concrete,
the deposits are generally calcium carbonate, which is not
readily soluble in water. Occasionally they contain sodium or
potassium sulfate or bicarbonate, which are easily dissolved
in water. Some of the abundant calcium hydroxide produced
by normal cement hydration reactions is brought to the
surface, deposited, and converted to calcium carbonate by
the carbon dioxide in the air (Ritchie 1 960; Taylor 1 964).
Incidence of efflorescence is regulated largely by the chem­
ical composition of the concrete, the permeability and texture
of the concrete surface, and the rate of surface drying. Use
of SCMs can provide further resistance to efflorescence by
reacting with calcium hydroxide and reduce permeability of
concrete and masonry.
CHAPTER 8-CEM ENT STORAGE A N D DELIVERY
The performance of cement in concrete can be affected
by the conditions under which the cement has been stored
and its handling during delivery. These effects are reviewed
to complete the discussions of factors affecting the perfor­
mance of cements. This chapter relates to the handling of
cement during delivery. Requirements for the protection of
workers is also reviewed.
8.1 -Storage
Cement can be stored for an indefinite period of time as
long as it is protected from moisture. This includes the mois­
ture present in the air. Storage life can be more limited in
small bins under conditions where moisture condenses on
the inside of the bins, but satisfactory storage for several
months is not unusual. The storage life of cement in paper
bags could be more limited.
Hard lumps are evidence of reaction with moisture. If the
lumps are screened out, the remaining cement is normally
satisfactory for use. Measures for minimizing the likelihood
of warehouse set of packaged cement include the following:
a) Use stock on a first-in, first-out basis
b) Keep storage areas dry
c) Store bags on pallets above ground
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24 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
d) Store bags under a cover that will protect them from
moisture
Soft lumps can occur in the lower bags in a high stack
simply from the pressure of the bags above. Rolling the bags
a few times normally breaks up these lumps. Measures for
minimizing the formation of hard lumps during bulk storage
and during transit include the following:
a) Periodically inspect the loading hatches of bulk carriers
for watertightness
b) Keep loading hatches closed when not in use
c) Compressed-air transit systems should have water traps
and, in areas of extremely high humidity, the air lines should
be equipped with air driers
d) Storage bins should be inspected periodically for
possible water leaks
Flowability problems can be caused by the formation of
syngenite crystals in storage, and is characterized by soft
lumps that break under light finger pressure, reduced flow­
ability, or both. This condition can develop within a few
days after production. Once the rigidity of the bulk material
has been reduced, the flowability of the material is typically
restored. The potential for reoccurrence of the flow problems
is low. The tendency of cements to form syngenite depends
on several factors, including chemical composition, storage
temperature, grinding temperature, and the moisture avail­
able during grinding. The effect of storage on the quality of
cement is generally negligible, but it can cause false setting
and a slight loss in strength development (Richartz 1 973 ;
Thiesen and Johansen 1 975).
8.2-Pack set (sticky cement)
Pack set of a cement material is evidenced by a higher­
than-normal resistance to the initiation of flow and is deter­
mined by ASTM C 1 565 . Pack set can be caused by mechan­
ical compaction or electrostatic attraction between particles.
The use of an appropriate amount of processing additions
that comply with ASTM C465 during the finish grinding
process will typically eliminate the occurrence of pack set.
Most often, a relatively small amount of mechanical effort
will overcome the resistance to flow
The generally accepted explanation of pack set is that the
surfaces created during grinding of portland-cement clinker
have areas with unsatisfied electrical forces. The active
surfaces cause interparticle attraction, resulting in agglom­
eration and pack set (Hansen and Offutt 1 969; Mardulier
1 96 1 ). The mechanism of pack set is different from that of
warehouse set, which, as mentioned previously, is a loss of
flowability caused by partial hydration of cement.
Most grinding aids are substances adsorbed on the
surfaces of the cement particles. They reduce the surface
energy so that no bonds remain to attract other particles and
cause agglomeration and pack set. In addition to inhibiting
pack set, grinding aids prevent ball coating and increase mill
efficiency.
ASTM C 1 50/C 1 50M permits the use of grinding aids
in the manufacture of portland cement, provided that such
materials in the amounts used have been shown not to be
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harmful to the quality of the finished cement. This is demon­
strated by tests in accordance with ASTM C465 .
8.3-Del ivery
Cement is available as a bulk powder or in paper bags.
Bulk powder is shipped using closed tanker trucks, covered
rail hopper cars, air-unloading tank cars, covered barges, or
ships with closed compartments. Occasionally, bulk cement
is delivered to very remote sites in large rubber containers
3 3
(approximately 1 yd [ 1 m ] in size).
8.4-Contamination and handling
Most contamination of cement occurs during shipping and
handling that is generally caused by failure to clean trucks
and railcars in which it is to be shipped (Kleinlogel 1 950).
Very small amounts of sugar and starch can cause signif­
icant retardation, as can small amounts of lead, zinc, and
copper compounds. Ammonium fertilizers in cement will
generate ammonia gas when the cement is in contact with
water. The smell of ammonia is unpleasant, even though the
amount of fertilizer could be small and not harmful. With
ammonium sulfate contamination, the sulfate content of
the concrete could be increased to a level at which unsound
concrete might result. Among other ammonium compounds,
phosphates can cause retardation and nitrates could promote
corrosion of reinforcing steel.
Contamination with dead-burned dolomite, which has a
slow reaction rate with water and is used in the manufacture
of refractories, can cause popouts or even unsound concrete.
Contamination as low as 0 . 1 percent by volume of concrete
can cause popouts, and an increase to 0.3 percent can result
in internal failure when the concrete is exposed to water
(Scanlon and Connolly 1 994).
Trace amounts of some contaminants could pose no
problems. They may be tolerable in noncritical concrete if
the concrete sets and gains strength in a normal manner. If
there is any doubt, the contaminant should be identified to
make sure that it will not cause problems with durability or
strength, and that the concentration of it is shown as minimal.
Despite the fact that small amounts of some contaminants
are tolerable in noncritical concrete, efforts should be made
to prevent contamination of it and cement as well.
Pneumatic transport of portland cement could cause
cement particle agglomeration, which is not normally a
problem unless the concrete mixing time is 3 minutes or less.
This particle agglomeration may be the result of electrostatic
attraction or particle hydration from water condensed out of
the compressed air, or is used in the transfer of cements, both
within cement plants and terminals and in delivery to mixers
in concrete plants. The amount of aeration in these processes
is normally so small that cement properties are not impaired.
Air handling frequently increases the apparent Blaine fine­
ness, though other properties are not affected. A fineness test on
a field sample may be 50 or 1 00 ft3/lb ( 1 0 or 20 m2/kg) higher
than that determined by the manufacturer during grinding.
Aeration for long periods should be avoided as it can induce
slump loss, increase water requirement, and increase false
set. Cement in paper bags is subject to aeration. As a conse-
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
quence, false set is not uncommon in bagged cement, and
can occur long before there is evidence of hard lumps.
The top 1 to 2 in. (25 to 50 mm) layer of cement in a bulk
truck or railroad car is aerated by the air above it. To mini­
mize this effect, cements should be transported and stored in
full, closed containers. A sample skimmed from the top could
show false set that is atypical of the shipment as a whole.
When the car or truck is unloaded and the top layer mixed
with the underlying cement, the cement usually performs
normally. For this reason, cement should be sampled by
digging below the surface layer.
8.5-Worker protection
Workers should protect their skin and eyes from cement and
mixtures containing cement, as they can cause serious derma­
titis and eye injuries. Skin contact with freshly mixed cement
paste, mortar, concrete, or grout should be avoided. When
contact occurs, skin areas should be washed promptly with
water. If any cement or cement mixture gets into the eyes, they
should be flushed immediately and repeatedly with water. The
person should receive prompt medical attention.
CHAPTER 9-SAM P L I N G AND TESTING O F
HYDRAU LIC C E M E NTS F O R CONFORMANCE TO
SPECIFICATIONS
Preceding chapters discussed factors affecting the perfor­
mance of cements in concretes; this chapter will look at the
main approaches that are customarily used for acceptance
testing of cements. To apply this knowledge, the user should
know if the cements being purchased meet the appropriate
specification limits and whether, within the specification
limits, a satisfactory degree of uniformity is being main­
tained. This chapter discusses the sampling and testing of
cements to show their conformance to specifications and
the magnitude of batch-to-batch variations. Guidance is
provided as to the types of information available from
the manufacturer if a sampling and testing program is not
conducted.
Most building codes and job specifications require cement
that meets the requirements of an applicable material speci­
fication such as ASTM C 1 5 0/C 1 50M, ASTM C595/C595M,
ASTM C l l 57/C l l 57M, AASHTO M 85, AASHTO M 240,
or CSA-A3000. ASTM C l 83/C l 83M is the standard proce­
dure for acceptance sampling and testing.
Although compliance with specification requirements
can be assured by sampling and testing by the producer,
the purchaser, or purchaser's representative, only a few
purchasers sample or test cement. Most often, the purchaser
accepts the results supplied by the producer after proper
certification or laboratory accreditation. There are several
reasons for this. First, complete tests are considered unduly
expensive by all but a few large specifiers or purchasers.
Second, few commercial testing laboratories have a suffi­
cient volume of cement testing to maintain an adequately
skilled staff to be able to offer competent, timely, cement­
testing services, whereas cement companies should maintain
competence in cement testing at all times. Third, it is usually
impractical to provide sufficient cement storage capacity
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25
to permit completion of tests requiring many days, such as
28-day strength or heat of hydration, before the cement is
used in concrete. As a result, almost all cement testing is
done by cement manufacturers. Among purchasers, only a
few large users, such as the U.S. Army Corps of Engineers
and state transportation departments, regularly test cement.
Tests carried out in the cement-plant laboratory are likely
to include chemical analysis (ASTM C l l 4), autoclave
expansion (ASTM C l 5 1 /C l 5 1 M), surface area (ASTM
C204), mortar cube strengths (ASTM C l 09/C l 09M), and
setting time (ASTM C l 9 1 or C266) . Some purchasers use
surface area measurements as an indication of uniformity.
9 . 1 -Cement m i l l test report
The cement producer tests the cement, generally as it is
being placed in a silo for shipment, and furnishes a mill
test report. The significance of the test data given in a mill
test report varies for each plant. In some cases, the data are
typical values that can be expected to be representative of
cement shipped from a given bin or silo. In other cases, a
composite sample or series of grab samples is collected from
the mill stream during the time the silo or bin is being filled,
and the data given in the mill test report are those obtained
by testing the composite sample. The sample can also be
obtained during transfer, or from storage by means of a tube
sampler. Because of such differences, there is usually no
assurance that the cement being shipped will have exactly
the same physical and chemical characteristics as given in
the mill test report.
The principal purpose of the mill test report is to certify
that the cement in question complies with either ASTM
specifications or others as required by contract and to
provide typical test data for the cement. The purchaser relies
primarily on the mill test results, although the purchaser may
occasionally take samples that are held for possible testing
if there is a change in the performance, color, or some other
characteristic of the concrete in which the cement was used.
The purchaser may require the producer's testing labora­
tory to have established its credibility by participation in
the reference sample and laboratory inspection programs
of the ASTM International's Cement and Concrete Refer­
ence Laboratory (CCRL). Another tool that can be used by
the purchaser to evaluate cement strength uniformity from
a single source is ASTM C9 1 7. The ASTM C9 1 7 report is
a statistical summary of ASTM C l 09/C l 09M compressive
strength tests on randomly sampled shipments.
9.2-Sealed si los
In the past, cement for special jobs was often placed in
silos reserved for a single user. After sampling and testing
by the user, the silo was sealed and reserved for the user's
exclusive use. In recent times, this practice has become rare,
as it requires special silos at the cement plant and reserved
bins at a concrete plant. Because it is unrealistic to expect
28-day results prior to shipment and it is often difficult for
a cement manufacturer to provide silo storage sufficient to
obtain 7-day results prior to shipment, the quality manage­
ment approach described in 9.4 is increasingly being used.
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26 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)

Fig. 9. 4. 1-Flowchart of a portland cement manufacturing operation showing points from

which quality-control samples might be taken by the producer.

9.3-Cement certification Table 9.4.1 -Example of a sampling and testing

The current trend with state transportation departments is schedu le
to accept certification by the cement producer that the cement
Sample
complies with specifications. As will be discussed in 9.4, the location
.
Sample Test Frequency
cement producer has a variety of types of information avail­
Limestone being
able, including production and quality-control records. These I C02 content ! /shift
fed to raw mill
records could permit conformance certification with minimal
H20 content (if wet
additional testing of the product as it is shipped. 2
Clay being fed
process) percent finer than I!shift
to raw mill
No. 200 (75 �m) sieve
9.4-Qual ity management
Raw mill C02 content 2/shift
Some federal and other government agencies operate 3 discharge and
using a cement quality management approach based on blending tank H20 content 2/shift
statistical analysis of cement company test results coupled C02 content 2/shift
with periodic sampling and testing.
H20 content (if wet
9.4.1 Testing by producer-Testing performed by the process)
2/shift
Kiln feed (from
cement producer during various phases of production varies 4 blending silo or Percent finer than No. 50
greatly in frequency, depending on uniformity of raw mate­ tank) (300 �m) sieve
2/shift
rial; uniformity of fuel, particularly coal; and the physical
Percent finer than No. 200
plant facilities. Generally, composite samples of each 2/shift
(75 �m) sieve
cement type are analyzed for chemical and physical proper­
Free CaO 2/shift
ties. Upon request, the mill test report can be furnished to
5 Clinker Complete chemical
the purchaser. I!shift
analysis
Figure 9.4. 1 shows a cement manufacturing flowchart.
The points at which quality-control samples are often taken Free CaO I!shift
are indicated by numbers. Table 9.4 . 1 shows an example of so3 4/shift
a sampling and testing schedule. Fineness (air permeability) 4/shift
9.4.1.1 Sampling point Each sampling point listed in
-
6 Cement
Complete chemical
Table 9.4. 1 is described in the following list, which refer to I!day
analysis
the sampling locations of Table 9.4. 1 .
Complete physical tests ! /day
a. Sampling of the various individual raw materials that
are to be blended. Retain sample for 1 20
7 Cement -

days
"Refer to F1g. 9.4. 1 .

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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
b. Checking of the ground and homogenized blend of
material for bulk chemical composition and fineness prior to
burning; this blend can be contained in one or more storage
containers and used directly or blended with the contents of
other storage containers until the desired composition of the
kiln feed is obtained prior to burning.
c. Sampling as the kiln feed is pumped to the kiln system
as a final check before burning.
d. Samples of the kiln-fired clinker can be taken by the
manufacturer. At this point, parameters such as bulk chem­
ical composition and free lime content can be determined.
Powder mount or polished section microscopic examina­
tion of the clinker is routinely used for additional process
quality control. From this information, the kiln firing system
is optimized and controlled as well as adjustments to the
kiln feed chemical composition to accommodate the effects
of kiln dust loss and coal combustion ash. After leaving the
kiln system, clinker can be stored in one or more storage
containers prior to finish mill grinding. Clinker and calcium
sulfate, most commonly gypsum, are ground in a mill to
the desired fineness and at the necessary ratio to achieve
the desired total sulfate content. The finished mill product
is sampled frequently during grinding to determine its fine­
ness and total sulfate content. Meanwhile, the clinker and
gypsum feeders are usually monitored by computer control
to confirm that the proper ratio of materials is being deliv­
ered to the grinding mill.
e. The finished product is stored in one or more storage
silos, which are typically constructed of metal or concrete,
until it is loaded into railcars, trucks, or until bagging opera­
tions occur.
f. Sampling of the finished cement can occur at the point
where the cement is discharged from the storage container,
along transfer lines, or at the point of discharge into the final
transport vehicle. Sampling can occur during or after the
transport vehicle is loaded.
9.4.2 Sampling by purchaser-When the purchaser desires
to sample and test the cement to verify compliance with the
applicable specification, sampling should be performed in
accordance with ASTM C 1 83. The procedures described in
that standard are not intended for use by the producer for
quality control in manufacturing.
Several standard methods of sampling hydraulic cement
are described in ASTM C l 83 . Cement samples can be
obtained as grab samples in one operation, or as composite
samples obtained by an automatic sampling device that
continuously samples a cement stream at predetermined
intervals. Grab samples, obtained at prescribed intervals,
may be combined to provide a composite or test sample. The
cement may be sampled at the conveyor delivering to bulk
storage, during transfer of cement, bulk storage at points of
discharge, bulk storage and bulk shipment by means of a
slotted tube sampler or sampling pipe, packaged cement by
means of a tube sampler, and from bulk shipment by car or
truck. Depending on where the sample is taken, the sample
can represent cement in production, cement in storage, or
cement being shipped.
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27
Samples of cement should be protected by placing them
directly in moisture-proof, airtight containers to avoid mois­
ture absorption and aeration. Before testing, the samples
should be passed through a No. 20 (850 11m) sieve. Caution
should be used to minimize aeration of the cement.
9.4.3 Testing by purchaser-The rate of testing should
depend on the historical consistency of the source and the
magnitude of the deviation to be detected. Samples for
testing from each lot of cement should be collected in accor­
dance with the ASTM C 1 83 method.
Testing by the purchaser to confirm product compliance
may include methods for either standard or optional require­
ments. ASTM C 1 50/C 1 50M, ASTM C 1 1 57/C 1 1 57M,
ASTM C595/C595M, and ASTM C845/C845M list both the
standard and optional requirements for each type of cement.
Additional information on special requirements should be
available on request from the producer.
CHAPTER 1 0-SUSTAINABILITY ASPECTS O F
HYDRAULIC C E M E NTS
Hydraulic cements are found in a wide variety of struc­
tures from buildings to roadways, bridges, and dams.
Structures made with hydraulic cements have found to be
extremely durable, with buildings as old as the Pantheon in
Rome, still standing after nearly 2000 years. Currently, in
North America, some structures are designed for 1 00+-year
service lives.
1 0.1 -Hydraulic cements
Hydraulic cements include portland, slag, blends of port­
land cement and slag cement, or portland cement and other
supplementary cementitious materials (SCMs). Fly ash,
slag cement, and silica fume are all preconsumer recycled
by-products from other industries. Their use as a replace­
ment for portland cement at the concrete plant or in the
manufacture ofblended cements is an efficient way to reduce
greenhouse gases and the consumption of energy resources.
S imilar environmental benefits result from use of limestone
as an ingredient in portland or other hydraulic cements.
1 0.2-Energy consumption
Modern cements are manufactured to accommodate
a wide range of specifications and performance criteria.
Concrete, one of the end-use products made from cement,
is the world's second-most-used substance next to water.
The production of portland cement is energy-intensive and
involves heating raw materials upward of 2700°F ( 1 480°C).
Yet cement production in the United States accounts for less
than one-fourth of 1 percent of the nation's energy consump­
tion while producing approximately 7 1 million metric tons
(78 million short tons) of product (U.S. Energy Informa­
tion Administration 20 1 3 ; U.S. Geological Survey 20 1 3).
For perspective, iron and steel production accounts for 6.7
percent of the nation's energy consumption while producing
1 1 8 million metric tons of products (Brueske et al. 20 1 2;
U.S. Geological Survey 2 0 1 3).
According to the U.S. Energy Information Administration
(20 1 5), in the United States, portland cement manufacturing
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28 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
accounts for 2.4 percent of all manufacturing-related carbon
dioxide (C02) emissions. In comparison, petroleum refin­
eries produce 20.6 percent of manufacturing emissions, iron
and steel mills produce 9. 7 percent, and the paper industry
produces 5.4 percent of manufacturing emissions.
1 0.3-Use of supplementary cementitious
materials (SCMs) as replacement for portland
cement
Within limits, portland cement can be replaced with
SCMs, either at the concrete plant or in blended cements.
These materials typically include slag cement, fly ash, lime­
stone, silica fume, or a combination of these. Limits on the
replacement factors vary by application and are based on
durability and design concerns, as well as practicality on the
jobsite during construction.
Blended cements are combinations of portland cement
blended or interground with various amounts of SCMs.
Currently, ASTM C595/C595M allows up to 95 percent
replacement of portland-cement clinker with granulated
blast-furnace slag, a preconsumer recycled material. It also
allows up to 40 percent replacement with fly ash, another
preconsumer recycled material, and up to 1 5 percent
replacement with limestone, a material commonly used in
the production of portland cement.
Performance-based cements manufactured in accordance
with ASTM C 1 1 57/C 1 1 57M can meet the attributes of port­
land or blended cements using less manufacturing energy
and overall improved sustainability. Performance-based
cement specifications place no restrictions on the ingredients
of the cement as long as the products meet the performance
and durability requirements specified. The specifications
for performance cements and concrete provide the designer
with flexibility to design a material that can be customized
to meet a variety of specifications, including:
a) Low permeability
b) Sulfate resistance
c) Alkali-silica reaction (ASR) mitigation
d) Low heat of hydration
e) Improved workability
f) Improved pumpability
g) High-performance concrete
1 0.4-Use of cement in concrete
In North America, the majority of hydraulic cements are
used to manufacture concrete. Portland cements and supple­
mentary cementitious materials (SCMs), on average, make
up a small part of a cubic yard (cubic meter) of concrete, with
absolute volumes ranging from 7 percent for a lean mixture
to 1 5 percent for a rich mixture. The rest of the materials
consist of coarse and fine aggregate, water, entrained air,
and various liquid admixtures. As a result of the relatively
low volume or mass of cement in concrete, comparison on a
volumetric or mass basis shows that the embodied energy for
concrete is lower than other construction materials (Ashby
2009). According to Ashby (2009) the embodied energy of
concrete is on the order of 1 MJ!kg (or several thousand MJ/
m3) while that for carbon steel is approximately 30 MJ/kg (or
(ciCiJ American Concrete Institute- Copyrighted© Material- www.concrete.org
several million MJ/m3). The embodied energy of concrete is
also lower than plywood on both a mass and volumetric basis.
1 0.5-Recycled raw materials as raw feed in the
manufacture of portland cement
For its raw material, cement draws upon minerals
containing the four essential elements: calcium, silica,
aluminum, and iron. The most common combination of
ingredients is limestone, combined with much smaller quan­
tities of clay, iron ore, and sand. The limestone provides
a source of calcium, whereas the clay, iron ore, and sand
provide sources of alumina, iron, and silica, respectively.
So common are these elements that a wide variety of raw
materials is suitable and cement manufacture can occur in
all parts of the world. Cement is made with everything from
sea shells and shale to industrial by-products such as blast­
furnace slag from steel plants and fly ash from the electric
power industry. Approximately 20 million tons of industrial
waste, including copper slag, foundry sand, mill scale, sand­
blast grit, synthetic gypsum, and waste glass, among other
materials, is used by the U.S. cement and concrete industry
annually (Sabnis 20 12).
1 0.6-Aiternate fuels
Most cement producers are continually searching for alter­
native sources of fuel to be used in the combustion process.
The high temperature needed for cement manufacturing
makes it an energy-intensive process. The average energy
input required to make 1 ton (0.9 metric ton) of cement is 4.7
million Btu-the equivalent of approximately 4 1 8 lb ( 1 90 kg)
of coal. The U.S. cement industry uses energy equivalent to
approximately 1 6 million tons of coal every year. The cement
industry has improved energy efficiency by over 4 1 percent
between 1 972 and 2012 (Portland Cement Association 20 1 3).
Although coal, petroleum coke, and other fossil fuels have
been traditionally burned in cement kilns, many cement
companies have turned to energy-rich alternative fuels. Today,
many plants meet between 20 and 70 percent of their energy
requirements with non-fossil fuels, including some that are
consumer wastes or by-products from other industries.
While carbon-rich fuels such as coal and coke release
tremendous quantities of heat when burned, energy can be
derived from other carbon-rich by-product or waste mate­
rials, reducing reliance on fossil fuels. For example, combus­
tion of hydrocarbons in automotive tires in a cement kiln
produces 25 percent more energy than coal and it can also
result in lower emissions (U.S. Environmental Protection
Agency 2005). In fact, any material with high carbon content
could be used as a fuel. Paper, packaging, plastics (including
those with are unrecyclable or difficult to recycle), saw dust,
waste oil, and solvents are all potential alternative fuels for
cement manufacture. Because of the extremely high temper­
atures in a kiln of well above 2700°F ( 1480°C), these mate­
rials burn quickly and efficiently.
Burning alternative fuels in cement kilns offers several
environmental benefits. This type of energy recovery
conserves fossil fuels for use by future generations while
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
safely accommodating wastes that would otherwise be
deposited in landfills.
1 0.7-Combustion emissions
The cement industry continues to develop new standards
and technology to ensure air quality to meet or exceed the
U.S. Environmental Protection Agency (20 1 2) and state
regulations. Investment in new equipment and technology
to reduce air pollutant emissions totals is in the millions of
dollars per year (Marceau et a!. 2007).
Cement companies also work with state and local offi­
cials to meet the National Ambient Air Quality Standards
(NAAQS). For example, the industry is conducting ongoing
cooperative efforts with federal, state, and local officials
to study emissions controls of fine particulates and other
pollutants. Further emission reductions are achieved by
using waste fuels that would otherwise be burned unproduc­
tively in incinerators.
The portland cement industry was among the first to tackle
the issue of climate change, and it has remained at the fore­
front of developing policies and improving the manufacturing
process. Since 1 975, the cement industry has reduced emis­
sions by 33 percent. In 2000, the industry created a way to
measure C02 emissions, and by the year 2020, the industry
plans to voluntarily reduce C02 emissions by 1 0 percent
below the 1 990 baseline (Portland Cement Association 2007).
10.8-Recent progress and strategy
Recent progress includes specifications that will allow
for use of limestone as an ingredient in portland cement,
which will ultimately reduce C02 by more than 2.5 million
tons (2.26 million metric tons) per year (Nisbet 1 996). In
Europe, cements containing up to 35 percent limestone
are sold for various applications. CSA-A300 1 and ASTM
C595/595M have adopted provisions for cements with up
to 1 5 percent limestone based on European experience. In
both cases, additional C02 reductions can be realized, along
with other environmental benefits, such as reductions in raw
materials, lower embodied energy, and lower greenhouse
gas emissions.
The cement industry has adopted a three-part strategy:
1 ) Improve energy efficiency by upgrading plants with
state-of-the-art equipment
2) Improve product formulation to reduce energy required
for production and minimize the use of natural resources
3) Conduct research and develop new applications for cement
and concrete that improve energy efficiency and durability
CHAPTER 1 1 -REFERENCES
Committee documents are listed first by document number
and year of publication followed by authored documents
listed alphabetically.
A merican Association ofState Highway and Transportation
Officials
AASHTO M 85-1 5-Standard Specification for Portland
Cement
American Concrete Institute- Copyrighted© Material- www.concrete.org
29
AASHTO M 240- 1 5-Standard Specification for Blended
Hydraulic Cement
AASHTO M 295- 1 1-Standard Specification for Coal
Fly Ash and Raw or Calcined Natural Pozzolan for Use in
Concrete
AASHTO M 302 - 1 5-Standard Specification for Ground
Granulated Blast-Furnace Slag for Use in Concrete and
Mortars
AASHTO M 307 - 1 3-Standard Specification for Silica
Fume Used in Cementitious Mixtures
AASHTO M 32 1 /M 32 1 M-04-Standard Specification
for High-Reactivity Pozzolans for Use in Hydraulic-Cement
Concrete, Mortar, and Grout
AASHTO PP65- 1 1 (2 0 1 6)-Standard Practice for Deter­
mining the Reactivity of Concrete Aggregates and Selecting
Appropriate Measures for Preventing Deleterious Expansion
in New Concrete Construction
A merican Concrete Institute
ACI 2 0 1 .2R-08-Guide to Durable Concrete
ACI 207.2R-07-Report on Thermal and Volume Change
Effects on Cracking of Mass Concrete
ACI 209R-92(08)-Prediction of Creep, Shrinkage, and
Temperature Effects in Concrete Structures
ACI 2 1 2 .3R- 1 6-Report on Chemical Admixtures for
Concrete
ACI 2 1 6. 1 - 1 4---Code Requirements for Determining Fire
Resistance ofConcrete and Masonry Construction Assemblies
ACI 22 1 . 1 R-98(08)---Report on Alkali-Aggregate Reactivity
ACI 222R-0 1 ( 1 0)-Protection of Metals in Concrete
against Corrosion
ACI 223R- 1 0-Guide for the Use of Shrinkage-Compen­
sating Concrete
ACI 224R-0 1 (08)-Control of Cracking in Concrete
Structures
ACI 232. 1 R- 1 2-Report on the Use of Raw or Processed
Natural Pozzolans in Concrete
ACI 232.2R-03-Use of Fly Ash in Concrete
ACI 233R-03 ( 1 1 )-Slag Cement in Concrete and Mortar
ACI 234R-06( 1 2)-Guide to the Use of Silica Fume in
Concrete
ACI 302. 1 R- 1 5-Guide to Concrete Floor and Slab
Construction
ACI 305R- 10-Guide to Hot Weather Concreting
ACI 308R- 1 6-Guide to External Curing of Concrete
ACI 3 1 8- 1 4-Building Code Requirements for Structural
Concrete and Commentary
ACI 350-06-Code Requirements for Environmental
Engineering Concrete Structures and Commentary
ACI 5 1 5 .2R- 1 3-Guide to Selecting Protective Treat­
ments for Concrete
ACI 530/530 . 1 - 1 3-Building Code Requirements and
Specification for Masonry Structures
A merican Petroleum Institute
API l OA (20 1 0)-Specification for Cements and Mate­
rials for Well Cementing
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30 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
ASTM International
ASTM C90- 1 5-Standard Specification for Loadbearing
Concrete Masonry Units
ASTM C91/C9 1 M-1 2-Standard Specification for
Masonry Cement
ASTM C l 09/C l 09M- 1 3-Standard Test Method for
Compressive Strength of Hydraulic Cement Mortars
ASTM C l l 4 - 1 5-Standard Test Methods for Chemical
Analysis of Hydraulic Cement
ASTM C l 50/C l 50M- 1 6-Standard Specification for
Portland Cement
ASTM C l 5 1 /C l 5 1 M- 1 5-Standard Test Method for
Autoclave Expansion of Hydraulic Cement
ASTM C 1 83/C 1 83M- I S-Standard Practice for Sampling
and Amount of Testing of Hydraulic Cement
ASTM C l 86- 1 5-Standard Test Method for Heat of
Hydration of Hydraulic Cement
ASTM C l 9 1 - 1 3-Standard Test Methods for Time of
Setting of Hydraulic Cement by Vicat Needle
ASTM C204- 1 6-Standard Test Methods for Fineness of
Hydraulic Cement by Air-Permeability Apparatus
ASTM C2 1 9- 1 4-Standard Terminology Relating to
Hydraulic Cement
ASTM C227- 1 0-Standard Test Method for Poten­
tial Alkali Reactivity of Cement Aggregate Combinations
(Mortar-Bar Method)
ASTM C266- 1 3-Standard Test Method for Time of
Setting of Hydraulic-Cement Paste by Gillmore Needles
ASTM C270- 1 4-Standard Specification for Mortar for
Unit Masonry
ASTM C465- 1 6-Standard Specification for Processing
Additions for Use in the Manufacture of Hydraulic Cements
ASTM C494/C494M- 1 5-Standard Specifications for
Chemical Admixtures for Concrete
ASTM C586- 1 1-Standard Test Method for Potential
Alkali Reactivity of Carbonate Rocks as Concrete Aggre­
gates (Rock-Cylinder Method)
ASTM C595/C595M- 1 6-Standard Specification for
Blended Hydraulic Cements
ASTM C6 1 8- 1 5-Standard Specification for Coal Fly Ash
and Raw or Calcined Natural Pozzolan for Use in Concrete
ASTM C845/C845M- 1 2-Standard Specification for
Expansive Hydraulic Cement
ASTM C9 1 7 -05(20 1 1 )-Standard Test Method for Evalu­
ation of Cement Strength Uniformity from a Single Source
ASTM C979/C979M- 1 6-Standard Specification for
Pigments for Integrally Colored Concrete
ASTM C989/C989M- 1 4-Standard Specification for
Slag Cement for Use in Concrete and Mortars
ASTM C l 0 1 2/C l 0 1 2M- 1 5-Standard Test Method for
Length Change of Hydraulic-Cement Mortars Exposed to a
Sulfate Solution
ASTM C l 0 1 7/C l 0 1 7M-1 3-Standard Specifications for
Chemical Admixtures for Use in Producing Flowing Concrete
ASTM C l 03 8/C l 03 8M- 14-Standard Test Method for
Expansion ofHydraulic Cement Mortar Bars Stored in Water
ASTM C 1 1 05-08-Standard Test Method for Length
Change of Concrete Due to Alkali-Carbonate Rock Reaction
American Concrete Institute- Copyrighted© Material- www.concrete.org
ASTM C 1 1 57/C 1 1 57M- l l-Standard Performance Spec­
ification for Blended Hydraulic Cement
ASTM C 1 240- 1 5-Standard Specification for Silica
Fume Used in Cementitious Mixtures
ASTM C 1 293-08(20 1 5)-Standard Test Method Deter­
mination of Length Change of Concrete Due to Alkali-Silica
Reactions
ASTM C l 328/C l 328M- 1 2-Standard Specification for
Plastic (Stucco) Cement
ASTM C l 329/C l 3 29M- 16-Standard Specification for
Mortar Cement
ASTM C l 3 65-06(20 1 1 )-Standard Test Method for
Determination of the Proportion of Phases in Portland
Cement and Portland-Cement Clinker Using X-Ray Powder
Diffraction Analysis
ASTM C 1 565-09-Standard Test Method for Determina­
tion of Pack-Set Index of Portland Cement
ASTM C l 567- 1 3-Standard Test Method for Deter­
mining the Potential Alkali-Silica Reactivity of Combina­
tions of Cementitious Materials and Aggregate (Accelerated
Mortar-Bar Method)
ASTM C l 600/C l 600M- l l-Standard Specification for
Rapid Hardening Hydraulic Cement
ASTM C 1 679- 14-Standard Practice for Measuring
Hydration Kinetics of Hydraulic Cementitious Mixtures
Using Isothermal Calorimetry
ASTM C 1 697- 1 0-Standard Specification for Blended
Supplementary Cementitious Materials
ASTM C 1 702- 1 5-Standard Test Method for Measure­
ment of Heat of Hydration of Hydraulic Cementitious Mate­
rials Using Isothermal Conduction Calorimetry
ASTM C 1 778- 1 4-Standard Guide for Reducing the Risk
of Deleterious Alkali-Aggregate Reaction in Concrete
British Standards Institution
BS EN 1 4647:2005-Calcium Aluminate Cement -
Composition, Specifications and Conformity Criteria
Canadian Standards Association
CSA-A3000- 1 3-Cementitious Materials Compendium
CSA-A300 1 - 1 3-Cementitious Materials for Use in
Concrete
CSA-A3002 - 1 3-Masonry and Mortar Cement
CSA-A23 .2-27A- 1 4-Standard Practice to Identify
Degree of Alkali-Reactivity of Aggregates and to Identify
Measures to Avoid Deleterious Expansion in Concrete
Authored documents
American Concrete Institute, 1 978, Refractory Concrete,
SP-57, American Concrete Institute, Farmington Hills, MI,
3 1 4 pp.
Alexander, K. M., 1972, "The Relationship between
Strength and the Composition and Fineness of Cement,"
Cement and Concrete Research, V. 2, No. 6, Nov., pp.
663-680. doi: 1 0 . 1 0 1 6/0008-8846(72)90004-X
Ashby, M. F., 2009, Materials and the Environment: £co­
Informed Materials Choice, Elsevier, Oxford, UK, 375 pp.
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 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
Bakker, R. F. M., 1 983, "Permeability of Blended Cement
Concretes," Fly Ash, Silica Fume, Slag, and Other Mineral
By-Products in Concrete, SP-79, V. M. Malhotra, ed., Amer­
ican Concrete Institute, Farmington Hills, MI, pp. 589-605 .
Bamforth, P. B., 1 984, "Mass Concrete," Concrete Society
Digest No. 2, The Concrete Society, UK, 8 pp.
Barger, G. S.; Lukkarila, M. R.; Martin, D. L.; Lane, S.
B.; Hansen, E. R.; Ross, M. W.; and Thompson, J. L., 1 997,
"Evaluation of a Blended Cement and a Mineral Admix­
ture Containing Calcined Clay Natural Pozzolan for High
Performance Concrete," Proceedings of the Sixth Interna­
tional Purdue Conference on Concrete Pavement Design
and Materials for High Performance, Purdue University,
West Lafayette, IN, pp. 1 3 1 - 1 47.
Bhatty, J. I., 1 995, "Role of Minor Elements in Cement
Manufacture and Use," PCA RD 1 09T, Portland Cement
Association, Skokie, IL.
Bhatty, J. I., and Tennis, P. D., 2008, "U.S. and Canadian
Cement Characteristics: 2004," SN2879, Portland Cement
Association, Skokie, IL, 67 pp.
Blaine, R. L.; Ami, H. T.; and DeFore, M. R., 1 968,
"Interrelations between Cement and Concrete Properties,"
Compressive Strengths of Portland Cement Test Mortars and
Steam-Cured Mortars, Part 3, Building Science Series No. 8,
National Bureau of Standards, Washington, DC, 98 pp.
Blanks, R. F., and Kennedy, H. L., 1955, The Technology
of Cement and Concrete: Concrete Materials, V. 1 , John
Wiley & Sons, New York, 422 pp.
Bogue, R. H., 1 955, The Chemistry of Portland Cement,
second edition, Reinhold Publishing Corp., New York, 793 pp.
Bowering, N.; Walker, G. S.; and Harrison, P. G., 2006,
"Photocatalytic Decomposition and Reduction Reactions of
Nitric Oxide over Degussa P25," Applied Catalysis-B Envi­
ronmental, V. 62, No. 3 and 4, Feb., pp. 208- 1 6 .
Brueske, S.; Sabouni, R . ; Zach, C.; and Howard Andres,
H., 20 1 2, "U.S. Manufacturing Energy Use and Greenhouse
Gas Emissions Analysis," ORNL/TM-20 1 2/504, Oak Ridge
National Laboratories, Nov. , 2 1 2 pp.
Bucher, B . ; Radlinska, A.; and Weiss, J., 2008, "Prelimi­
nary Comments on Shrinkage and Shrinkage Cracking
Behavior of Cement Systems that Contain Limestone,"
Concrete Technology Forum, National Ready Mixed
Concrete Association, Silver Spring, MD, May, 9 pp.
Buck, A. D., 1 983, "Alkali Reactivity of Strained Quartz
as a Constituent of Concrete Aggregate," Cement, Concrete
and Aggregates, V. 5, No. 2, pp. 1 3 1 - 1 33. doi: 1 0. 1 520/
CCA1 0264J
Bush, E. G. W. ; Copeland, R. E.; Lewis, R. K.; and Hanson,
J. A., 1 963, discussion of "Optimum Steam Curing Proce­
dure in Precasting Plants" by J. A. Hanson," A CI Journal
Proceedings, V. 60, No. 9, Sept., pp. 1 287- 1 299.
Cain, C. J., 1 994, "Mineral Admixtures," Significance
of Tests and Properties of Concrete and Concrete-Making
Materials, P. Klieger and J. F. Lamond, eds., ASTM STP
1 69C, pp. 500-5 1 0 .
Counto, U. J . , 1 964, "The Effect o f the Elastic Modulus
of the Aggregate on the Elastic Modulus, Creep, and Creep
American Concrete Institute- Copyrighted© Material- www.concrete.org
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Recovery of Concrete," Magazine of Concrete Research, V.
1 6, No. 48, pp. 1 29- 1 3 8 . doi: 1 0 . 1 6 80/macr. l 964. 1 6.48. 129
Diamanti, M. V.; Ormellese, M.; and Pedeferri, M.,
2008, "Characterization of Photocatalytic and Superhydro­
philic Properties of Mortars Containing Titanium Dioxide,"
Cement and Concrete Research, V. 38, No. 1 1 , pp. 1 349-
1 3 5 3 . doi: 1 0 . 1 0 1 6/j .cemconres.2008.07.003
Detwiler, R. J., and Taylor, P. C., 2005, "Specifier's Guide
to Durable Concrete," PCA Engineering Bulletin 22 1 , Port­
land Cement Association, Skokie, IL, 72 pp.
Detwiler, R. J.; Bhatty, J. I.; and Bhattacharja, S., 1 996,
"Supplementary Cementing Materials for Use in Blended
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IL, 96 pp.
Dolar-Mantuani, L., 1983, Handbook of Concrete Aggre­
gates: A Petrographic and Technological Evaluation, Noyes
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Gage, M., 1 970, Guide to Exposed Concrete Finishes,
Architectural Press/Cement and Concrete Association,
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Famy, J. A., and Kerkhoff, B., 2007, Diagnosis and Control
of A lkali-Aggregate Reactions in Concrete, IS4 1 3 .02, Port­
land Cement Association, Skokie, IL, 26 pp.
Garboczi, E. J., and Bentz, D. P., 1 992, "Computer
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Giannantonio, D. J.; Kurth, J . C.; Kurtis, K. E.; and
Sobecky, P. A., 2009, "Effects of Concrete Properties and
Nutrients on Fungal Colonization and Fouling," Interna­
tional Biodeterioration & Biodegradation, V. 63, No. 3,
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32 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
Helmuth, R.; Hills, L. M.; Whiting, D. A.; and Bhat-
tacharja, S., 1 995, "Abnormal Concrete Performance in the
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A CI Journal Proceedings, V. 72, No. 1 0, Oct., pp. 526-527.
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Content on the Behaviour of Portland Cement Mortars,"
World Cement Technology, V. 8, pp. 75-76 and 79-85.
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Cement Pastes Containing Fly Ash, Slag, and Silica Fume,"
Blended Cements, V. 897, pp. 1 28- 1 43 .
Hooton, R. D.; Gruber, K.; and Boddy, A. M., 1 997, 'The
Chloride Penetration Resistance of Concrete Containing
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Hooton, R. D.; Nokken, M.; and Thomas, M. D. A., 2007,
"Portland-Limestone Cement: State-of-the-Art Report and
Gap Analysis for CSA A 3000," SN3053, Portland Cement
Association, Skokie, IL, 53 pp.
Husken, G.; Hunger, M.; and Brouwers, H. J. H., 2009,
"Experimental Study of Photocatalytic Concrete Products
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cCiC"iJ American Concrete Institute- Copyrighted© Material- www.concrete.org
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Licensed to: Florida Suncoast Chapter
 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
Nisbet, M., 1 996, "The Reduction of Resource Input and
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Panarese, W. C., 2005, "Environmental Performance of
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Popovics, S., 1 976, "Phenomenological Approach to the
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Popovics, S., 1 980, "Composite Averages for the Estima-
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Portland Cement Association, 1 987, "Concrete for Mass
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Portland Cement Association, 1 997, "Portland Cement,
Concrete, and the Heat of Hydration," Concrete Technology
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Portland Cement Association, 2007, "Life Cycle Inven-
tory of Portland Cement Concrete," PCA R&D Serial No.
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Portland Cement Association, 2 0 1 3 , U.S. and Canadian
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29 1 6 . 1 958.tb l 3494.x
Powers, T. C.; Copeland, L. E.; Hayes, J. C.; and Mann,
H. M., 1 954, "Permeability of Portland Cement Paste," A CI
Journal Proceedings, V. 5 1 , No. 3, Mar., pp. 285-298.
Ramachandran, V. S., ed., 1 995, Concrete Admixtures
Handbook Properties, Science and Technology, second
edition, Noyes Publications, Park Ridge, NJ, 1 1 53 pp.
Rasheeduzzafar; Hussain, S. E.; and Al-Saadoun, S., 1 992,
"Effect ofTricalcium Aluminate Content of Cement on Chlo-
ride Binding and Corrosion ofReinforcing Steel in Concrete,"
A CI Materials Journal, V. 89, No. I , Jan.-Feb., pp. 3-12.
Richartz, W., 1 973, "Effect of Storage on Properties of
Cement," Zement-Kalk-Gips, V. 2, pp. 67-74.
Ritchie, T., 1 960, "Efflorescence," Canadian Building
Digest, Division of Building Research, National Research
Council, Feb., No. 2, 4 pp.
Robson, T. D., 1 962, High Alumina Cements and
Concretes, John Wiley & Sons, New York, 263 pp.
Roy, D. M., and Goto, S., 1 9 8 1 , "The Effect of w/c Ratio
and Curing Temperatures on the Permeability of Hardened
Cement Paste," Cement and Concrete Research, V. 1 1 , No.
4, pp. 575-579. doi: 1 0. 1 0 1 6/0008-8846(8 1 )90087-9
American Concrete Institute- Copyrighted© Material- www.concrete.org
33
Sabnis, G. M., ed., 2012, Green Building with Concrete:
Sustainable Design and Construction, CRC Press, Taylor &
Francis Group, Boca Raton, FL, 3 0 1 pp.
Scanlon, J. M., and Connolly, J. D., 1 994, "Laboratory
Studies and Evaluations of Concrete Containing Dead-
Burned Dolomite," Durability of Concrete, Proceedings
of the Third International Conference, SP- 145, V. M.
Malhotra, ed., American Concrete Institute, Farmington
Hills, MI, pp. 1 1 1 5 - 1 1 34.
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Cement," Proceedings of the 5th International Symposium
on the Chemistry of Cement, Part 4, Cement and Concrete
Association of Japan, Tokyo, 1 86 pp.
Short, N. L., and Page, C. L., 1 982, "Diffusion of Chloride
Ions through Portland and Blended Cement Pastes," Silcates
Industriels, V. 47, No. 1 0, Oct., pp. 237-240.
Smolczyk, H. G., 1 984, "State of Knowledge on Chloride
Diffusion in Concrete," Betonwerk + Fertigteil-Technik, No.
1 2, pp. 837-843 .
Sobolev, K.; Sanchez, F.; and Flores-Vivian, I., 2 0 1 2 ,
"The Use ofNanoparticle Admixtures to Improve the Perfor-
mance of Concrete," 1 2th International Conference on
Recent Advances in Concrete Technology and Sustainability
Issues, pp. 455-469.
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Chemical Publishing Co., Revere, MA.
Stark, D . C., 2002, "Performance of Concrete in Sulfate
Environments," RD 1 29, Portland Cement Association,
Skokie, IL, 28 pp.
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Skokie, IL.
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Academic Press, London, V. 1 , 460 pp., and V. 2, 442 pp.
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"State-of-the-Art Report on Use of Limestone in Cements
at Levels of up to 1 5%," SN3 1 48, PCA, Skokie, IL, 78 pp.
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Ceramic Society, V. 54, pp. 787-79 1 .
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Materials in Concrete," SN978 1 46657280, CRC Press,
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Concrete," Transportation Research Circular 494, Section
on Concrete (A2EOO), TRB, Washington, DC, 63 pp.
cCiC'iJ
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34 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)
Tuthill, L. H., 1 936, "Resistance of Cement to the Corro­
sive Action of Sodium Sulfate Solutions," A CI Journal
Proceedings, V. 33, No. 12, Dec., pp. 83- 1 06.
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revised eighth edition, Denver, pp. 8- 1 2 .
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Energy Outlook, with Projections to 2040," DOE/EIA-0383,
Apr.
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Energy Outlook 20 1 5 with Projections to 2014," Energy
Information Administration, Washington, DC, 1 54 pp.
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Fuel (TDF)," EPA530-F-05-006, Apr., Washington, DC.
U.S. Environmental Protection Agency, 20 1 2, "Portland
Cement: New Source Performance Standards and National
Emissions Standards for Hazardous Air Pollutants: Proposed
Amendments on Reconsideration: Fact Sheet," June 22,
Washington, DC.
U.S . . Geological Survey, 20 1 3 , "Mineral Commodity
Summaries," U.S. Department of the Interior, U.S. Geolog­
ical Survey, Reston, VA, 1 98 pp.
Verbeck, G. J., 1 966, "Cements for Elevated Curing Condi­
tions," RD-M 1 84, Portland Cement Association, Skokie, IL.
Verbeck, G. J., 1 968, "Field and Laboratory Studies of the
Sulfate Resistance of Concrete," Peiformance ofConcrete­
Resistance of Concrete to Sulfate and Other Environmental
Conditions, Thorvaldson Symposium, University ofToronto
Press, pp. 1 1 3 - 1 24.
Whiting, D., and Nagi, M., 1 998, "Manual on Control of
Air Content in Concrete," EB 1 1 6, Portland Cement Asso­
ciation, Skokie, IL, 52 pp.
Whiting, D., and Stark, D., 1 983, "Control of Air Content
in Concrete," NCHRP Report No. 258, Transportation
Research Board, Washington, DC, 84 pp.
APPENDIX A-CALCIU M-ALUMINATE C E M ENTS
A.1 -Manufacture and properties
Calcium-aluminate cements are hydraulic cements
obtained by pulverizing a solidified melt or clinker that
consists predominantly of hydraulic calcium aluminates
formed from proportioned mixtures of aluminous and
calcareous materials (Lea 1 998; Robson 1 962). They are
generally divided into three groups based on the alumina
and iron oxide contents (Table A. l ). The cements of higher
alumina content are suitable for higher temperature applica­
tions. BS EN 1 4647:2005 is a standard for calcium-alumi­
nate cements.
The density of calcium-aluminate cements generally ranges
from 1 80 to 203 lb/ft3 (2.90 to 3.25 Mg/m3). The higher values
reflect larger amounts of iron oxide in melted low-purity
cements and free alumina in high-purity cements. The loosely
compacted bulk density of the powdered product for shipping
is approximately 65 to 1 00 lb/ft3 ( 1 04 1 to 1 602 kg/m3).
Calcium-aluminate cements range in color from dark gray
to white, depending on the amount and oxidation state of
iron oxide and the manufacturing process. The more iron
American Concrete Institute- Copyrighted© Material- www.concrete.org
oxide present in the cement, either as ferrous oxide, ferric
oxide, or both, the darker the color.
Potential users of calcium-aluminate cements should
contact the manufacturer of the product under consider­
ation for information on mixture proportioning, aggregate
selection, handling, placing, and curing requirements. They
should be aware of the possible conversion of the hydration
products from larger volume metastable hexagonal prod­
ucts such as CAH 1 0 to smaller volume stable cubic products
(C3AH6) resulting in strength retrogression (Robson 1 962).
A.2-lnfluences of admixtures and supplementary
cementitious materials
Supplementary cementitious materials (SCMs) and
admixtures used with portland and blended cements may
not be satisfactory for use with calcium-aluminate cements.
Whereas some will behave in a similar manner, the dosages
required may differ greatly. Other admixtures may be of
little value, be harmful, or act in an opposite fashion when
used with calcium-aluminate cements. In addition, various
types of calcium-aluminate cements may produce different
results. Whenever possible, trial batches should be made
with the intended cement and technical advice sought from
the manufacturer of the admixture or the cement.
A.3-lnfluence of environment
Curing temperatures during the first 24 hours influence
the strength development of calcium-aluminate cements
concretes. Temperatures below 75°F (24°C) produce a high
initial strength that will generally increase within 6 months
and then decrease because of volume change resulting from
phase conversion to strength values approaching the 1 -day
strength. Initial curing temperatures above 90°F (32°C)
may provide lower 24-hour strengths in calcium-aluminate
cements, but retrogression of strength with time is minimized.
Curing compounds are effective in sealing the concrete
surface temporarily to prevent water evaporation. Curing
compounds should be applied as soon as possible after
finishing is complete. Fog-spray curing should begin only
after initial set of the concrete surface.
Potential users of calcium-aluminate cements should
obtain further information on curing methods from the
manufacturer of the product under consideration.
A.4-Heat of hydration
The hydration of calcium-aluminate cements can produce
large amounts of heat during the first 24 hours. Provisions
for dissipating this heat should be considered, especially in
thick sections of concrete (for example, those greater than
6 in. [ 1 50 mm] in thickness).
A.5-Setting characteristics
Calcium-aluminate cements frequently have quite different
setting characteristics from portland and blended hydraulic
cements. When tested according to standard needle penetra­
tion tests (Vicat test [ASTM C l 9 1 ] or Gillmore test [ASTM
C266]), different calcium-aluminate cements provide a wide
range of times of setting, as shown in Table A. l . In addition,
Licensed to: Florida Suncoast Chapter
 GUIDE TO THE SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16) 35

Table A.1 -0xide analyses and property ranges for calciu m-al u m i nate cements
Low purity Intermediate purity High purity

AhOJ, % 39 to 50 54 to 66 70 to 90

Fe203, % 7 to 1 6 I to 3 0.0 to 0.4

CaO, % 35 to 42 26 to 36 9 to 28

Si02, % 3 to 9 3 to 9 0 to 0.5
2
Wagner surface, m /kg 1 40 to 1 80 1 60 to 200 Greater than 220
2
Blaine surface, m /kg 260 to 440 320 to 1 000 360 to 1 1 50

Time of setting

Vi cat initial (h:min) 3 :00 to 9:00 3 :00 to 9:00 0:30 to 6:00

Minimum compressive strength (ASTM CI09/CI09M, 2 in. 150 mm] cubes), MPa (psi)

I day 24. 1 (3500) 4 1 . 1 (6000) 1 7.2 (2500)

7 days 4 1 .4 (6000) 58.6 (8500) 34.5 (5000)

28 days 48.3 (7000) 68.9 (I 0,000) -

the period between time of initial and final setting is gener­ Table A.7-Manufacturing plants and aggressive
ally much shorter than with portland cements. Blends of agents
portland cement and calcium aluminate cement can greatly Plant types Aggressive agents
affect setting times (Odler 2000).
Ammunition Nitric, sulfuric, and other acids
The slump cone should not be used for determining the
Breweries Dilute organic acids
workability characteristics of calcium-aluminate cements.
Because some calcium-aluminate cements lose slump rather Corn products plants Dilute sulfurous acids and starch
quickly, special care may be required in mixing, handling, Dairies and ice cream plants Dilute lactic acid and brine
placing, and finishing. Other calcium-aluminate cements
Milk product plants Dilute lactic acid
remain workable longer than many portland cements. The
manufacturer of the particular product under consideration Sugar mills and refineries Can juice and molasses

should be consulted in this regard. Dilute tannic acid and dilute chromic
Tanneries
and organic acids
A.6-Strength Distilleries Dilute organic acids
Calcium-aluminate cements gain strength much faster Chocolate plants Cocoa butter
than portland cements (Table A. l ). Although calcium­
Fertilizer plants Dilute ammonium sulfate
aluminate cements can produce mortars and concretes with
very high early strengths, the strength may fall signifi­ Meat packing plants Dilute organic acids, blood, and brine
cantly at later ages if the w/c and curing temperature are Wastewater plants and sewers Hydrogen sulfide and sulfuric acid
not controlled as specified. This strength loss is associated Water and wastewater Chemicals used in processes
with the conversion to the stable hydrate of the metastable
calcium aluminate hydrates that form first, at temperatures
A.7-Resistance to chemical attack
below approximately 75°F (24°C). The rate at which the
Calcium-aluminate cement concretes are resistant to a
conversion occurs and its effect on the strength and perme­
number of aggressive acidic agents that attack portland­
ability due to shrinkage microcracking increases with the
cement concretes. Calcium-aluminate cement was originally
amount of water available above the critical w!c, the curing
developed to resist attack by sulfates in soil, seawater, and
temperature (above approximately 86°F [30°C]), the relative
industrial waste waters. Experience has shown that concretes
humidity, and the time of exposure. The residual strength
made with calcium-aluminate cement are more resistant to
after complete conversion depends on the original w!c of the
sulfate attack than concretes made with Type V portland
concrete. Because of the probability of conversion, the use of
cement. Mortars and concretes made with calcium-alumi­
calcium-aluminate cements in load-bearing concrete struc­
nate cements and suitable aggregates are more resistant to
tures should either be avoided or anticipated strength retro­
mild acids and acid industrial waste liquors than those made
gression calculated when designing the structure. Blends of
with portland cement. Calcium-aluminate cement has been
portland and calcium-aluminate cement can provide rapid
used successfully for lining fossil fuel power plant stacks
strength gain, with appreciable strengths in as early as 1
to resist mild sulfurous and sulfuric acid solutions. They
hour, but ultimate strengths are typically lower than either
have also been used in the following types of manufacturing
material used alone (Odler 2000).
plants to resist specific aggressive agents shown in Table A. 7
(ACI 350; ACI 5 1 5.2R).

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36 GUIDE TO TH E SELECTION AND USE OF HYDRAULIC CEMENTS (ACI 225R-16)

As a general guideline, the use of calcium-aluminate
cements for resistance to acidic solutions is limited to appli­
cations where the pH is not less than 3 .5 to 4.0. Whenever
possible, however, and particularly when a new application
is encountered, a trial section should be installed.
A.S-Resistance to high temperatures
If resistance to temperatures higher than approximately
570°F (300°C) is needed, the properties of both the cement
and the aggregate should be considered. For the most
demanding applications, calcium-aluminate cement is
combined with selected refractory aggregates to produce
refractory concretes suitable for use at temperatures up to
3400°F ( 1 870°C). ACI SP-57 (American Concrete Institute
1978) provides more information on refractory concretes
using hydraulic-cement binders.

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