CHAPTER 3

Portland, Blended and Other Hydraulic Cement

Portland cements are hydraulic cements composed now know it.

primarily of hydraulic calcium silicates (Figure 3-1).
Hydraulic cements set and harden by reacting chem-
ically with water and maintain their stability
underwater. Hydraulic cements include portland
cement and blended cements. Other types of hydraulic
cements include natural cement and slag cement. They
are used in all aspects of concrete construction.

Figure 3-1. Portland cement is a fine powder that when mixed with
water becomes the glue that holds aggregates together in concrete.

The development of portland cement was the result of

persistent investigation by science and industry to
manu- facture a product superior in quality to natural
cement. The invention of portland cement is generally
credited to Joseph Aspdin, an English mason. In 1824, he
obtained a patent for his product, which he named
portland cement because in its final state, it resembled
the color of the natural limestone quarried on the Isle of
Portland in the English Channel (Figure 3-2) (Aspdin
1824). The name has endured and is used throughout the
world, with many manufacturers adding their own
trade or brand names.

Aspdin was the first to prescribe a formula for portland

cement and the first to have his product patented. How-
ever, in 1845, I. C. Johnson, of White and Sons, Swans-
combe, England, claimed to have “burned the cement
raw materials with unusually strong heat until the mass
was nearly vitrified,” producing a portland cement as we

1
Figure 3-2. Isle of Portland quarry stone (after which portland
cement was named) next to a cylinder of modern concrete.

Manufacture of Portland Cement

Portland cement is manufactured by combining precise

proportions of raw materials. These materials are then
fired in a rotary cement kiln at high temperatures to
form new chemical compounds which are hydraulic in
nature.
These compounds or phases are formed from
oxides of calcium, silica, alumina, and iron. Table 3-
1 lists the
predominant sources of raw materials used in the
manu- facture of portland cement.

Numerous waste materials and industry byproducts

are also used to supplement some or all of these
compo-
nents. Most of these by-products often contain some
fuel component. Some examples of industry waste or
by- products are tires, spent pot liners, bottom ashes, or
various incinerator ashes.

Steps in the manufacture of cement are illustrated in

the flow chart in Figure 3-3. While the operations of
all
cement plants are basically the same, no flow diagram
can adequately illustrate the unique characteristics of
any one specific plant. Every plant has significant
differences in layout, equipment, or general appearance
(Figure 3-4).

2
Design and Control of Concrete Mixtures ◆ EB001

Drilling rig
Overburden

To Crusher
Shale Each raw material
is stored separately

Limestone

Raw materials consist of

combinations of limestone,
cement rock, and shale, clay,
sand, or iron ore
Primary crusher
Raw materials conveyed
Secondary crusher to grinding mills
3
1. Stone is first reduced to 125 mm (5 in.) size, then to 20 mm ( /4 in.), and stored.

High-pressure grinding rolls

(optional, usually used in
conjunction with a ball mill)
Feed

To
preheater

Discharge Dust
collector
Product
discharge
Raw materials port
are proportioned Raw material

Roller mill To pneumatic pump

Air Classifier
blade
Dry mixing and Ground raw
blending silos material storage

2. Raw materials are ground to powder and blended. Feed sprout

Grinding roller Gas intake
port

Hot gas from

kiln, preheater
or cooler
Hot gases from preheater or clinker cooler to raw mill Detail of a vertical roller mill, which combines crushing,
grinding, drying, and classifying in one vertical unit.
These units may also be used for finish grinding.
Raw material feed

Preheater. Hot gases from kiln heat

raw feed and provide about 40%
calcination before feed enters kiln

Some installations include a Flash

Furnace that provides about 85% to 95% Materials are
calcination before feed enters kiln stored separately
Clinker
Dust Tertiary air duct
collector
Gypsum

Air
Fan Dust collector Rotating kiln Clinker cooler

Clinker and gypsum conveyed

to grinding mills

3. Burning changes raw mix chemically into cement clinker. Note four-stage preheater, flash furnaces, and shorter kiln.

High
efficiency Cement
Exhaust product
gas dust High efficiency
collector and air
separator
to dust
collector Mill product
Fan and air
Secondary
Air
additions
Inorganic

Primary air from

process

mill air sweep

Groun
limest
one

Finished cement
d

product to silo
Separator rejects
Materials are (tails) return to mill Air
proportioned Ambient
air Mill
Twin high-pressure roll discharge
press to precrush clinker
Grinding mill
entering the ball mill Solids
(optional) Bucket
elevator
to separator Cement
pump Bulk storage Bulk Bulk Box Packaging Truck
truck car car machine

4. Clinker with gypsum is ground into portland cement and shipped.

Figure 3-3. Steps in the manufacture of portland cement.

3
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Table 3-1. Sources of Raw Materials Used in Manufacture of Portland Cement

Calcium Iron Silica Alumina Sulfate

Alkali waste Blast-furnace flue dust Calcium silicate Aluminum-ore refuse* Anhydrite
Aragonite* Clay* Cement rock Bauxite Calcium sulfate
Calcite* Iron ore* Clay* Cement rock Gypsum*
Cement-kiln dust Mill scale* Fly ash Clay*
Cement rock Ore washings Fuller’s earth Copper slag
Chalk Pyrite cinders Limestone Fly ash*
Clay Shale Loess Fuller’s earth
Fuller’s earth Marl* Granodiorite
Limestone* Ore washings Limestone
Marble Quartzite Loess
Marl* Rice-hull ash Ore washings
Seashells Sand* Shale*
Shale* Sandstone Slag
Slag Shale* Staurolite
Slag
Traprock
Note: Many industrial byproducts have potential as raw materials for the manufacture of portland cement.
*Most common sources.

and rotational speed of the kiln. Fuel (pulverized coal,

petroleum coke, new or recycled petroleum oil, natural
gas, tire-derived fuels, and byproduct fuel) is forced into

Figure 3-4. Aerial view of a cement plant.

Figure 3-5. Limestone, a primary raw material
Selected raw materials are transported from the quarry providing calcium in making cement, is quarried near
(Figure 3-5), crushed (Figure 3-6), milled, and proportioned the cement plant.
so that the resulting mixture has the desired chemical
composition. The raw materials are generally a mixture of
calcareous (calcium carbonate bearing) material, such as
limestone, and an argillaceous (silica and alumina) mate-
rial such as clay, shale, fly ash, or blast-furnace slag. Most
modern cement manufacturing technology uses the dry
process, in which grinding and blending are accomplished
with dry materials. In the wet process, the grinding and
blending operations are performed with the materials
mixed with water to form a slurry. In other respects, the
dry and wet processes are similar.

After blending, the ground raw materials are fed into

the upper or back end of a kiln (Figure 3-7). The raw Figure 3-6. Quarry rock is trucked to the primary
mix passes through the kiln at a rate controlled by the crusher.
slope

4
Design and Control of Concrete Mixtures ◆ EB001

the lower end of the kiln where it ignites and generates

material temperatures of 1400°C to 1550°C (2550°F to
2800°F). Most modern kilns (post 1980) have increased
energy efficiencies by transfering a portion of the kiln
into a series or string of vertical heat exchange devices
known as preheater cyclones and precalciner vessels. The
remain- ing horizontal portion of the kiln in the newest
plants are only used for the final burning zone reaction.

Figure 3-8. Portland cement clinker is formed by burning

calcium and siliceous raw materials in a kiln. This particular
clinker is about 20 mm ( 3 ⁄4 in.) in diameter.

The clinker is rapidly cooled and then pulverized into a

fine material. During this operation, small amounts of
gypsum (Figure 3-10) are added to regulate the setting
time of the cement and to improve shrinkage and
strength development properties (Lerch 1946 and Tang
1992).
Limestone and inorganic processing additions may also
be added, each in amounts up to 5% by mass. Organic
processing additions may be added in amounts up to
1% by mass. These additions provide significant environ-
Figure 3-7. Rotary kiln (furnace) for manufacturing portland cement
clinker. Inset view inside the kiln. mental benefits as well as manufacturing improvements
(Hawkins and others 2005 and Taylor 2008). In the final
The final product from the intense heating of these raw stage of manufacture, finish grinding, clinker and other
materials in the kiln is portland cement clinker. In the ingredients are ground so fine that nearly all of the mate-
kiln, the materials reach approximately 1450°C (2700°F) rial passes through a 45 µm (No. 325 mesh) sieve. This
and a number of chemical reactions occur, changing the extremely fine gray powder is now portland cement.
raw material into cement clinker, grayish black pellets
predominantly the size of marbles (Figure 3-8) . During The past century has seen dramatic developments in
nearly every aspect of cement manufacturing. Process
manufacture, chemical analyses of all materials are
improvements have greatly improved the uniformity and
made frequently to ensure a uniform, high-quality
quality of portland cement. One particularly significant
cement.
improvement is the rate of strength gain of the finished
When the material (clinker) emerges from the kiln it
product.
consists predominantly of four phase compounds: trical-
cium silicate (C3S), also known as alite, dicalcium silicate Quality control has continued to improve throughout the
(C2S), also known as belite, tricalcium aluminate (C3A), history of portland cement production. Cement manufac-
and tetracalcium aluminoferrite (C4AF). (These phase turers now offer a wider range of commercial cements,
compounds are noted using cement chemists notation; including blended cements suitable for numerous
discussed in further detail under Chemical Phases applica- tions. The cement industry has focused resources
(Com- pounds) and Hydration of Portland Cement.) towards reducing the environmental impact of cement
Figure 3-9 shows the clinker production process from production, particularly carbon dioxide generation as
raw feed to the final product. described in the following sections.

5
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Cross-section view of kiln Nodulization process Clinkering reactions

Particles are solid.
No reaction between particles. Water
is lost. H2 O
To 700C Dehydrated
(1290F) clay re- H2 O
Raw materials
are free-flowing crystallizes
powder
Clay particle
Limestone particle

Particles are still solid. As calcination continues, free

lime
increases CO2 CO2
700-900C
(1290-1650F) Reactive silica
combines with
Powder
is still CaO to begin
forming C2S. CO2
free-flowing Calcination
maintains
feed temperature at 850C (1560F).

Reactions start happening When calcination Free CaO

between solid particles. is complete,
temperature
1150-1200C increases
(2100-2190F) rapidly.
Particles start Small belite
to become crystals
“sticky” form from
combination
of silicates and CaO.
1200 -1350C (2190-2460F) Capillary forces of the liquid keep Above 1250C Round belite crystals
As particles start to particles together. (2280F),
agglomerate, they liquid phase
are held together by is formed.
the liquid. Liquid allows
The rotation of the reaction
kiln initiates between
coalescing of belite and free
agglomerates and CaO to
layering of particles. form alite. Angular alite crystals

Nodules will form with Belite crystals

1350-1450C sufficient liquid. decrease
(2460-2640F) in amount,
Agglomeration Insufficient increase in
and layering of liquid will result
size.
particles continue in dusty clinker.
as material falls on Alite
top of each other. increases
in size
and amount.

Clinker nodules remain Upon cooling, the

unchanged during C3A and C4AF
cooling crystallize in the
liquid phase.
Cooling Lamellar
structure
appears in
belite
crystals

Figure 3-9. Process of clinker production from raw feed to the final product (Hills 2000).

6
Design and Control of Concrete Mixtures ◆ EB001

Three by-products of the iron and steel industries can be

used in the manufacture of portland cement: foundry
sand, mill scale, and slag. Foundry sand can provide
silica and possibly iron for the production of clinker. Mill
scale contains iron oxides that can replace other iron-
bearing materials in the kiln feed. Slag contains high
percentages of calcium oxide and silicon dioxide along
with varying amounts of aluminum oxide and iron
oxides. Also, select slags can be combined with portland
cement as a mineral process addition or used to produce
a blended cement product.

Figure 3-10. Gypsum, a source of sulfate, is interground Fly ash and bottom ash from electric power plants
with portland clinker to form portland cement. It helps provide a source of silica, alumina, iron and calcium in
control setting, drying shrinkage properties, and strength the raw mix. Fly ash can also be used as a mineral process
development. addi- tion in portland cement and in the production of
blended cement. Coal combustion byproducts with a
high carbon content (that are not suitable for use in
Cement’s Role in Sustainability concrete as an SCM) also provide fuel value in the kiln.

Cement manufacturing is energy intensive, due to the Land Stewardship

high temperature processing required. As with any Limestone for use in production of cement usually comes
industry burning fossil fuels, the cement industry also from a quarry at or near the plant while other materials
generates combustion by-products and other gaseous such as clay, shale, iron ore, and sand are typically ob-
emissions. However, less than half of the emissions tained from other nearby sources. Because these raw
produced by the cement industry are attributable to the materials are among the most common on Earth, cement
combustion of fuels. The calcination of limestone that producers can mitigate environmental impact through
occurs during a chemical reaction in the manufacturing careful site selection and operating procedures.
process – fundamental to the creation of portland
cement At the end of their useful life, cement quarries can be
– generates approximately 60% of the CO2 emissions reclaimed as parks, recreational areas, or other develop-
from the process. The cement industry emits, on average, ments. Many cement companies have developed
0.92 tons of CO2 for each ton of cement produced closure, reclamation, and reuse plans for their quarries,
(Marceau, Nisbet, and VanGeem 2006). The emissions which include careful soil and water contouring and
per ton vary because the types of equipment, process landscape designs to optimize the environmental
energy efficien- cies, and product compositions vary benefits of the reclaimed areas (Figure 3-11).
from plant to plant. Blended cements and cements
containing limestone typi- cally embody less CO2 per ton
than portland cement made without mineral process
additions or limestone.
Marceau, Nisbet, and VanGeem (2006) provide a life
cycle inventory of portland cement. For more
information on cement sustainability, see the PCA Report
on Sustainable Manufacturing at
[Link]/smreport09 and the World Business
Council for Sustainable Development Cement
Sustainability Initiative at [Link].

Alternative Raw Materials

The U.S. cement industry is increasingly turning to the Figure 3-11. The Sunken Garden at the Butchart Gardens in Victoria,
use of alternative raw materials to replace or supplement British Columbia was once a limestone quarry for cement production
tradi- tional materials – limestone, clay, iron ore, and (Courtesy of Jeffrey Beall).
sand, as sources of calcium, alumina, iron, and silica. The
increased use of these alternative sources to produce Solid Waste Reduction
cement reduce the amount of virgin materials required. Byproducts generated during cement making are either
Many cement plants utilize industrial by-products and recycled into the process or used in other beneficial appli-
wastes such as steel slag from steel plants and fly ash cations. Cement kiln dust (CKD) is removed from the kiln
from coal-fired electric power plants in the manufacture
of clinker.
7
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

exhaust gases by pollution-control devices. Through im- of all U.S. cement plants now incorporate alternative fuels
provements in the manufacturing process, the industry in their energy consumption strategy (Sullivan 2009).
has nearly eliminated the amount of CKD that is land-
filled. Recycling CKD back into the manufacturing
process offsets the use of limestone and other virgin raw
materials and conserves energy.

CKD that cannot be recycled back into the process can be

sold for a variety of beneficial uses such as soil solidifica-
tion/stabilization, waste solidification/stabilization, and
agricultural soil amendment. Because of the recent manu-
facturing changes and advances in analytical testing equip-
ment, the cement manufacturer is now able to control the
quality of the resulting CKD from the plant. As a result,
cement plants have been able to utilize previously
landfilled CKD for other beneficial uses. Recently, landfilled
CKD has also become a valuable commodity. The goal of
the U.S. cement industry is to reduce the amount of CKD
disposed per ton of clinker by 60% by 2020 (from a 1990
baseline).

Energy and Fuel

The high temperature needed for cement manufacturing
makes it an energy-intensive process. The average
energy input required is 4.53 million Btu per metric ton
(PCA 2010). The cement industry has improved energy
effi- ciency by 37% from 1972 (Figure 3-12). Cement
produc- tion now accounts for 2.4% of U.S. energy
consumption. In comparison, iron and steel mills
account for 11% while paper mills account for 15% (PCA
2009).
Energy reduction of U.S. portland cement plants
8.5
8.0

7.5
million BTU per equivalent
Enercy consumption,

7.0
6.5

6.0
5.5

5.0

4.5
4.0
74 76 78 80 82 84 86 88 90 92 94 96 98 00 02 04 06 08
Year
All plants Wet process Dry process (all types)
Preheater Precalciner No preheater (long dry)
No data available

Figure 3-12. Energy consumption data 1974 thru 2008 for U.S.
cement industry (PCA 2009).

Although coal, petroleum coke, and other fossil fuels

have been traditionally used in cement kilns, many
cement companies are turning to energy-rich alternative
fuels.
Many plants meet a substantial portion (20% to 70%) of
their energy requirements using alternative fuels. These
fuels often include consumer wastes or by-products from
other industries. Cement plants carefully utilize these al-
ternative fuels and materials so their cements conform to
ASTM and AASHTO standards. Slightly more than 65%
8
Alternative fuels are carefully selected for the benefit of
heat value while complying with increasingly restrictive
emission standards and regulations. Over the past
decade, the consumption of tire-derived fuels has
increased 80% with the U.S. cement industry efficiently
combusting 479,000 metric tons (528,000 short tons) of
tire-derived waste along with increased volumes of
other waste fuels, such as plastics, diapers, roofing
material, and various biosolids. In 2007, the energy
obtained from waste fuels increased to 9.4% of the total
energy demand at cement plants. Some plants also use a
significant amount of wind- generated electricity. A goal
of the U.S. cement industry is to improve the energy
efficiency by 20% on a per unit basis by 2020 (from a
1990 baseline) (PCA 2009).

Use of Tire-Derived Fuel

The high temperature processing of cement manufac-
turing enables the industry to utilize scrap tires as an
alternative fuel source. The rubber elements of tires are
comprised of hydrocarbon compounds which, like coal
and oil, have tremendous fuel value. Tires have 25%
more fuel value than coal on an equal mass basis (PCA
2008).
Approximately 300 million used tires are generated
annu- ally in the United States (RMA 2009). The EPA
recognizes tire derived fuel (TDF) as an environmental
best practice and encourages industries to use this
resource. Using
tire-derived fuel in cement manufacturing (Figure 3-13)
recovers energy and conserves fossil fuel resources
other- wise destined for landfills or unregulated
disposal loca- tions. The intense heat of the kiln ensures
complete destruction of the tires. There are no visible
emissions from the tires, rather, the use of tires as fuel
can actually reduce certain emissions (PCA 2008).

Figure 3-13. Whole rubber tires introduced directly into the kiln by
conveyor as an alternative fuel.

Combustion Emissions
The U.S. cement industry has a goal of reducing CO2
emissions by 10% per ton of cement (from 1990 baseline
levels) by the end of 2020. In addition, 90% of U.S.
plants will adopt auditable and verifiable
environmental man- agement systems by 2020 (PCA
2009). The most recent progress in reduction of
combustion emissions involves

9
Design and Control of Concrete Mixtures ◆ EB001

changes in cement specifications. The changes, Type III High early strength
introduced in ASTM C150, Standard Specification for
Type IIIA High early strength, air-entraining
Portland Cement, in 2004 and harmonized with AASHTO
M 85 in 2007, permit up to 5% by mass of the final Type IV Low heat of hydration
cement product to consist of naturally occurring, finely Type V High sulfate resistance
ground limestone.
This allows for use of unburned or uncalcined ground
limestone as a component in finished cement ultimately
reducing CO2 (by calcination) by approximately 2.5
million metric tons (2.8 million short tons) per year
(Ashley and Lemay 2008 and Nisbet 1996). In 2009, ASTM
C150 and AASHTO M 85 were again changed to also
allow up to 5% inorganic processing additions, such as
fly ash and slag.
The use of limestone and inorganic processing additions
reduces the amount of raw materials and electricity used
in cement manufacture. For more on the effects of lime-
stone and inorganic processing addition on the properties
of cement and concrete, see Hawkins, Tennis, and
Detwiler (2005), and Taylor 2008. Further emission
reductions are achieved by using alternative waste fuels.
In most cases these waste fuels would otherwise be
disposed of in incin- erators decreasing their value as an
energy source. For more information on emission
reductions, see the PCA Report on Sustainable
Manufacturing at [Link]. org/smreport09 and the
World Business Council for Sustainable Development
Cement Sustainability Initiative at
[Link].

Types of Portland Cement

Different types of portland cement are manufactured to

meet various physical and chemical requirements for
specific purposes. Portland cements are manufactured to
meet the specifications of ASTM C150 or AASHTO M 85,
(also see Performance Based Hydraulic Cements for
port- land cements meeting ASTM C1157, Standard
Performance Specification for Hydraulic Cement). The
requirements of AASHTO M 85 and ASTM C150 are
equivalent. AASHTO specifications are used by some
state departments of transportation in lieu of ASTM
standards.
ASTM C150 (AASHTO M 85) provides for ten types of
portland cement:
Type I Normal
Type IA Normal, air-entraining
Type II Moderate sulfate resistance
Type IIA Moderate sulfate resistance,
air-
entraining
Type II (MH) Moderate heat of hydration and
moderate sulfate resistance
Type II (MH)A Moderate heat of hydration and
moderate sulfate resistance,
air- entraining

10
A detailed review of ASTM C150 (AASHTO M 85)
cements follows.
Type I
Type I portland cement is a general-purpose cement
suitable for all uses where the special properties of other
cement types are not required. Its uses in concrete
include pavements, floors, reinforced concrete buildings,
bridges, tanks, reservoirs, pipe, masonry units, and
precast concrete products (Figure 3-14).

Figure 3-14. Typical uses for normal or general use cements include
(left to right) highway pavements, floors, bridges, and buildings.

Type II
Type II portland cement is used where protection
against moderate sulfate attack is necessary. It is used
in normal structures or elements exposed to soil or
ground waters where sulfate concentrations are higher
than normal, but not unusually severe (see Table 3-2,
and Figures 3-15
to 3-17). Type II cement has moderate sulfate resistant
properties because it contains no more than 8%
tricalcium aluminate (C3A).

Sulfates in moist soil or water may enter the concrete

and react with the hydrated C3A, resulting in
expansion, scaling, and cracking of concrete. Some
sulfate com- pounds, such as magnesium sulfate,
directly attack calcium silicate hydrate.

The use of Type II cement in concrete must be accompa-

nied by the use of a low water-to-cementitious materials
ratio and low permeability to effectively control sulfate
attack. Figure 3-15 (left) illustrates the improved sulfate
resistance of Type II cement over Type I cement.
Concrete exposed to seawater is often made with Type
II cement. Seawater contains significant amounts of
sulfates and chlorides. Although sulfates in seawater are
capable of attacking concrete, the presence of chlorides in
seawater inhibits the expansive reaction that is
characteristic of sulfate attack. Thus, a marine
environment is an applica- tion requiring a moderate
sulfate exposure class. Observa- tions from a number of
sources show that the performance

11
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Table 3-2. Types of Cement Required for Concrete Exposed to Sulfate in Soil or Water*

Sulfate exposure** Cementitious materials requirements†

Water-soluble sulfate Dissolved sulfate Maximum
Exposure class in soil, % by mass in water, ppm C150 C595 C1157 w/cm

S0 Negligible SO4 < 0.10 SO4 < 150 NSR NSR NSR None

IP(MS)
IS(< 70)(MS)
IT(P  S)(MS)
S1 Moderate‡ 0.10 < SO4 < 0.20 150 < SO4 < 1500 II or II(MH) IT(P < S < 70)(MS) MS 0.50

IP(HS)
IS(< 70)(HS)
IT(P  S)(HS)
S2 Severe 0.20 < SO4 < 2.00 1500 < SO4 < 10,000 V IT(P < S < 70) HS 0.45
(HS)
IP(HS)
IS(< 70)(HS)
IT(P  S)(HS)
S3§ Very severe SO4 > 2.00 SO4 > 10,000 V IT(P < S < 70) HS 0.40
(HS)
* Adapted from Bureau of Reclamation Concrete Manual, ACI 201 and ACI 318. “NSR” indicates no special requirements for sulfate
resistance.
** Soil is tested per ASTM C1580 and water per ASTM D516.
† Pozzolans and slag that have been determined by testing according to ASTM C1012 or by service record to improve sulfate resistance may
also be used in concrete. Maximum expansions when using ASTM C1012: Moderate exposure – 0.10% at 6 months; Severe exposure –
0.05% at 6 months or 0.10% at 12 months; Very Severe exposure – 0.10% at 18 months. Refer to ACI 201.2R for more guidance. ASTM
C595 Type IT was adopted in 2009 and has not been reviewed by ACI at the time of printing.
‡ Includes seawater.
§ ACI 318 requires SCMs (tested to verify improved sulfate resistance) with Types V, IP(HS), IS(< 70)(HS) and HS cements for exposure class
S3. ACI 318 requires a maximum water:cement ratio of 0.45 for exposure class S3.

1 1

w/c = 0.38
w/c = 0.47
2 2 w/c = 0.68

ASTM Type V, 4% C3A

w/c = 0.37
3 ASTM Type II, 8% C3A 3
Visual
Visual

w/c = 0.38
ASTM Type I, 13% C3A
w/c = 0.39
4 4

Cement content = 390 kg/m3 (658 lbs/yd3)

5
0 2 4 6 8 10 12 14 16 5
Age, years 0 2 4 6 8 10 12 14 16
Age, years

Figure 3-15. (left) Performance of concretes made with different cements in sulfate soil. Type II and Type V cements have lower C3A contents that
improve sulfate resistance. (right) Improved sulfate resistance results from low water to cementitious materials ratios as demonstrated over time for
concrete beams exposed to sulfate soils in a wetting and drying environment. Shown are average values for concretes containing a wide range of
cementitious materials, including cement Types I, II, V, blended cements, pozzolans, and slags. See Figure 3-17 for rating illustration and a descrip-
tion of the concrete beams (Stark 2002).

12
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-16. Moderate sulfate resistant cements and high sulfate resistant cements improve the sulfate resistance of concrete elements, such as
(left to right) slabs on ground, pipe, and concrete posts exposed to high-sulfate soils.

of the need for sulfate resistance. Some cements are also

labeled with more than one type designation, for example
Type I/II. This simply means that such a cement meets the
requirements of both cement Types I and II.
Type II (MH)
Type II (MH) cements are manufactured to generate heat
at a slower rate than Type I or most Type II cements by
limiting the heat index to a maximum of 100. (The heat
index is the sum of C3S + 4.75 C3A). This requirement is
roughly equivalent to heat of hydration measurements
of 335 kJ/kg at 7 days using ASTM C186, Standard Test
Method for Heat of Hydration of Hydraulic Cement (Poole
2009). As an alternate to the heat index requirement, an
optional requirement can be specified limiting the heat
of hydration to 290 kJ/kg as determined by ASTM C186.
Type II (MH) (or Type IV, if available) can often be used in
structures of considerable mass, such as large piers, large
foundations, and thick retaining walls (Figure 3-18). Using
MH cements will reduce temperature rise, peak tempera-
ture and, minimize temperature related cracking. Thermal
control is especially important when concrete is placed in
warm weather (see Chapter 16).

Figure 3-17. Specimens used in the outdoor sulfate test plot in

Sacramento, California, are 150 x 150 x 760-mm (6 x 6 x 30-in.)
beams. A comparison of ratings is illustrated: (top) a rating of
5 for 12-year old concretes made with Type V cement and
a water-to-cement ratio of 0.65; and (bottom) a rating of 2
for
16-year old concretes made with Type V cement and a water-to-
cement ratio of 0.37 (Stark 2002).

of concretes in seawater with portland cements having

C3A contents as high as 10%, have demonstrated satisfac-
tory durability, providing the permeability of the concrete
is low and the reinforcing steel has adequate cover Figure 3-18. Moderate heat and low heat cements minimize heat
generation in massive elements or structures such as (left) very thick
(Zhang, Bremner, and Malhotra 2003). Chapter 11
bridge supports, and (right) dams. Hoover dam, shown here, used a
provides more information on sulfate attack. Type IV cement to control temperature rise.
Because of its increased availability, Type II cement is
sometimes used in all aspects of construction, regardless

13
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Type II(MH) cements are also moderately sulfate ASTM C150 (AASHTO M 85) allows both a chemical
resistant, as the maximum tricalcium aluminate content approach (for example, limiting C3A) and a physical
(C3A) is limited to a maximum of 8% by mass. approach (ASTM C452 expansion test) to assure the
Type III sulfate resistance of Type V cement. Either the chemical
or the physical approach can be specified, but not both.
Type III portland cement provides strength at an earlier
period than normally expected. For example, strength Air-Entraining Portland Cements
may be achieved in a matter of days as compared to the
Specifications for four types of air-entraining portland
typical expectation of 28 days. Type III is chemically cement (Types IA, IIA, II [MH]A, and IIIA) are given in
similar to Type I cement, except that its particles have ASTM C150 and AASHTO M 85. They correspond in
been ground finer. It is used when forms need to be composition to ASTM Types I, II, II(MH), and III, respec-
removed as soon tively, except that small quantities of air-entraining addi-
as possible or when the structure must be put into tions are interground with the clinker during
service quickly. In cold weather its use permits a manufacture. These cements produce concrete with
reduction in the length of the curing period (Figure 3- improved resistance to freezing and thawing. When
19). mixed with proper inten- sity and for an appropriate
Type IV duration, such concrete con- tains minute, well-
distributed, and completely separated air bubbles. Air
Type IV portland cement is used where the rate and entrainment for most concretes is achieved through the
amount of heat generated from hydration must be mini- use of an air-entraining admixture, rather than through
mized. It develops strength at a slower rate than other the use of air-entraining cements. Air-entraining cements
cement types. Type IV cement is intended for use in mas- are available only in certain areas, so it is advis- able to
sive concrete structures, such as large gravity dams (Fig- check on local availability.
ure 3-18), where the temperature rise resulting from heat
generated during hardening must be minimized. Type IV White Portland Cements
cement is not commonly manufactured in North America
White portland cement is a portland cement that differs
as there are other, more economical, measures for control- from gray cement chiefly in color. It is made to conform
ling heat rise in concrete available; such as the use of to the specifications of ASTM C150, usually Type I or
blended cements and supplementary cementing Type
materials.
III. The manufacture of white cement is accomplished by
Type V limiting the amount of iron and magnesium oxides in the
raw materials. These two oxides are responsible for port-
Type V portland cement is used in concrete exposed to land cement’s characteristic gray color. White portland
severe sulfate environments – principally where soils or cement is used primarily for architectural purposes in
groundwaters have a high sulfate content. It gains structural walls, precast and glass fiber reinforced
strength more slowly than Type I cement. Table 3-2 lists concrete (GFRC) facing panels, terrazzo surfaces, stucco,
sulfate concentrations requiring the use of Type V cement paint, tile grout, and decorative concrete (Figure
cement. The high sulfate resistance of Type V cement is 3-20). Its use is recommended wherever white or colored
attributed to a low tricalcium aluminate content, not concrete, grout, or mortar is desired and should be
more than 5%. The use of a low water to cementitious specified as white portland cement meeting the
materials ratio and low permeability are critical to the specifications of ASTM C150, Type [I, II, III, or V]. White
performance of any con- crete exposed to sulfates. Even cement is also used to manufacture white masonry
Type V cement concrete cannot withstand a severe cement meeting ASTM C91 and white plastic cement
sulfate exposure if the concrete has a high water- meeting ASTM C1328 (PCA 1999). White cement was first
cementitious materials ratio (Figure 3-17 top). Type V manufactured in the United States in York, Pennsylvania
cement, like other portland cements, is not resistant to in 1907. See Farny (2001) for more information on white
acids and other highly corrosive substances. cement.

14
Figure 3-19. High early strength cements are used where early concrete strength is needed, such as in (left to right) cold weather concreting, fast
track paving to minimize traffic congestion, and rapid form removal for precast concrete.

15
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-20. White portland cement is used in white or light-colored architectural concrete, ranging from (left to right) terrazzo for floors shown here
with white cement and green granite aggregate , to decorative and structural precast and cast-in-place elements, to building exteriors. The far right
photograph shows a white precast concrete building housing the ASTM Headquarters in West Conshohocken, Pennsylvania (Courtesy of ASTM).

Blended Hydraulic Cements

Blended hydraulic cements are produced by intimately and
uniformly intergrinding or blending two or more types of
fine materials. The primary materials are portland cement,
slag cement, fly ash, silica fume, calcined clay, other poz-
zolans, hydrated lime, and preblended combinations of
these materials (Figure 3-21). Blended hydraulic cements
must conform to the requirements of ASTM C595 or
AASHTO M 240, Specification for Blended Hydraulic Cements
(also see Performance Based Hydraulic Cements for
blended cements meeting ASTM C1157).

AASHTO M 240 also uses class designations for blended Figure 3-21. Blended cements use a combination of portland
cement. The requirements of M 240 are nearly identical cement or clinker and gypsum blended or interground with
pozzolans, slag, or fly ash. Shown is blended cement (center)
to those in ASTM C595.
surrounded by (right and clockwise) clinker, gypsum, portland cement,
fly ash, slag, silica fume, and calcined clay.
ASTM C595 recognizes three primary classes of blended
cements as follows:
Blended cements are used in all aspects of concrete
Type IS (X) Portland blast-furnace slag construction in the same manner as portland cements.
cement Type IP (X) Portland-pozzolan cement Blended cements can be used as the sole cementitious
Type IT(AX)(BY) Ternary blended cement material in concrete or they can be used in combination
with other supplementary cementitious materials added
The letters “X” and “Y” represent the nominal mass at the concrete plant.
percentage of the SCM included in the blended cement
with the remaining mass percentage being portland A detailed review of ASTM C595 and AASHTO M 240
cement. For example, a cement designated as Type IS(50) blended cements follows:
contains 50% by mass of slag cement (and 50% portland
cement). For ternary blended cements, “A” is the type of Type IS
SCM present in the largest amount (“X”) while “B” is the Portland blast-furnace slag cement is manufactured by
remaining SCM type. “A” or “B” may be either S for slag either: (1) intergrinding portland cement clinker and
cement, or P for pozzolan. “X” and “Y” are the gran- ulated blast-furnace slag (or slag cement), (2)
correspon- ding percentages of those SCMs. As an blending portland cement and slag cement, or (3) a
example, Type IT(S25)(P10) indicates a ternary blended combination of intergrinding and blending. Portland
cement with 25% slag cement and 10% pozzolan for a blast-furnace slag is classified into two categories
total of 35% by mass of SCMs. In this example, portland depending on its slag cement content: Type IS(< 70) has
cement accounts for 65% of the total cementitious less than 70% by mass of slag cement and is suitable for
content. general concrete construction, while Type IS( 70) has
70% slag cement or more by mass, may contain hydrated
Types IS(<70), IP, and IT(P< S< 70), and Type IT(P  S) lime, and is used in conjunction with portland cement in
are general purpose cements; these and their associated
making concrete or with lime in making mortar, but is
sub- category types are reviewed in the following
not used alone for structural
discussion.

16
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

concrete applications. Both types of Type IS cement in- cement and blended hydraulic cements. Cements meeting
clude subcategories for optional special properties such the require- ments of ASTM C1157 meet physical
as air-entrainment, moderate sulfate resistance, high performance test requirements, as opposed to prescriptive
sulfate resistance, or moderate heat of hydration. They restrictions on
may be specified by adding the suffixes A, MS, HS, or
MH, re- spectively. For example, an air-entraining
portland blast- furnace slag cement with 40% slag that
has high sulfate resistance would be designated as Type
IS(40)-A (HS).
For more information on blended cements with slag
cement, see Klieger and Isberner (1967) and PCA
(1995).

Type IP
Portland-pozzolan cements are designated as Type IP.
Type IP cement may be used for general construction.
These cements are manufactured by intergrinding port-
land cement clinker with a suitable pozzolan, by
blending portland cement and a pozzolan, or by a
combination of intergrinding and blending. The pozzolan
content of these cements is up to 40% by mass.
Laboratory tests indicate that performance of concrete
made with Type IP cement as a group is similar to that of
Type I cement concrete.
Type IP may be designated as air-entraining, moderate
sulfate resistant, high sulfate resistant, low heat of
hydra- tion, or with moderate heat of hydration by
adding the suffixes A, MS, HS, LH, or MH.

Type IT
Ternary blended cements can sometimes offer advantages
over binary blended cements. The combinations of dif-
ferent cementitious materials provided by ternary
blended cements may optimize the overall performance
of these cements for a specific application. For example, a
rapidly reacting pozzolan like silica fume might be
combined with a slower reacting material such as fly ash
to enhance both early and longer term strength
development. Other crete properties might be improved
as well, such as reduced permeability and resistance to
ASR.

Type IT ternary blended cements meet the same

chemical and physical requirements as for binary
blended cements for the SCM present in the largest
amount. For instance, if slag cement is present in the
highest amount in a Type IT cement, the provisions of
Type IS apply, while if a pozzo- lan is present in the
highest amount, then the requirements of Type IP apply.
The provisions of Type IP also apply if the pozzolan and
slag cement content are the same.

Performance Based Hydraulic Cements

All portland and blended cements are hydraulic
cements. “Hydraulic cement” is merely a broader term.
(See also ASTM C219 for terms relating to hydraulic
cements.) ASTM C1157 can apply to both portland

17
ingredients or cement chemistry as found in other
cement specifications. ASTM C1157 provides for six
types of hydraulic cement as follows:
Type GU General use
Type HE High early strength
Type MS Moderate sulfate
resistance Type HS High sulfate
resistance Type MH Moderate heat
of hydration Type LH Low heat of
hydration

In addition, these cements can also include an Option R

– Low Reactivity with Alkali-Reactive Aggregates – spe-
cified to help control alkali-silica reactivity. An “R” is
appended to the cement type: for example, Type GU-R
is a general use hydraulic cement that has low reactivity
when used with alkali-reactive aggregates.

A detailed review of ASTM C1157 cements follows:

Type GU
Type GU is a general purpose cement suitable for all
applications where the special properties of other types
are not required. Its uses in concrete include pavements,
floors, reinforced concrete buildings, bridges, pipe,
precast concrete products, and other applications where
Type I
is used.

Type HE
Type HE cement provides higher strengths at an early
age, usually a week or less. It is used in the same
manner as Type III portland cement, and has the same
1- and 3-day strength requirements.

Type MS
Type MS cement is used where precaution against
moderate sulfate attack is important. Applications may
include drainage structures where sulfate
concentrations in ground waters are higher than
normal but not unusu- ally severe (see Table 3-2). It is
used in the same manner as Type II and II(MH)
portland cement. Like Type II and II(MH), Type MS
cement concrete must be designed with a low water-
cementitious materials ratio to provide ade- quate
sulfate resistance. ASTM C1157 also requires that
mortar bar specimens demonstrate resistance to
expansion while exposed to solution containing a high
concentration of sulfates (ASTM C1012).

Type HS
Type HS cement is used in concrete exposed to severe
sulfate action – principally where soils or ground waters
have a high sulfate content (see Table 3-2). It is used in
the same manner as Type V portland cement. As noted
previ- ously, low water-cementitious materials ratios are
criti- cally important to assure performance of concrete
exposed to sulfate exposures. Similar to MS cements,
ASTM C1157

18
Design and Control of Concrete Mixtures ◆ EB001

also requires that mortar bar specimens demonstrate one or more properties such as setting time, workability,
resistance to expansion while exposed to solution water retention, and durability. These components are
con- taining a high concentration of sulfates (ASTM proportioned and packaged at a cement plant under
C1012). controlled conditions to assure uniformity of
performance.
Type MH
Type MH cement is used in applications requiring a mod-
erate heat of hydration and a controlled temperature rise.
Type MH cement is used in the same manner as Type
II(MH) portland cement.

Type LH
Type LH cement is used where the rate and amount of
heat generated from hydration must be minimized. It
develops strength at a slower rate than other cement
types. Type LH cement is intended for use in massive
concrete structures where the temperature rise
resulting from heat generated during hardening must
be mini- mized. It is used as an alternative to Type IV Figure 3-22. Masonry cement and mortar cement are used to
portland cement or in the same manner as a Type make mortar to bond masonry units together.
IP(LH) or IT(PS)(LH) blended cement.
Masonry cements meet the requirements of ASTM C91,
Table 3-3 provides a matrix of commonly used Standard Specification for Masonry Cement. ASTM C91
cements and their typical applications in concrete classifies masonry cements as Type N, Type S, and Type
construction. M. White masonry cement and colored masonry cements
meeting ASTM C91 are also available in some areas.
Mortar cements meet the requirements of ASTM C1329,
Special Cements Standard Specification for Mortar Cement. Mortar cements
are further classified as Type N, Type S, and Type M. A
Special cements are produced for particular applications. brief description of each type follows:
Table 3-4 summarizes the special cements discussed
below. See Odler (2000) and Klemm (1998) for more Type N masonry cement and Type N mortar cement are
information. used to produce ASTM C270 Type N and Type O mortars.
They may also be used with portland or blended cements
Masonry and Mortar Cements to produce Type S and Type M mortars.
Masonry cements and mortar cements are hydraulic Type S masonry cement and Type S mortar cement are
cements designed for use in mortar for masonry construc- used to produce ASTM C270, Standard Specification for
tion (Figure 3-22). They consist of a mixture of portland Mortar for Unit Masonry, Type S mortar. They may also be
cement or blended hydraulic cement and plasticizing used with portland or blended cements to produce Type
materials (such as limestone or hydrated or hydraulic M mortar.
lime), together with other materials introduced to enhance

Table 3-3. Applications for Hydraulic Cements Used in Concrete Construction*

Resistance to
Cement General Moderate heat of High early Low heat of Moderate sulfate High sulfate alkali-silica
specification purpose hydration strength hydration resistance resistance reaction (ASR)**
ASTM C150
Low-alkali
portland I II(MH) III IV II, II(MH) V
option
cements

ASTM C595 IP IP(MH) IS(<70) IP(MS) IS(<70) IP(HS) IS(<70)

IP(LH)
blended IS(<70) (MH) (MS) (HS) Low reactivity
— IT(PS)(LH)
hydraulic IT(P<S<70) IT(P<S<70)(MH) IT(P<S<70)(MS) IT(P<S<70)(HS) option
cements IT(PS) IT(PS)(MH) IT(PS)(MS) IT(PS)(HS)
ASTM C1157
hydraulic GU MH HE LH MS HS Option R
cements
*Check the local availability of specific cements as all cements are not available everywhere.

19
**The option for low reactivity with ASR-susceptible aggregates can be applied to any cement type in the columns to the left.

20
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Table 3-4. Applications for Special Cements

Special cements Type Application

White portland cements, I, II, III, V White or colored concrete, masonry, mortar,
ASTM C150 grout, plaster, and stucco
White masonry cements, M, S, N White mortar between masonry units
ASTM C91
Masonry cements, ASTM C91 M, S, N Mortar between masonry units*, plaster,
and stucco**
Mortar cements, ASTM C1329 M, S, N Mortar between masonry units*
Plastic cements, ASTM C1328 M, S Plaster and stucco**
Expansive cements, ASTM C845 E-1(K), E-1(M), E-1(S) Shrinkage compensating concrete
Oil-well cements, API-10A A, B, C, D, E, F, G, H Grouting wells
Water-repellent cements Tile grout, paint, and stucco finish coats
Regulated-set cements Early strength and repair***
Cements with functional additions, General concrete construction needing special
ASTM C595 (AASHTO M 240), ASTM C1157 characteristics such as: water-reducing, retarding,
air entraining, set control, and accelerating properties
Finely ground (ultrafine) cement Geotechnical grouting***
Calcium aluminate cement Repair, chemical resistance, high temperature
exposures
Magnesium phosphate cement Repair and chemical resistance
Geopolymer cement General construction, repair, waste stabilization***
Ettringite cements Waste stabilization***
Sulfur cements Repair and chemical resistance
Rapid hardening hydraulic URH, VRH, MRH, GRH General paving where very rapid (about 4
cement, ASTM C1600 hours) strength development is required
Natural cement, ASTM C10 Historic restoration of natural cement mortar, cement
plaster, grout, whitewash, and concrete
* Portland cement Types I, II, and III and blended cement Types IS and IP are also used in making mortar.
** Portland cement Types I, II, and III and blended cement Types IP and IS(70) are also used in making plaster.
*** Portland and blended hydraulic cements are also used for these applications.

Type M masonry cement and Type M mortar cement

through the use of modern manufacturing controls. In
are used to produce ASTM C270 Type M mortar
addition to mortar for masonry construction, masonry
without the addition of other cements or hydrated lime.
cements and mortar cements are commonly used for
Types N, S, and M generally have increasing levels of parging. Masonry cements are also used in portland-
port- land cement and higher strength with Type M cement based plaster or stucco (Figure 3-20) construction
providing the highest strength. Type N masonry and (see ASTM C926, Standard Specification for Application of
mortar cements are most commonly used for above Portland Cement-Based Plaster). Masonry cement and
grade masonry. mortar cement are not suitable for use in concrete
production.
The increased use of masonry in demanding structural
applications, such as high seismic areas, resulted in the Plastic Cements
relatively recent development of mortar cement. Mortar Plastic cement is a hydraulic cement that meets the
cement is similar to masonry cement in that it is a requirements of ASTM C1328, Standard Specification for
factory- prepared cement primarily used to produce Plastic (Stucco) Cement. It is used to produce portland
masonry mortar with higher strength and lower air cement-based plaster or stucco (ASTM C926). These
content. ASTM C1329 places lower maximum air content cements are popular throughout the southwest and west
limits on mortar cement than the limits for masonry coast of the United States (Figure 3-23). Plastic cements
cements, Also, ASTM C1329 is the only ASTM masonry consist of a mixture of portland and blended hydraulic
material specification that includes bond strength cement and plasticizing materials (such as limestone,
performance criteria. hydrated or hydraulic lime), together with materials
intro- duced to enhance one or more properties such as
The workability, strength, and color of masonry cements setting time, workability, water retention, and durability.
and mortar cements remain at a high level of
uniformity
21
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-23. Masonry cement and plastic cement are used to make plaster or stucco for commercial, institutional, and residential buildings. Shown
are a church and home with stucco exteriors. Inset shows a typical stucco texture.

ASTM C1328 defines separate requirements for Type M contains portland cement, calcium aluminate cement, and
and Type S plastic cement with Type M having higher calcium sulfate. Type E-
strength requirements. The International Building Code
(IBC) does not classify plastic cement into different types,
but does specify that it must meet the requirements of
ASTM C1328 plastic cement. When plastic cement is
used, lime or any other plasticizer may not be added to
the plaster at the time of mixing.

The term “plastic” in plastic cement does not refer to

the inclusion of any organic compounds in the
cement.
Instead, “plastic” refers to the ability of the cement to
introduce a higher degree of workability (“plasticity”) to
the plaster. Plaster using this cement must remain work-
able long enough for it to be reworked to obtain the de-
sired densification and texture. Plastic cement should
not be used to make concrete. For more information on
the use of plastic cement and plaster, see Melander,
Farny, and Isberner (2003).

Finely-Ground Cements (Ultrafine Cements)

Finely-ground cements, also referred to as ultrafine
cements, are hydraulic cements that are ground very
fine for use in grouting into fine soil or thin rock
fissures (Figure 3-24). The cement particles are less than
10 µm
in diameter with 50% of particles less than 5 µm. Blaine
surface area of these cements often exceeds 800 m2/kg.
These very fine cements consist of portland cement,
slag cement, and other mineral additives.

Expansive Cements
Expansive cement is a hydraulic cement that expands
slightly during the early hardening period after initial
set. It must meet the requirements of ASTM C845,
Standard Specification for Expansive Hydraulic Cement,
where it is designated as Type E-1. Currently, three
varieties of ex- pansive cement are recognized. They are
designated as K, M, and S. These designations are added
as a suffix to the type. Type E-1(K) contains portland
cement, tetracalcium trialuminosulfate, calcium sulfate,
and uncombined cal- cium oxide (lime). Type E-1(M)

22
1(S) contains portland cement with a high
tricalcium aluminate content and calcium sulfate.
Type E-1(K) is the most readily available
expansive cement in North America.

Expansive cement may also contain formulations

other than those noted. The expansive properties of
each type can be varied over a considerable range.

When expansion is restrained, for example by

reinforcing steel, expansive cement concrete (also
called shrinkage compensating concrete) can be used
to: (1) compensate for the volume decrease associated
with drying shrink- age, (2) induce tensile stress in
reinforcement (post- tensioning), and (3) stabilize the
long-term dimensions
of post-tensioned concrete structures in comparison
to the original design dimensions.

Figure 3-24. (top) A slurry of

finely ground cement and water
can be injected into the ground,
as shown here, to stabilize in-
place materials, to provide
strength for foundations, or to
chemically retain contami- nants
in soil. Illustration (right) of grout
penetration in soil.

23
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

One of the major advantages of expansive cement in C1600, Standard Specification for Rapid Hardening
concrete as noted above, is the compensation for volume Hydraulic Cement, as
changes caused by drying shrinkage. Expansive cement
can control and reduce drying shrinkage cracks
commonly associated with the use of portland cement.
Figure 3-25 illustrates the length change (early expansion
and drying shrinkage) history of shrinkage-compensating
concrete and conventional portland cement concrete. For
more information see Pfeifer and Perenchio (1973),
Russell (1978), and ACI Committee 223 (1998).
0.10
Moist-cured for 7 days, followed by air drying at 23C (73F)
0.08 Restrained by reinforcing steel, p = 0.35%

0.06 Shrinkage-compensating concrete

Length change, percent

0.04

0.02

-0.02
Portland cement concrete
-0.04

-0.06
0 7 50 100 150 200
Time, days

Figure 3-25. Length-change history of shrinkage compensating

concrete containing Type E-1(S) cement and Type I portland cement
concrete (Pfeifer and Perenchio 1973).

Oil-Well Cements
Oil-well cements are used for oil-well grouting. (This
procedure is often called oil-well cementing). Oil-well
cements are usually made from portland cement clinker
or from blended hydraulic cements. Generally they must
be slow-setting and resistant to high temperatures and
pres- sures. The American Petroleum Institute’s Specification
for Cements and Materials for Well Cementing (API
Specifica- tion 10A) includes requirements for eight
classes of well cements (Classes A through H) and three
grades (Grades O
– ordinary, MSR – moderate sulfate resistant, and HSR –
high sulfate resistant). Each class is applicable for use at a
certain range of well depths, temperatures, pressures,
and sulfate environments. The petroleum industry also
uses conventional types of portland cement with
suitable cement-modifiers. (ASTM C150 Type II or Type V
cements may meet requirements for API Class G and H
cements, while API Class A, Class B, and Class C cements
are similar to ASTM Types I, II, and III respectively.)
Expansive cements have also performed adequately as
well cements.

Rapid Hardening Cements

Rapid hardening, high-early strength, hydraulic
cement is used in construction applications, such as
fast-track paving, where fast strength development is
required (design or load-carrying strength in about
four hours). They are classified according to ASTM
24
Type URH – ultra rapid hardening, Type VRH – very not contain organic poly- mers or plastics.
rapid hardening, Type MRH – medium rapid
hardening, and Type GRH – general rapid hardening.

Cements with Functional Additions

Functional additions can be interground with cement
clinker to beneficially change the properties of hydraulic
cement. These additions must meet the requirements of
ASTM C226, Standard Specification for Air-Entraining Addi-
tions for Use in the Manufacture of Air-Entraining Hydraulic
Cement, or ASTMC688, Standard Specification for Functional
Additions for Use in Hydraulic Cements. ASTM C226
addresses air-entraining additions while ASTM C688
addresses the following types of additions: water-
reducing, retarding, accelerating, water-reducing and
retarding, water-reducing and accelerating, and set-
control additions. Cement specifi- cations ASTM C595
(AASHTO M 240) and C1157 allow functional additions.
These additions can be used to en- hance the performance
of the cement for normal or special concrete construction,
grouting, and other applications.

Water-Repellent Cements
Water-repellent cements, sometimes called
waterproofed cements, are usually made by adding a
small amount of water-repellent additive such as
stearate (sodium, alum- inum, or other) to cement
clinker during final grinding (Lea 1971).
Manufactured in either white or gray color, water-
repellent cements reduce capillary water transmis-
sion provided there is little to no hydrostatic pressure.
However, they do not stop water-vapor
transmission. Water-repellent cements are used in
tile grouts, paint, stucco finish coats, and in the
manufacture of specialty precast units.

Regulated-Set Cements
Regulated-set cement is a calcium fluoroaluminate hy-
draulic cement that can be formulated and controlled
to produce concrete with setting times ranging from a
few minutes to one hour and with corresponding rapid
early strength development (Greening and others
1971). It is a portland-based cement with functional
additions that can be manufactured in the same kiln
used to manufacture conventional portland cement.
Regulated-set cement in- corporates set control and
early-strength-development components. The final
physical properties of the resulting concrete are in
most respects similar to comparable concretes made
with portland cement.

Geopolymer Cements
Geopolymer cements are inorganic hydraulic cements
that are based on the polymerization of minerals
(Davidovits, Davidovits, and James 1999 and
[Link]).
The term more specifically refers to alkali-activated
alumino-silicate cements, also called zeolitic or
polysia- late cements. These cements often contain
industrial by- products, such as fly ash. They have
been used in general construction, high-early strength
applications, and waste stabilization. These cements do

25
Design and Control of Concrete Mixtures ◆ EB001

Ettringite Cements make sulfur cement concrete for repairs and chemically
resistant applications. Sulfur cement melts at tempera-
Ettringite cements are calcium sulfoaluminate cements
that are specially formulated for particular uses, such as
the stabilization of waste materials (Klemm 1998). They
can be formulated to form large amounts of ettringite to
stabilize particular metallic ions within the ettringite
structure. Ettringite cements have also been used in
rapid setting applications, including use in coal mines.
Also see “Expansive Cements” above.

Calcium Aluminate Cements

Calcium aluminate cement is not portland cement based.
It is used in special applications for early strength gain
(for example, to achieve design strength in one day),
resistance to high temperatures, and resistance to sulfates,
weak acids, and seawater. Portland cement and calcium
aluminate cement combinations have been used to make
rapid setting concretes and mortars. Typical applications
for calcium aluminate cement concrete include:
chemically resistant, heat resistant, and corrosion
resistant industrial floors; refractory castables; and repair
applications. Stan- dards addressing these cements
include British Standard BS 915-2 and French Standard
NF P15-315.

Calcium aluminate cement concrete must be used at

low water-cement ratios (less than 0.40); this minimizes
the potential for conversion of less stable hexagonal
calcium aluminate hydrate (CAH10) to the stable cubic
tricalcium aluminate hydrate (C3AH6), hydrous
alumina (AH3), and water. Given sufficient time and
particular moisture conditions and temperatures, this
conversion causes a 53% decrease in volume of
hydrated material. However, this internal volume
change occurs without a dramatic
alteration of the overall dimensions of a concrete
element, resulting in increased paste porosity and
decreased compressive strength. At low water-cement
ratios, there is insufficient space for all the calcium
aluminate to react and form CAH10. The released water
produced by the conversion reacts with additional
calcium aluminate, par- tially compensating for the
effects of conversion. Concrete design strength must
therefore be based on the converted strength. Because of
the unique concerns associated with
the conversion phenomenon, calcium aluminate cement
is often used in nonstructural applications and is rarely,
if ever used within structural applications (Taylor 1997).

Magnesium Phosphate Cements

Magnesium phosphate cement is a rapid setting, early
strength gain cement. It is usually used for special
applica- tions, such as repair of pavements and concrete
structures, or for resistance to certain aggressive
chemicals. It does not contain portland cement.

Sulfur Cements
Sulfur cement is used with conventional aggregates to

26
tures between 113°C and 121°C (235°F and 250°F). usually carried in stock and is furnished when no other
Sulfur concrete is maintained at temperatures around
130°C (270°F) during mixing and placing. The material
gains strength quickly as it cools and is resistant to
acids and aggressive chemicals. Sulfur cement does not
contain portland or hydraulic cement.

Natural Cements
Natural cements were used in the 1800s before
portland cement became popular. It is a coarse ground
hydraulic cement with slow strength gain properties
and was used in mortar, plaster, whitewashing, and
concrete. It was used extensively in canal, bridge, and
building construc- tion. It is still available for use in
restoring historic struc- tures and must meet ASTM
C10, Standard Specification for Natural Cement.

Other Cements
Magnesium silicates, fly ash cement, special alkali-
activated cements, and countless other cements with
unique chem- istry exist throughout the world. It is
beyond the scope of this document to address them. For
more information on special cements consult Odler (2000)
and other references.

Selecting and Specifying Cements

When specifying cements for a project, the availability

of cement types should be verified. Specifications
should allow flexibility in cement selection. Limiting a
project to only one cement type, one brand, or one
standard cement specification can result in project
delays and it may not allow for the best use of local
materials. Cements with special properties should not
be required unless special characteristics are necessary.
In addition, the use of SCMs should not inhibit the use
of any particular portland or blended cement. The
project specifications should focus on the needs of the
concrete structure and allow use of a variety of
materials to accomplish those needs. A typical
specification may call for portland cements meeting
ASTM C150 (AASHTO M 85), blended cements
meeting ASTM C595 (AASHTO M 240), or for
performance based hydraulic cements meeting ASTM
C1157.

If no special properties, (such as low-heat generation

or sulfate resistance) are required, all general use
cements should be permitted, including: Types I, GU,
IS(<70), IP, IT(PS), or IT(P<S< 70). Also, it should be
noted that some cement types meet more than one
specification requirement. For example, nearly all
Type II cements meet the requirements of Type I, but
not all Type I cements meet the requirements of Type
II. See Tables
3-3 and 3-4 for guidance on using different cements.

Availability of Cements
Some types of cement may not be readily available in all
areas of the United States.

ASTM C150 (AASHTO M 85) Type I portland cement is

27
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

type of cement is specified. Type II cement is usually standards other than those in ASTM or AASHTO. For
available, especially in areas of the country where mod- example, the European cement standard, EN 197-1, some-
erate sulfate resistance is needed. Cement Types I and II times appears on project specifications. EN 197 cement
represent about 80% of the cement shipped from plants
in the United States. Type III cement and white cement
are usually available in larger metropolitan areas and
repre- sent about 4% of cement produced. Type IV
cement is manufactured only when specified for
particular projects (massive structures like dams) and
therefore is usually not readily available. Type V cement
is available only in regions of the country having high
sulfate environments. Air-entraining cements are
sometimes difficult to obtain. Their use has decreased as
the popularity of air-entraining admixtures has
increased. Masonry cement is available in most areas. See
PCA (2010) for statistics on cement use.

If a given cement type is not available, comparable

results can frequently be obtained with another cement
type that is available. For example, high-early-strength
concrete can be made using concrete mixtures with
higher cement contents and lower water-cement ratios.
Also, the effects of heat of hydration can be minimized
using leaner mix- tures, smaller placing lifts, artificial
cooling, or by adding an SCM to the concrete. Type V
cement may at times be difficult to obtain, but because of
the range of phase com- position permitted in cement
specifications, a Type II cement may also meet the
requirements of a Type V.

Blended cements can be obtained throughout most of

the United States. However, certain types of blended
cement may not be available in some areas. When ASTM
C595 (AASHTO M 240) blended cements are required,
but are not available, similar properties may be obtained
by adding pozzolans meeting requirements of ASTM
C618, Standard Specification for Coal Fly Ash and Raw or
Calcined Natural Pozzolan for Use in Concrete (AASHTO
M 295) or slag cement meeting requirements of ASTM
C989, Stan- dard Specification for Slag Cement for Use in
Concrete and Mortars (AASHTO M 302) to the concrete at
a ready mix plant using normal portland cement. Like
any concrete mixture, these mixes should be tested for
time of set, strength gain, durability, and other
properties prior to their use in construction.

Drinking Water Applications

Concrete has demonstrated decades of safe use in
drinking water applications. Materials in contact with
drinking water must meet special requirements to
control elements entering the water supply. Some
localities may require that cement and concrete meet the
special require- ments of the American National
Standards Institute/ National Sanitation Foundation
standard ANSI/NSF 61, Drinking Water System
Components – Health Effects.

Canadian and European Cement Specifications

In some instances, projects in the United States designed
by engineering firms from other countries refer to cement

28
Types CEM I, II, III, IV, and V do not correspond to the medium (between 15% and 20% CaO by mass), and
cement types in ASTM C150, nor can ASTM cements be high cal- cium oxide (more than 20% CaO by mass)
substituted for EN specified cement without the contents.
designer’s approval. CEM I is a portland cement and
CEM II through V are blended cements. EN 197 also
includes strength classes and ranges (32.5, 42.5, and 52.5
MPa).

Some countries outside North America use ASTM stan-

dards to specify cement and concrete. However, for
other countries, there is typically no direct equivalency
between ASTM and international cement standards
because of differences in test methods and limits on
required proper- ties. EN 197 cements are usually not
available in the United States; therefore, the best
approach is to inform the designer about locally
available cements and request changes in the project
specifications that allow use of an ASTM or AASHTO
cement.

In Canada, portland cements are manufactured to meet

the specifications of the Canadian Standards Association
(CSA) Standard A3001 Cementitious Materials for Use in
Concrete. CSA A3001 includes portland cements,
blended cements, portland-limestone cements, and
portland-lime- stone blended cements.

CSA A3001 uses two-letter descriptive type designations

for portland cements similar to ASTM C1157 with
require- ments similar to ASTM C150. Six types of
portland cement are covered in CSA A3001 and are
identified as follows:
GU: General use hydraulic cement
MS: Moderate sulfate-resistant hydraulic
cement MH: Moderate heat of hydration
hydraulic cement HE: High early-strength
hydraulic cement
LH: Low heat of hydration hydraulic
cement HS: High sulfate-resistant hydraulic
cement

The nomenclature for blended hydraulic cements is a

three-letter descriptive designation (GUb, MSb, MHb,
HEb, LHb, and HSb) to address its equivalent
perform- ance to portland cements with up to three
supplementary cementing materials. Upon request, the
designations for blended cements can also provide
information on the composition of blended hydraulic
cements. The designa- tions then follow the form:
BHb-Axx/Byy/Czz, where BHb is the blended
hydraulic cement type, xx, yy, and zz are the
supplementary materials used in the cement in
proportions A, B, and C.
Supplementary cementitious materials
include: Ground granulated blast furnace slag
(S),
Silica fume (SF),
Natural pozzolans (N), and
Fly ash (Classes F, CI, and CH). Class F, CI, and CH
fly ashes are low (less than 15% CaO by mass),
29
Design and Control of Concrete Mixtures ◆ EB001

Examples: C4AF

MS – portland cement (with no supplementary cementi-

tious materials) for use when moderate sulfate
resistance is required.

GUb-30F/5SF – general use blended cement containing

30% by mass Class F fly ash (F) and 5% silica fume
(SF).

In addition, CSA A3001 includes provisions for portland-

limestone cements (PLC) with 5% to 15% by mass of
lime- stone. Four types of portland limestone cements are
defined and are designated by an “L” suffix: Type GUL,
Type HEL, Type MHL, and Type LHL. For the limestone
used in these cements, requirements are that: 1) the
calcium carbonate content is at least 75% by mass, 2) the
methylene blue index of the limestone (an indication of
clay content) in not more than 1.2 g/100 g, and 3) the
Total Organic Carbon (TOC) content of the limestone is
below 0.5% by mass.

CSA A3001 includes provisions for portland-limestone

blended cements, which contain between 5% and 15%
limestone, as well as SCMs. Type designations are GULb,
HELb, MHLb, LHLb, MSLb, and HSLb.

Chemical Phases (Compounds) and Hydration of

Portland Cement

During the burning operation in the manufacture of port-

land cement clinker, calcium combines with the other
com- ponents of the raw mix to form four principal
phases that make up about 85% to 90% of cement by
mass. Gypsum, or other calcium sulfate forms, limestone,
and grinding aids or other processing additions are also
added during finish grinding.

Cement chemists use the following chemical

shorthand (abbreviations):
A = Al2O3, C = CaO, F = Fe2O3, H = H2O, M = MgO,
S= SiO2, and … = SO3.

The term “phases” is generally used to describe the

components of clinker, because the word “compounds”
generally refers to specific, ideal compositions, while
the compositions of the phases in cement often include
trace elements. Following are the four primary phases
in port- land cement, their approximate chemical
formulas, and abbreviations:
Tricalcium silicate
3CaO • SiO2 = C3S
Dicalcium silicate
2CaO• SiO2 = C2S
Tricalcium aluminate
3CaO• Al2O3 = C3A
Tetracalcium aluminoferrite
4CaO• Al2O3 • Fe2O3 =
30
The forms of calcium sulfate, their chemical formulas,
and abbreviations are:
Anhydrous calcium sulfate
(anhydrite) CaSO4 = CaO• SO3 =
C…
Calcium sulfate dihydrate (gypsum)
CaSO4 • 2H2O = CaO • SO3 • 2H2O = C…H2
Calcium sulfate hemihydrate
CaSO4• 1⁄2H2O = CaO• SO3 • 1⁄2H2O = C…H1⁄2

Gypsum, calcium sulfate dihydrate, is the

predominant source of sulfate used in cement. Finish
grinding is often controlled to produce a balance of
hemihydrate and gyp- sum. The heat generated
during finish grinding will dehydrate a portion of the
calcium sulfate dehydrate into calcium sulfate
hemihydrate.

Primary Phases
C3S and C2S in clinker are also referred to as alite and
belite, respectively. Alite generally constitutes 50% to
70% of the clinker, whereas belite accounts for only
about
10% to 25% (Figure 3-26). Aluminate phases constitute
up to about 10% of the clinker and ferrite compounds
gener- ally up to as much as 15% (Bhatty and Tennis
2008). These and other phases may be observed and
analyzed through the use of microscopy (ASTM C1356,
ASTM C1365, and Campbell 1999).

Figure 3-26. (top) Polished thin-section examination of port-

land clinker shows alite (C3S) as light, angular crystals. The
darker, rounded crystals are belite (C2S). Magnification ap-
proximately 400X. (bottom) Scanning electron microscope
(SEM) micrograph of alite (C3S) crystals in portland clinker.
Magnification 3000X.

31
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

In the presence of water, these phases hydrate nate hydrate), calcium monosulfoaluminate, and other
(chemically react with water) to form new solids that are related compounds. C4AF reacts with water to form cal-
the infra- structure of hardened cement paste in concrete cium aluminoferrite hydrates. These basic reactions are
(Figure shown in Table 3-5. Brunauer (1957), Copeland and
3-27). The calcium silicates, C3S and C2S, hydrate to form others (1960), Lea (1971), Powers and Brownyard (1947),
calcium hydroxide and calcium silicate hydrate (archaic- Powers (1961), and Taylor (1997) addressed the pore
ally called tobermorite gel). Hydrated portland cement structure and chemistry of cement paste. Figure 3-29
paste typically contains 15% to 25% calcium hydroxide shows estimates of the relative volumes of the phases in
and about 50% calcium silicate hydrate by mass. The hydrated portland cement pastes. The Concrete
strength and other properties of hydrated cement are Microscopy Library (Lange and Stutzman 2009) provides
due primarily to calcium silicate hydrate (Figure 3-28). a collection of micrographs of cement hydration and
C3A, sulfates (gypsum, anhydrite, or other sulfate concrete.
source), and water combine to form ettringite (calcium
trisulfoalumi-

Figure 3-27. Electron micrographs of (left) dicalcium silicate hydrate, (middle) tricalcium silicate hydrate, and (right) hydrated normal portland
cement. Note the fibrous nature of the calcium silicate hydrates. Broken fragments of angular calcium hydroxide crystallites are also present (right).
The aggregation of fibers and adhesion of the hydration particles are responsible for the strength development of portland cement paste. Reference
(left and middle) Brunauer 1962 and (right) Copeland and Schulz 1962.

Table 3-5. Portland Cement Phase Hydration Reactions (Oxide Notation)

= 3CaO • 2SiO2 • 8H2O

2 (3CAO • SiO2) + 11 H2O Calcium silicate + 3 (CaO • H2O)
Tricalcium silicate Water hydrate (C-S-H) Calcium hydroxide
= 3CaO • 2SiO2 • 8H2O
2 (2CaO • SiO2) + 9 H2 O Calcaium silicate + CaO • H2O
Dicalcium silicate Water hydrate (C-S-H) Calcium hydroxide
3CaO • Al2O3 + 3 (CaO • SO3 • 2H2O) + 26 H2O = 6CaO • Al2O3 • 3SO3 • 32H2O
Tricalcium aluminate Gypsum Water Ettringite
2 (3CaO • Al2O3) + 6CaO • Al2O3 • 3SO3 • 32H2O + 4 H2O = 3 (4CaO • Al2O3 • SO3 •
Tricalcium aluminate Ettringite Water 12H2O)
Calcium monosulfoaluminate)
3CaO • Al2O3 + CaO • H2O + 12 H2O = 4CaO • Al2O3 • 13H2O
Tricalcium aluminate Calcium hydroxide Water Tetracalcium aluminate hydrate
4CaO • Al2O3 • Fe2O3 + 10 H2O + 2 (CaO • H2O) = 6CaO • Al2O3 • Fe2O3 • 12H2O
Tetracalcium aluminoferrite Water Calcium hydroxide Calcium aluminoferrite hydrate

Note: This table includes only primary reactions and not several additional minor reactions. The composition of calcium silicate hydrate (C-S-H) is

32
not stoichiometric (Tennis and Jennings 2000).

33
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-28. Scanning-electron micrographs of hardened cement paste at (left) 500X, and (right) 1000X.

100 capillary
Porosity C-S-H
porosity

C-S-H
75
calcium
hydroxide
Relative volume,

Ca(OH)2
AFt and
50 AFm
Amou

calcium
sulfate
C4(A, F)H13
25 C4 AF

C3 A
Ettringite 0
C2 S
0 5 30 1 2 6 1 2 7 28 90 0 25 50 75 100
C3 S
Degree of hydration, %
Age: Minutes Hours Days
other
Figure 3-29. Relative volumes of the cement phases and hydration products in the microstructure of hydrating portland cement
pastes (left) as a function of time (adapted from Locher, Richartz, and Sprung 1976) and (right) as a function of the degree of hydration as esti-
mated by a computer model for a water to cement ratio of 0.50 (adapted from Tennis and Jennings 2000). Values are given for an average Type I
cement composition (Gebhardt 1995): C3S=55%, C2S=18%, C3A=10% and C4AF=8%. “AFt and AFm” includes ettringite (AFt) and calcium
mono- sulfoaluminate (AFm) and other hydrated calcium aluminate compounds. See Table 3-5 for cement phase reactions.

The percentage of each cement phase can be estimated phase composition and fineness for each of the principal
from a chemical oxide analysis (ASTM C114, Standard types of portland cement.
Test Methods for Chemical Analysis of Hydraulic Cement,
or AASHTO T 105) of the unhydrated cement using the
Bogue equations, a form of which are provided in
ASTM
C150 (AASHTO M 85). X-ray diffraction (XRD)
techniques (ASTM C1365, Standard Test Method for
Determination of the Proportion of Phases in Portland Cement
and Portland- Cement Clinker Using X-Ray Powder
Diffraction Analysis) can generally be used to determine
phase composition.
Since the production of clinker depends on natural raw
materials, there can be a significant level of trace
elements in the major phases, which are not accounted
for in the Bogue equations, Bogue calculations also
assume a “per- fect combination” (complete equilibrium)
in the high tem- perature chemical reactions. XRD helps
eliminate this bias. Table 3-6 shows typical oxide and

34
Although elements are reported as simple oxides for
consistency, they are usually not found in that oxide
form in the cement. For example, sulfur from the
gypsum is reported as SO3 (sulfur trioxide), however,
cement does not contain any sulfur trioxide. The
amount of calcium, silica, and alumina establish the
amounts of the primary phases in the cement and
effectively the properties of hydrated cement. Sulfate is
present to control setting, as well as drying shrinkage
and strength gain (Tang 1992). Minor and trace
elements and their effect on cement prop- erties are
discussed by Bhatty (1995) and PCA (1992). The primary
cement phases have the following properties:

Tricalcium Silicate, C3S, hydrates and hardens rapidly

and is largely responsible for initial set and early
strength (Figure 3-30). In general, the early strength
of portland cement concrete is higher with
increased percentages of C3S.

35
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Dicalcium Silicate, C2S, hydrates and hardens slowly

100%
and contributes largely to strength increase at ages
beyond one week.
80%
Tricalcium Aluminate, C3A, liberates a large amount of

Degree of reaction, % by mass

heat during the first few days of hydration and
hardening. It also contributes slightly to early strength
60%
development. Cements with low percentages of C3A are
more resistant to soils and waters containing sulfates.
C 3S
Tetracalcium Aluminoferrite, C4AF, is the product result- 40%
C 2S
ing from the use of iron and aluminum raw materials to
C 3A
reduce the clinkering temperature during cement manu-
20% C4AF
facture. It contributes little to strength. Most color effects
that give cement its characteristic gray color are due to Overall

the presence of C4AF and its hydrates.

0%
0 20 40 60 80 100
Calcium Sulfate, as anhydrite (anhydrous calcium sul-
Age, days
fate), gypsum (calcium sulfate dihydrate), or Figure 3-30. Relative reactivity of cement compounds. The curve
hemihydrate, (calcium sulfate hemihydrate, often called labeled “Overall” has a composition of 55% C3S, 18% C2S, 10% C3A,
plaster of paris or bassanite) is added to cement during and 8% C4AF, an average Type I cement composition (Tennis and
final grinding to provide sulfate to react with C3A to form Jennings 2000).
ettringite (calc- ium trisulfoaluminate). This controls the
hydration of C3A. Without sulfate, cement would set Water (Evaporable and Nonevaporable)
much too rapidly. In addition to controlling setting and Water is a key ingredient of pastes, mortars, and concretes.
early strength gain, the sulfate also helps control drying The phases in portland cement must chemically react with
shrinkage and can influence strength through 28 days water to develop strength. The amount of water added to
(Lerch 1946). a mixture controls the durability as well. The space initially
occupied by water in a cementitious mixture is either par-
In addition to the above primary phases, portland cement tially or completely replaced over time as the hydration
may contain up to 5% limestone and numerous other reactions proceed (Table 3-5). If more than about 35%
lesser compounds (PCA 1997 and Taylor 1997). water by mass of cement (a water to cement ratio of 0.35)
is used,

Table 3-6. Composition and Fineness of Cements*

Potential phase
Chemical composition, % composition,% Blaine
Type of fineness
portland cement SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O eq C3 O C2S C3A C4AF m2/ kg
I (min-max) 19.0-21.8 3.9-6.1 2.0-3.6 61.5-65.2 0.8-4.5 2.0-4.4 0.2-1.2 45-65 6-21 6-12 6-11 334-431
I (mean) 20.2 5.1 2.7 63.2 2.5 3.3 0.7 57 15 9 8 384
II (min-max) 20.0-22.5 3.8-5.5 2.6-4.4 61.3-65.6 0.6-4.5 2.1-4.0 0.2-1.2 48-68 8-25 4-8 8-13 305-461
II (mean) 20.9 4.6 3.3 63.7 2.0 2.9 0.56 57 17 7 10 377
III (min-max) 18.6-22.1 3.4-7.3 1.3-4.2 61.6-64.9 0.8-4.3 2.6-4.9 0.1-1.2 48-66 8-27 2-12 4-13 387-711
III (mean) 20.4 4.8 2.9 63.3 2.2 3.6 0.61 56 16 8 9 556
IV** (min-max) 21.5-22.8 3.5-5.3 3.7-5.9 62.0-63.4 1.0-3.8 1.7-2.5 0.29-0.42 37-49 27-36 3-4 11-18 319-362
IV** (mean) 22.2 4.6 5.0 62.5 1.9 2.2 0.36 42 32 4 15 340
V** (min-max) 20.3-22.8 3.3-4.8 3.2-5.8 62.3-65.2 0.8-4.5 2.0-2.8 0.3-0.6 47-64 12-27 0-5 10-18 312-541
V** (mean) 21.6 3.8 3.9 63.9 2.2 2.3 0.45 58 18 4 12 389
White** (min-max) 22.0-24.4 2.2-5.0 0.2-0.6 63.9-68.7 0.3-1.4 2.3-3.1 0.09-0.38 51-72 9-25 5-13 1-2 384-564
White** (mean) 22.7 4.1 0.3 66.7 0.9 2.7 0.18 64 18 10 1 482

*Values represent a summary of combined statistics. Air-entraining cements are not included. For consistency in reporting, elements are
reported in a standard oxide form. This does not mean that the oxide form is present in the cement. For example, sulfur is reported as SO 3,
sulfur trioxide, but, portland cement does not have sulfur trioxide present. “Potential phase composition” refers to ASTM C150 (AASHTO M 85)
calculations using an oxide analysis of the cement. The actual phase composition may differ due to incomplete or alternate chemical reactions.
**Type IV and White Cement data are based on limited data in Gebhardt (1995) and PCA (1996). Type IV is not commonly available. Adapted
from Bhatty and Tennis (2008).

36
Design and Control of Concrete Mixtures ◆ EB001

then the porosity in the hardened material will remain, To estimate the degree of hydration of a hydrated
even after complete hydration. This phenomenon is called material, the nonevaporable water content is often used.
capillary porosity. Figure 3-31 shows that cement pastes To convert the measured nonevaporable water into
with high and low water to cement ratios have equal degrees of hydra- tion, it is necessary to know the value
masses after drying (thus indicating that evaporable water of nonevaporable water-to-cement ratio (wn/c) at
was removed). The cement consumed the same amount of complete hydration. This can be experimentally
water in both pastes resulting in more bulk volume in the determined by preparing a high water-to-cement ratio
higher water-cement ratio paste. As the water to cement cement paste (for example, 1.0) and continuously
ratio increases, the capillary porosity increases, and the grinding the paste sample while it hydrates in a roller
strength decreases. Also, transport properties such as per- mill. In this procedure, complete hydration of the cement
meability and diffusivity are increased. This degradation will typically be achieved after 28 days.
in transport properties allows detrimental chemicals to
more readily attack the concrete or reinforcing steel. Alternatively, an estimate of the quantity of nonevapor-
able water-to-cement ratio (wn/c) at complete hydration
can be obtained from the potential Bogue composition
of the cement. Nonevaporable water contents for the
major phases of portland cement are provided in Table
3-7. For a typical Type I cement, these coefficients will
generally result in a calculated wn/c for completely
hydrated cement somewhere between 0.22 and 0.25.

Table 3-7. Nonevaporable Water Contents for Fully Hydrated Major

Cement Phases
Nonevaporable (combined)
Hydrated cement water content
compound (g water/g cement compound)
C3S hydrate 0.24
C2S hydrate 0.21
C3A hydrate 0.40
C4AF hydrate 0.37
Figure 3-31. Cement paste cylinders of equal mass and equal Free lime (CaO) 0.33
cement content, but mixed with different water to cement ratios, after
all water has evaporated from the cylinders.
Physical Properties of Cement
Water is observed in cementitious materials in different
forms. Free water includes mixing water that has not yet Specifications for cement place limits on both its physical
reacted with the cement phases. Bound water is chemi- properties and often its chemical composition. An under-
cally combined in the solid phases or physically bound to standing of the significance of some of the physical prop-
the solid surfaces. A reliable separation of the chemically erties is helpful in interpreting results of cement tests
combined water from the physically adsorbed water is (Johansen, Taylor, and Tennis 2006). Tests of the physical
not possible. Accordingly, Powers (1949) distinguished properties of the cements should be used to evaluate the
between evaporable and nonevaporable water. The non- properties of the cement, rather than the concrete.
evaporable water is the amount retained by a sample Cement specifications limit the properties with respect to
after it has been subjected to a drying procedure the type of cement. Cement should be sampled in
intended to remove all the free water (traditionally, by accordance
heating to 105°C [221°F]). Evaporable water was with ASTM C183 (AASHTO T 127), Standard Practice for
originally consid- ered to be free water, but it is now Sampling and the Amount of Testing of Hydraulic Cement.
recognized that some bound water is also lost as the During manufacture, cement is continuously
sample is heated. All nonevaporable water is bound monitored for its chemistry and the following
water, yet not all bound water is nonevaporable. properties reported.

For complete hydration of portland cement to occur, only Compressive Strength

about 40% water (a water-cement ratio of 0.40) is The strength development characteristics of cement are
required. If a water-cement ratio greater than about 0.40 determined by measuring the compressive strength of
is used, the excess water not needed for cement 50-mm (2-in.) mortar cubes tested in accordance with
hydration remains in the capillary pores or evaporates. If ASTM C109 (AASHTO T 106), Standard Test Method for
a concrete mixture has a water-cement ratio less than Compressive Strength of Hydraulic Cement Mortars (Using
about 0.40, some cement will remain unhydrated. 2-in. or [50-mm] Cube Specimens (Figure 3-32).

Compressive strength is influenced by the cement type,

specifically: the phase composition, sulfate content, and
37
fineness of the cement. Minimum strength requirements
in cement specifications are typically exceeded
comfortably.

38
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

used to predict concrete strengths with any degree of

accuracy because of the many variables that influence
concrete strength, including: aggregate characteristics,
concrete mixture proportions, construction procedures,
and environmental conditions in the field (Weaver,
Isabelle and Williamson 1974 and DeHayes 1990). There-
fore, it should never be assumed that two types of cement
meeting the same minimum requirements will produce
the same strength of mortar or concrete without modifi-
cation of mix proportions.

Figures 3-33 and 3-34 illustrate the strength development

for standard mortars made with various types of
portland cement. Wood (1992) provides long-term
Figure 3-32. 50-mm (2-in.) mortar cubes are cast (left) and crushed strength proper- ties of mortars and concretes made with
(right) to determine strength characteristics of cement. portland and blended cements. The strength uniformity
of a cement from a single source may be determined by
Table 3-8 shows the minimum compressive strength following the procedures outlined in ASTM C917,
requirements as given in US specifications. In general, Standard Test Method for Evaluation of Cement Strength
cement strengths (based on mortar-cube tests) cannot be from a Single Source.

Table 3-8. Minimum Compressive Strength Requirements in US Cement Specifications (MPa*)

Limits
Specification Type 1 day 3 days 7 days 28 days
I —** 12.0 19.0 28.0***
II, II(MH) — 10.0 17.0 28.0***
ASTM C150 III 12.0 24.0 — —
(AASHTO M 85)
IV — — 7.0 17.0
V — 8.0 15.0 21.0
IP, IS(<70),
— 13.0 20.0 25.0
IT(P<S<70), IT(PS)
IP(MS), IS(<70)(MS),
ASTM C595 IT(P<S<70)(MS), IT(PS)(MS),
— 11.0 18.0 25.0
IP(HS), IS(<70)(HS)
(AASHTO M 240)
IT(P<S<70)(HS), IT(PS)(HS)
IS(70), IT(S70) — — 5.0 11.0
IP(LH), IT(PS)(LH) — — 11.0 21.0
GU — 13.0 20.0 28.0
HE 12.0 24.0 — —
MS — 11.0 18.0 28.0***
ASTM C1157
HS — 11.0 18.0 25.0
MH — 5.00 11.0 22.0***
LH — — 11.0 21.0
*For complete details, review the relevant standards. As determined by ASTM C109, which is similar to AASHTO T 106. To convert to psi,
multiply by 145.0377. Air-entraining cements are not included, but have somewhat lower requirements, as do some cement types when addi-
tional optional requirements are invoked.
**Key: — = no requirement at this age.
***Optional requirement that applies only if specifically requested.

39
Design and Control of Concrete Mixtures ◆ EB001

100 Setting Time

2004 survey The setting properties of hydraulic cement are
measured to ensure that the cement is hydrating
80 normally. Two arbitrary setting times are used: initial
set – which is considered to represent the time that
elapses from the moment water is added until the paste
28-day strength,

60 ceases to be fluid and plastic, and final set–the time

required for the paste to acquire a certain degree of
hardness.
40
Cement To determine if a cement sets according to the time limits
Type I Type II Type III Type V
specified in cement specifications, tests are performed
20 using the Vicat apparatus (ASTM C191, Standard Test
Methods for Time of Setting of Hydraulic Cement by Vicat
Needle, or AASHTO T 131), or more rarely, the Gillmore
0
0 5 10 15 20 25 30 needle (ASTM C266, Standard Test Method for Time of
Time, days Setting of Hydraulic-Cement Paste by Gillmore Needles,
Figure 3-33. Relative strength development of portland cement or AASHTO T 154).
mortar cubes as a percentage of 28-day strength. Mean values
adapted from Bhatty and Tennis (2008). The setting times indicate if a paste is undergoing normal
hydration reactions. Sulfate (from gypsum or other sources)
in the cement regulates setting time, but setting time is also
affected by cement fineness, water-cement ratio, and any

60 60
Type I 8000 Type II 8000
50 50

Compessive strength, psi

Compessive strength, MPa

Compessive strength, MPa

6000
Compessive strength, psi

40 40 6000

30 30
4000
4000

20 20

2000
2000
10 10

0 0
0 5 10 15 20 25 30 0 0
Time, days 0 5 10 15 20 25 30
Time, days
60
60
Type III 8000 Type V 8000
50
50
Compessive strength, psi
Compessive strength, MPa

Compessive strength, MPa

6000
Compessive strength, psi

40 40 6000

30 30
4000
4000

20 20

2000
2000
10 10

0 0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time, days Time, days

40
Figure 3-34. Mean values of ASTM C109 mortar cube strengths from a 2004 survey (Bhatty and Tennis 2008). Range of reported values indicated
by shaded areas, and mean values by the dashed lines.

41
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

admixtures that may be used. Setting times of concretes do

to form plaster. Stiffening is caused by the rapid crystal-
not correlate directly with setting times of pastes because of
lization of interlocking needle-like secondary gypsum.
water loss to the air or substrate, presence of aggregate,
Additional mixing without added water breaks up these
and because of temperature differences in the field (as
crystals to restore workability. Ettringite precipitation can
contrasted with the controlled temperature in a testing
also contribute to false set.
lab). Figure
3-35 illustrates mean set times for portland cements. Flash set or quick set is evidenced by a rapid and early
loss of workability in paste, mortar, or concrete. It is
usually accompanied by the evolution of considerable
Type I
heat resulting primarily from the rapid reaction of alumi-
Initial set Final set nates. If the proper amount or form of calcium sulfate is
Type II not available to control tricalcium aluminate hydration,
stiffening becomes apparent. Flash set cannot be
dispelled, nor can the plasticity be regained by further
Type III
mixing without the addition of water.

Type IV* Proper stiffening results from the careful balance of the
sulfate and aluminate compounds, as well as the
tempera- ture and fineness of the materials (which control
Type V**
the disso- lution and precipitation rates). The amount of
0 50 100 150 200 250 300 350 400 450
sulfate in the form of plaster has a significant effect. For
Time of set, minutes (Vicat Method) example, with one particular cement, 2% plaster provided
a 5-hour set time, while 1% plaster caused flash set to
*Average of two values for initial set; one value for final set
**Average of two values for final set
occur, and 3% demonstrated false set (Helmuth and
others 1995).
Figure 3-35. Time of set for portland cements (Bhatty and Tennis
2008). Type IV setting times are based on limited data in Gebhardt Cements are tested for early stiffening using ASTM C451,
(1995). Standard Test Method for Early Stiffening of Hydraulic
Cement (Paste Method), (AASHTO T 186), and ASTM
Early Stiffening (False Set and Flash Set) C359, Standard Test Method for Early Stiffening of Hydraulic
Early stiffening is the early development of stiffness in Cement (Mortar Method), (AASHTO T 185), which use the
the working characteristics or plasticity of cement penetration techniques of the Vicat apparatus. However,
paste, mortar, or concrete. This includes both false set these tests do not address all the variables that can influ-
and flash set. ence early stiffening including: mixing, placing, tempera-
ture, and field conditions. These tests also do not address
False set is evidenced by a significant loss of plasticity early stiffening caused by interactions with other
without the evolution of much heat shortly after concrete ingredients. For example, concretes mixed for
mixing. From a placing and handling standpoint, false- very short periods, less than one minute, tend to be more
set ten- dencies in cement will cause no difficulty susceptible to early stiffening (ACI 225).
provided the concrete is mixed for a longer time than
usual or if it is remixed without additional water before Particle Size and Fineness
being trans- ported or placed. False set occurs when a Portland cement consists of individual angular particles
significant amount of gypsum dehydrates in the with a range of sizes, the result of pulverizing clinker in
cement finish mill the grinding mill (Figure 3-36 left). Approximately 95% of

100 Typical particle size distribution curve for Type I or Type II cement

80
Cumulative mass, percent

60

40

20

0
100 50 20 10 5 2 1 0.5
Equivalent spherical diameter, m
Figure 3-36. (left) Scanning-electron micrograph of powdered cement at approximately 1000× magnification and (right) particle

42
size distribution of portland cement.

43
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-37. Blaine test apparatus (left) and Wagner turbidimeter (right) for determining the fineness of cement.

cement particles are smaller than 45 µm, with the average excessive
particle around 15 µm. Figure 3-36 (right) illustrates the
particle size distribution for a portland cement. The
fineness is, at best, a general indication of the particle size
distribu- tion of a cement. Finer cements, as indicated by
higher Blaine fineness measurements, are typically
indicative of finer individual cement particles. The fineness
of cement affects heat released and the rate of hydration.
Greater cement fineness (smaller particle size) increases the
rate at which cement hydrates and thus accelerates strength
devel- opment. The effects of greater fineness on paste
strength are manifested principally during the first seven
days.

Fineness is usually measured by the Blaine air-perme-

ability test (ASTM C204, Standard Test Methods for Fineness
of Hydraulic Cement by Air-Permeability Apparatus, or
AASHTO T 153 – Figure 3-37) that indirectly measures the
surface area of the cement particles per unit mass.
Cements with finer particles have more surface area in
square meters per kilogram of cement. (The use of square
centimeters per gram for reporting fineness is now
considered archaic.) ASTM C150 and AASHTO M 85 have
minimum Blaine fineness limits of 260 m2/kg for all
cement types except Type III, and maximum limits on
fineness for Type II(MH) and Type IV cements of 430
m2/kg. The Wagner turbi- dimeter test (ASTM C115,
Standard Test Method for Fineness of Portland Cement by the
Turbidimeter, or AASHTO T 98 – Figure 3-37), the 45-
micrometer (No. 325) sieve (ASTM C430, Standard Test
Method for Fineness of Hydraulic Cement by the 45-µm (No.
325) Sieve, or AASHTO T 192 – Figure
3-38) and electronic (x-ray or laser) particle size
analyzers (Figure 3-39) can also be used to determine
values for fineness, although the results are not
equivalent among different test methods. Blaine fineness
data are given in Table 3-6.

Soundness
Soundness refers to the ability of a hardened cement
paste to retain its volume after setting. Lack of soundness
or delayed destructive expansion can be caused by

44
Figure 3-38. Quick tests, such as washing cement over this 45-
micrometer sieve, help monitor cement fineness during production.
Shown is a view of the sieve holder with an inset top view of a cement
sample on the sieve before washing with water.

Figure 3-39. A laser particle analyzer uses laser

diffraction to determine the particle size distribution of
fine powders.

amounts of hard-burned free lime or magnesia. Most

specifications for portland cement limit the magnesia
(periclase) content and require that the maximum ex-
pansion must not exceed 0.80% for portland, blended,
or hydraulic cement as measured by the autoclave-
expansion test. Since adoption of the autoclave-
expansion test

45
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

(ASTM C151, Standard Test Method for Autoclave Expansion

of Hydraulic Cement, or AASHTO T 107) in 1943, there
have been exceedingly few cases of abnormal expansion
attributed to unsound cement (Figure 3-40). See Gonner-
man, Lerch, and Whiteside (1953), Helmuth and West
(1998) and Klemm (2005) for extensive reviews of the
autoclave expansion test.

Figure 3-41. Normal consistency test for paste using the Vicat
plunger.

Figure 3-40. In the soundness test, 25-mm square bars are exposed
to high temperature and pressure in the autoclave to determine the
volume stability of the cement paste.

Consistency
Consistency refers to the relative mobility of a freshly
mixed cement paste or mortar or to its ability to flow.
During cement testing, pastes are mixed to normal
consistency as defined by a penetration of 10 ± 1 mm of
the Vicat plunger (see ASTM C187 or AASHTO T 129
and Figure 3-41). Mortars are mixed to obtain either a
fixed water-cement ratio or to yield a flow within a Figure 3-42. Consistency test for mortar using the flow table. The
prescribed range. The flow is determined on a flow mortar is placed in a small brass mold centered on the table (inset).
table For skin safety the technician wears protective gloves while handling
as described in ASTM C230, Standard Specification for Flow the mortar. After the mold is removed and the table undergoes a
succession of drops, the diameter of the pat is measured to deter-
Table for Use in Tests of Hydraulic Cement, (AASHTO M mine consistency.
152) and ASTM C1437, Standard Test Method for Flow of
Hydraulic Cement, (Figure 3-42). Both the normal consis- evolution. The water-cement ratio, fineness of the cement,
tency method and the flow test are used to regulate and temperature of curing also are factors. An increase in
water contents of pastes and mortars, respectively, to be the fineness, cement content, and curing temperature
used in subsequent tests; both allow comparing increases the heat of hydration. Although portland
dissimilar ingre- dients with the same penetrability or cement can evolve heat for many years, the rate of heat
flow. generation is greatest at early ages. A large amount of
heat evolves within the first three days with the greatest
Heat of Hydration
rate of heat liberation usually occurring within the first 24
Heat of hydration is the heat generated when cement and hours (Copeland and others 1960). The heat of hydration
water react. The amount of heat generated is dependent is
chiefly upon the chemical composition of the cement,
with C3A and C3S phases primarily responsible for high
heat

46
Design and Control of Concrete Mixtures ◆ EB001

tested in accordance with ASTM C186, Standard Test Table 3-9 provides heat of hydration values for a variety
Method for Heat of Hydration of Hydraulic Cement, or may of portland cements. These limited data show that Type
also be performed by conduction calorimetry according III cement has a higher heat of hydration than other
to ASTM C1702, Standard Test Method for Measurement types.
of
Heat of Hydration of Hydraulic Cementitious Materials Using Cements do not generate heat at a constant rate. The
Isothermal Conduction Calorimetry (Figure 3-43). ASTM heat output during hydration of a typical Type I
C1679, Standard Practice for Measuring Hydration Kinetics portland cement is illustrated in Figure 3-44. The first
peak shown in the heat profile is caused by heat
of Hydraulic Cementitious Mixtures Using Isothermal
generated from the initial hydration reactions of cement
Calorimetry, also provides information on isothermal
compounds such
conduction calorimetry testing. Often heat of hydration
as tricalcium aluminate. Sometimes called the heat of
is also tested in both the laboratory and field using
wetting, this initial heat peak is followed by a period of
semi- adiabatic calorimetry to predict heat evolution
slow thermal activity known as the induction period.
maturity of the concrete.
After several hours, a broad second heat peak attributed
For most concrete elements, such as slabs, heat to tricalcium silicate hydration emerges, signaling the
generation is not a concern because the heat is quickly onset of the paste hardening process. Finally, a third
dissipated into the environment. However, in structures peak due to the renewed activity of tricalcium aluminate
of considerable mass, greater than a meter (yard) thick, is experienced; its intensity and location are normally
the rate and amount of heat generated are critical. If this dependent on the amount of tricalcium aluminate and
heat is not rapidly dissipated in massive elements, a sulfate present in the cement.
significant rise in concrete temperature can occur. This
may be undesir- able, since, after hardening at an In calorimetry testing, the first heat measurements are
elevated temperature, non-uniform cooling of the typically obtained 5 to 7 minutes after mixing the paste;
concrete to ambient tempera- ture may create excessive as a result, often only the downward slope of the first
tensile stresses. On the other hand, a rise in concrete peak is observed (Stage 1, Figure 3-44). The second peak
temperature caused by heat of hydration is often (C3S peak) generally occurs between 6 and 12 hours.
beneficial in cold weather, as it helps maintain favorable The third peak (renewed C3A peak) occurs between 12
curing temperatures. and 90 hours. This information can be helpful when
trying to control temperature rise in mass concrete
(Tang 1992).

Figure [Link] of hydration can be determined by (left) ASTM C186 or by (right) a conduction calorimeter.

Table 3-9. Summary of ASTM C186 Heat of Hydration Data in 2007 Survey, kJ/kg*

Type I Type II** Type III*** Type V****

7 days 28 days 7 days 28 days 7 days 7 days 28 days
Mean 352 408 333 376 355 322 368
St. Dev. 23.1 12.5 23.3 33.4 56.6 21.2 23.4
Max 380 416 393 431 399 346 398
Min 315 389 269 287 291 279 336
N 6 4 53 27 3 15 7
* Table is based on limited data for several cement types. To convert to cal/g, divide by 4.184.
** Includes 22 Type I/II cements.
47
 *** Includes 1 Type II/III cement.
**** Includes 7 Type II/V cements.

48
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

Stage 1 ranges from 3.10 to 3.25, averaging 3.15 Mg/m3. Portland-

blast-furnace-slag and portland-pozzolan cements have
Stage 2 Stages 3 and 4 C3S hydration Stage 5 densities ranging from 2.90 to 3.15, averaging 3.05 Mg/m3.
C3A hydration
The density of a cement, determined by ASTM C188,
Standard Test Method for Density of Hydraulic Cement,
(AASHTO T 133) (Figure 3-46), is not an indication of
Heat

the cement’s quality; rather, its principal use is in mixture

proportioning calculations (see Chapter 12).

For mixture proportioning, it may be more useful to ex-

Time press the density as relative density (also called specific
Figure 3-44. Heat evolution as a function of time for cement paste. cement
Stage 1 is heat of wetting or initial hydrolysis (C3A and C3S hydration).
Stage 2 is a dormant period related to initial set. Stage 3 is an accel-
erated reaction of the hydration products that determines rate of
hardening and final set. Stage 4 decelerates formation of hydration
products and determines the rate of early strength gain. Stage 5 is a
slow, steady formation of hydration products establishing the rate of
later strength gain.

When heat generation must be minimized in concrete,

designers should choose a lower heat cement, such as
an ASTM C150 (AASHTO M 85) Type II(MH) portland
cement. Type IV cement can also be used to control
temper- ature rise, but it is rarely available. Moderate-heat
and low- heat cements are also available in ASTM C595
(AASHTO M 240; with (MH) or (LH) suffixes) and C1157
(Type MH or LH) specifications. Supplementary
cementitious materials are also often used to reduce
temperature rise.

ASTM C150 (AASHTO M 85) has both a chemical

approach and a physical approach to control heat of
hy- dration. Either approach can be specified, but not
both. ASTM C595 (AASHTO M 240) and ASTM C1157
use
physical limits. See Poole (2007) for more information.

Loss on Ignition
Loss on ignition (LOI) of portland cement is determined
by heating a cement sample of known weight up to a
temperature between 900°C and 1000°C until a constant
weight is obtained. The weight loss of the sample is then
determined. Loss on ignition values range from 0% to
3%. Traditionally, a high LOI has been an indication of
prehy- dration and carbonation, which may have been
caused by improper or prolonged storage, or
adulteration during transport. Modern cements may
have an LOI over 2% due to the use of limestone as an
ingredient in portland cement. The test for loss on
ignition is performed in accor- dance with ASTM C114
(AASHTO T 105) (Figure 3-45).

Density and Relative Density (Specific Gravity)

The density of cement is defined as the mass of a unit
volume of the solids or particles, excluding air between
particles. It is reported as megagrams per cubic meter or
grams per cubic centimeter (the numeric value is
identical for both units). The particle density of portland

49
gravity). The relative density is a dimensionless number
determined by dividing the cement density by the
density of water at 4°C, which is 1.0 Mg/m3 (1.0 g/cm3
or 1000 kg/m3) or 62.4 lb/ft3.

A relative density of 3.15 is assumed for portland

cement in volumetric computations of concrete mix
proportion- ing. However, as mix proportions list
quantities of con- crete ingredients in kilograms or
pounds, the relative density must be multiplied by the
density of water at 4°C to determine the particle
density in kg/m3 or lb/ft3. This product is then divided
into the mass or weight of cement to determine the
absolute volume of cement in cubic meters or cubic
feet. (See Chapter 12 for more information on
proportioning concrete mixtures.)

Figure 3-45. Loss on ignition test of cement.

Figure 3-46. Density of cement can be determined by (left) using

a Le Chatelier flask and kerosene or by (right) using a helium
pycnometer.

50
Design and Control of Concrete Mixtures ◆ EB001

Bulk Density
• estimating the reactivity of pozzolans and slags
The bulk density of cement is defined as the mass of for use in blended cements
cement particles plus air between particles per unit
• identifying the organic matter content and
volume. The bulk density of cement can vary considerably
variations in a quarry
depending on how it is handled and stored. Portland
cement that is aerated or loosely deposited may weigh • quantifying the amount of carbonation that has
only 830 kg/m3 (52 lb/ft3), but with consolidation caused taken place in an exposed sample
by vibration, the same cement can weigh as much as • analyzing durability problems with concrete.
1650 kg/m3 (103 lb/ft3) (Toler 1963). For this reason alone,
good practice dictates that cement must be weighed for Specific thermal analysis techniques are discussed
each batch of concrete produced, as opposed to using a
volumetric measure (Figure 3-47). below.

Figure 3-47. Both 500-mL beakers contain 500 grams of dry Figure 3-48. Thermal analysis equipment.
powdered cement. On the left, cement was simply poured into the
beaker. On the right, cement was slightly vibrated – imitating consoli- Thermogravimetric Analysis (TGA)
dation during transport or packing while stored in a silo. The 20%
difference in bulk volume demonstrates the need to measure Thermogravimetric analysis (TGA) is a technique that
cement by mass instead of volume for batching concrete. measures the mass (weight) of a sample as it is being
heated (or cooled) at a controlled rate. The weight change
of a sample depends on the composition of the sample,
Thermal Analysis the temperature, the heating rate, and the type of gas in
the furnace (air, oxygen, nitrogen, argon, or other gas). A
Thermal analysis techniques have been available for change in mass within a specific temperature range can
years to analyze hydraulic reactions and the identify the presence of a particular chemical compound.
interactions of cement with both mineral and chemical The magnitude of the weight change indicates the
admixtures (Figure 3-48). Thermal analysis is useful for amount of that compound in the sample.
analyzing chemical and physical properties of
cementitious mate- rials and raw materials for cement One example of the use of TGA is the split loss on ignition
manufacture (Bhatty 1993, Shkolnik and Miller 1996, procedure, which is often used to estimate the amount of
and Tennis 1997). limestone in an unhdyrated portland cement (see ASTM
C114). In this procedure, the CO2 content of a cement is
Thermal analysis involves heating a small sample at a determined as the mass loss between 550°C and 950°C
controlled rate to high temperature (up to 1000°C or and the percentage of limestone is determined by
more). As materials react or decompose, changes in the dividing the CO2 content of the cement by the CO2
sample’s weight, temperature, energy, or state (gas, content of the limestone. The procedure can be done as a
solid, liquid) that occur as a function of time or series of steps in furnaces at specific temperature, but
temperature are recorded. Typical uses for thermal TGA can provide similar data as a single procedure.
analysis include:
Differential Thermal Analysis (DTA)
• identifying which hydration products have
formed and in what quantities Differential thermal analysis (DTA) is an analytical
method in which the difference in temperature between
• solving early stiffening problems a sample and a control is measured as the samples are
• identifying impurities in raw materials heated. The control is usually an inert material, like
• determining the amount of weathering in clinker pow- dered alumina, that does not react over the
or cement temperature

51
range being studied. If a sample undergoes a reaction at
a certain temperature, then its temperature will increase
or

52
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

decrease relative to the (inert) control as the reaction

gives off heat (exothermic) or adsorbs heat (endothermic). Virtual Cement Testing
A thermocouple measures the temperature of each
material, allowing the difference in temperature to be Computer technology now allows simulation of cement
recorded. hydration (Figure 3-50), microstructure development, and
DTA is ideal for monitoring the transformation of cement physical properties. Combinations of materials, cement
phases during hydration. DTA can be performed phases, or particle size distributions can be modeled to
simulta- neously with TGA. predict cement performance. Just some of the properties
that can be simulated and predicted include: heat of hy-
Differential Scanning Calorimetry (DSC) dration, adiabatic heat signature, compressive strength,
In differential scanning calorimetry (DSC), the heat ab- setting time, rheology (yield stress and viscosity), percola-
sorbed or released is measured directly as a function of tion, porosity, diffusivity, thermal conductivity, electrical
temperature or time and compared to a reference. An conductivity, carbonation, elastic properties, drying
advantage of DTA and DSC methods is that no mass profiles, susceptibility to degradation mechanisms, auto-
change is required; thus if a sample melts without vapor- genous shrinkage, and volumes of hydration reactants
izing, measurements can still be obtained. and products as a function of time. The effects from
varying sulfate and alkali contents can also be examined,
Like DTA, DSC can be used to determine what phases along with interaction with supplementary cementitious
are present at different stages of hydration. Figure 3-49 materials and chemical admixtures. Computer modeling
shows two differential scanning calorimetry curves or predicts performance without the expense and time
thermo- grams. The upper curve (a) shows a portland requirements of physical testing. Garboczi and others
cement paste after 15 minutes of reaction. The peaks in (2009) provide a web-based computer model for hydra-
the curve between 100°C and 200°C are due to the tion and microstructure development.
endothermic (heat adsorbing) decomposition of gypsum
and ettringite, while the peak around 270°C is due to
syngenite (potas- sium calcium sulfate hydrate). Near
450°C, a smaller peak can be seen, due to calcium
hydroxide.

The lower curve (b) in Figure 3-49 shows the same

cement paste after 24 hours of hydration. Note the
disappearance of the peak due to gypsum, the reduction
in the size of the peak due to syngenite and the growth of
those due to ettringite and calcium hydroxide. The size of
the areas under the curves is related to the quantity of
the material in the sample.

a
C Figure 3-50. Two-dimensional image of portland cement. Colors are:
red – tricalcium silicate, aqua–dicalcium silicate, green – tricalcium
S b aluminate, yellow – tetracalcium aluminoferrite, pale green – gypsum,
white – free lime, dark blue – potassium sulfate, and magenta – peri-
GS clase. The image was obtained by combining a set of SEM backscat-
tered electron and X-ray images (NIST 2007).

C
E
Transportation and Packaging

Around 100 million metric tons of cement are shipped

Exother
mic

per year throughout the United States. Most portland

cements are shipped in bulk by rail, truck, barge, or ship
(Figure
E
3-51). Pneumatic (pressurized air) loading and unloading
of the transport vehicle is the most popular means of
100200300400500
handling bulk cement. However, the recent introduction
Temperature, C
of large sacks holding one to twelve tons of cement pro-
Figure 3-49. Differential scanning calorimetry thermogram of a port- vides a new alternative to bulk cement handling. Bulk
land cement paste after (a) 15 minutes and (b) 24 hours of hydration. cement is measured by the metric ton (1000 kg) or short
C = calcium hydroxide; E = ettringite; G = gypsum; and S = syngenite.
ton (2000 lb).

53
Design and Control of Concrete Mixtures ◆ EB001

Figure 3-51. Portland cements are shipped from the plant silos to the user in bulk by (left to right) rail, truck, or water.

Cement is also bagged for convenient use at construction should be closed. Cement bags should not be stored on
sites (Figure 3-52) and for small jobs. In the United States damp floors but should rest on pallets. Bags should be
a bag of portland cement has a mass of 42 kg (92.6 lb) stacked closely together to reduce air circulation but
and a volume of 28 liters. Traditionally a U.S. bag should never be stacked against outside walls. Bags to be
contained 94 lb (42.6 kg) and had a volume of 28 L (one stored for long periods should be covered with
cubic foot). In Canada, a bag of portland cement has a tarpaulins or other waterproof covering. Bags should be
mass of 40 kg, and in other countries a bag of cement can stored so that the first in are the first out.
have a mass
of 25 kg or 50 kg. On small jobs where a shed is not available, bags should
be placed on raised wooden platforms (pallets) above the
ground. Waterproof coverings should fit over the pile and
extend over the edges of the platform to prevent rain
from reaching the cement and the platform (Figure 3-53).
Rain- soaked platforms can damage the bottom bags of
cement.

Figure 3-52. A small amount of cement is shipped in bags, primarily

for masonry applications and for small projects.

The mass of masonry cement and mortar cement by

the bag is 36 kg for Type M, 34 kg for Type S, and 32
kg for Type N. Plastic cement has a mass of 42 kg for
Type M and 35 kg for Type S. All bag weights are Figure 3-53. When stored on the job, cement should be protected
based on a 28 liter (1 ft3) volume standard. Information from moisture.
for quantities of blended and specialty cements can be
found on the bag. Partial bag sizes are also available in Cement stored for long periods may develop what is
some areas. called warehouse pack. This can usually be corrected by
rolling the bags on the floor. At the time of use, cement
Storage of Cement should be free-flowing and free of lumps. If lumps do
not break up easily, the cement should be tested before
it is used in important work. Standard strength tests or
Cement is a moisture-sensitive material; while dry, it will loss- on-ignition tests should be made whenever the
retain its quality indefinitely. Cement stored in contact
quality of cement is in question.
with damp air or moisture sets more slowly and has less
strength than cement that is kept dry. At the cement Ordinarily, cement does not remain in storage long, but
plant, and at ready mixed concrete facilities, bulk cement it can be stored for long periods without deterioration.
is stored in silos. The relative humidity in a warehouse Bulk cement should be stored in weather tight concrete
or shed used to store bagged cement should be as low as or steel bins or silos. Dry low-pressure aeration or
possible. All cracks and openings in walls and roofs vibration
54
 Chapter 3 ◆ Portland, Blended and Other Hydraulic Cement

should be used in bins or silos to keep the cement flow- Bhatty, Javed I., and Tennis, Paul D., U.S. and Canadian
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because of loose packing of aerated cement.
Brunauer, S., Some Aspects of the Physics and Chemistry of
Cement, Research Department Bulletin RX080, Portland
Hot Cement Cement Association, [Link]
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When cement clinker is pulverized in the grinding mill
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grinding mechanism generates heat. Freshly ground Research Department Bulletin RX138, Portland Cement
cement is therefore hot when placed in storage silos at the Association, [Link]
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concrete is not significant (Lerch 1955). The temperatures pretation of Portland Cement and Clinker, SP030, Portland
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58