Chapter 6 — Portland Cement (PC), Mix Wa-

ter and Admixtures

A. First, What Are Concretes — General Description of Concretes
1. All concretes are filler – binder materials
a) Aggregates, such as gravel and sand, constitute the filler
b) Cements (e.g., asphalt cement) or cementitious materials (e.g.,
portland cement and mix water, or lime (CaO — quicklime,
originally — and water) constitute the binder
c) Therefore, portland cement (PC), mix water, and admixtures
(chemicals mixed to modify or enhance the properties of the
portland cement concrete (PCC) would be the paste of the PCC,
representing the cementitious material (binder) of the PCC

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2. Most common concretes are portland cement concrete (PCC) and
asphalt concrete (AC), and, of course, both are filler – binder mate-
rials
a) Gravel is the coarse aggregate (CA)
b) Sand is the fine aggregate (FA)
c) Where portland cement (PC), mix water, and admixtures com-
bines form the paste of the portland cement concrete (PCC)
constitute the binder in portland cement concrete (PCC), the
asphalt binder with viscosity improvers (where applicable)
constitute the binder in asphalt concrete (AC)
d) PCC = CA + FA + PC + mix H2O + admixtures
AC = CA + FA + asphalt binder + viscosity modifiers

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• Cement paste = cement + water
Glue (or binder) that bonds aggregates together to make concrete

• Mortar = cement paste + sand

• Concrete = cement + water + sand + gravel:

Portland cement (7.5% - 15% of volume)
Water
Aggregates (60% - 75% volume)
Air voids (1% - 15% of volume)
Sometimes admixtures

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 w/c Ratio w/c Ratio
Air Entrained Concrete Non-air Entrained Concrete
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Hydraulic cements vs. Non-hydraulic cement:

- Non-hydraulic cement will not set in wet conditions or underwa-

ter; rather, it sets as it dries and reacts with carbon dioxide (Co2)
in the air.

- Hydraulic cements (e.g., Portland cement) set and become adhe-

sive due to a chemical reaction between the dry ingredients and
water. They can set while submerged in water.

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B. Second, What Are the Types of Cements Used
1. Before hydraulic cements dominated construction, there were non-
hydraulic cements.
The dominant non-hydraulic cement, lime (CaO) — combines or
chemically reacts with CO2 (in the air) forming the hard limestone:
CaO + CO2 ← → CaCO3
through a process known as carbonation
a) Lime, in the form of quicklime or caustic lime (CaO) and hy-
drated lime or slaked lime (Ca(OH)2), the foremost non-
hydraulic cement is no longer used as a cement
b) Gypsum is fully hydrated lime sulfate (CaSO4 · 2H2O) and is
soluble in water
c) The ancient Romans mixed lime in their concrete (Roman

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 Concrete), as in the dome of the Pantheon; however, Roman
Concrete was not reinforced, and hence, there was no danger
of the carbonation causing corrosion of the reinforcing steel
Lime cures by combining with the carbon dioxide of the air to
cure to form limestone (CaCO3) and result in the hardening of
the mortar

2. The other non-hydraulic cement used in the past was natural as-
phalt, used, say, in the Byzantine Empire (or the Eastern Roman
Empire) where the natural asphalt was used as the binder in ma-
sonry mortar

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 Today, petroleum-derived asphalt is used widely for the manufac-
turing of asphalt concrete (AC) used in the construction of pave-
ments
Asphalt cement cures or hardens by cooling down or by having its
solvents evaporate

3. Hydraulic cements — combine with water, through a non-chemical

hydration, exothermic process, to cure (harden)
a) Portland cement (PC) is a manufactured cement, although a
similar cement is also present in nature (natural cement).
Important PC properties include fineness, compressive
strength, soundness, time of setting, and heat of hydration

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 6.1 Portland Cement Production
1. Crushing and grinding of raw materials
Calcium Oxide (calcareous material)
 limestone, chalk, or oyster shells
Silica & Alumina (argillaceous material)
 clay, shale, blast furnace slag
o o
2. Heat and melt in a kiln at 1400-1650 C (2500-3000 F) which forms cement
clinker
3. Add gypsum (delays set time) to clinker and pulverize to fine powder
11
7 x 10 particles / lb
 small particles produce a large surface area for more complete hy-
dration

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Manufacturing of Portland Cement (Wet or Dry Methods)

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C. Portland Cement (PC) — the Quintessential Hydraulic Cement
1. Primary constituents by proportions are calcareous materials (con-
taining over 75 % limestone (CaCO3 > 75 %), argillo-calcareous
materials (40 % < CaCO3 < 75 %), and argillaceous materials
(CaCO3 < 15 %).
2. Production of portland cement (PC) from the above three major
feedstocks:
a) Calcareous material or lime (CaO), from limestone, chalk
(CaCO3), gypsum (CaSO4 · 2H2O), or oyster shell (CaCO3)

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b)Argillaceous material or a combination of silica (SiO2) and alu-
mina (Al2O3) from clay (containing minerals such as iron, mag-
nesium, and other alkali earth metals), shale (clay, minerals, and
quartz (SiO2)), and blast furnace slag (CaO, SiO2, Al2O3, and
MgO)

c) Thus, the primary components in the manufacture of PC are:

Lime (CaO) — 60 % – 65 %
Silica (SiO2) — 20 % – 25 %
Iron oxide (Fe2O3) and alumina (Al2O3) — 7 % – 12 %

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3. Manufacture of portland cement (PC) employs either the dry or the
wet method where limestone (CaCO3) and sand or silica (SiO3), and
all other constituents are ground and placed in a sloping, rotating kiln
a) The ingredients or the raw materials are mixed in different
proportions to effect different properties of the cement in the
heated mixer, or the sloping, rotating kiln
b) In the kiln, some of the ingredients decompose, and undergo
solid-state chemical reaction; for example, lime (CaO) com-
bines with the iron oxide (Fe2O3) and iron sulfide (FeS2) in the
limestone. Unfortunately, the sulfur and the sulfurous com-
pounds, such as hydrogen sulfide (H2S) trapped in the lime-
stone (CaCO3), are released, producing toxic air contaminants

c) The kiln output, namely, the cement clinker, is ground to a pre-

specified granularity

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4. Chemical composition of PC — main ingredients
a) Tricalcium silicate (3CaO · SiO2) (or C3S) — 45–60 wt% —
provides high early strength, albeit producing high heat of hydration
b) Dicalcium silicate (2CaO · SiO2) (or C2S) — 15–30 wt% —
provides slow hydration, and high later strength, with low ear-
ly heat of hydration
c) Tricalcium aluminate (3CaO · Al2O3) (or C3A) — 6–12 wt% —
has poor cementing capabilities, however, provides fast early
strength, but releases high heat of hydration and reduces re-
sistance to sulfates
d) Tetracalcium aluminoferrite (4CaO · Al2O3 · Fe2O3) (or C4AF)
— 6–8 wt% — does not contribute to strength, but reduces the
clinkering temperature, which is important during the manu-
facture of the portand cement (PC)

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5. Strength of the portland cement (PC) is a function of the different
concentrations of the ingredients, primarily, the dicalcium and
tricalcium silicates

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Summary: Main Compounds of PC

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The following are considered supplementary cementitious materials
b) Slag cement is ground blast furnace slag, and is the slag with
hydrated lime (Ca(OH)2)
c) Pozzolana (natural) is essentially volcanic ash (mostly alumi-
num silicates, e.g., Al2SiO5), and has little cementing capabili-
ties; however, if ground and given time for it to react with hy-
drated lime or calcium hydroxide (Ca(OH)2), it obtains ce-
menting properties — hence the appellation of “a latent hy-
draulic cement”

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d) Fly ash is a “man-made” pozzolana, which is obtained from the
discharge of smoke stacks of furnaces burning ground or pow-
der coal

e) Silica fume is very fine silica (SiO2), produced as the byproduct

of reducing quartz, and has pozzolanic properties

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6. Standard types of portland cement concrete (PC) — produced by
varying ingredient (tricalcium silicate, dicalcium silicate, tricalcium
aluminate, and tetracalcium aluminoferrite) proportions — are avail-
able for different applications of portland cement concrete (PCC)

PC Types: I, II, III, IV, V, and E

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a) Type I and Type I A — general purpose use portland cement
.

concrete (PC)
b) Type II and Type II A — moderate resistance to sulfates
c) Type III and Type III A — high early strength (high heat of hydration)
d) Type IV — low heat of hydration (high latent strength)
e) Type V — resistance to severe sulfate action which produce ex-
pansion
(The suffix “A” refers to air entrained versions or the types of PC)
f) Type E–1 (K), (M), or (S) Expansive Cements — cements that expand
somewhat during hydration, but do not shrink subsequently, for
shrinkage compensating concrete (the cement contains lime, gypsum,
and tetracalcium trialuminate sulfate)
Useful for gravity dams, water reservoirs, waste water treatment
plants, and other concrete constructions that cannot accommodate

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 cracking and/or jointing
Also useful when expansion of the portland cement concrete (PCC) is
restricted by reinforcing steel, and can help stabilize the post-tension
volume of the PCC
This type of portland cement (PC) resists shrinkage, which is the result
of the removal — via drying — water in the capillary voids (but not in
the larger voids)

g) Masonry cements are same as above, plus lime (CaO or Ca(OH)2)

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Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Fourth Edition. Copyright © 2017 Pearson Education, Inc.
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D. Desirable Attributes and Qualities of Portland Cement (PC)
1. Chemical inertness of portland cement (PC) is important; particular-
ly, there should be no chemical reactivity between some of the com-
ponents, such as sodium oxide (Na2O) and potassium oxide (K2O) —
the alkalis — in the portland cement (PC), and the silica (SiO2 com-
ponent.

Alkali–silica reactivity can cause production of gases, and thus inter-

nal expansion in the concrete, and cracking of the concrete

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 Results of Alkali–Silica Reactivity

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2. Fineness of the grain of the portland cement (PC) is important be-
cause the grain size affects the surface area of the PC, which affects
the:
a) Hydration rate of the portland cement (PC),
b) Heat of hydration generated in the portland cement concrete
(PCC),
c) Rate of gain in strength of the portland cement concrete (PCC),
and
d) Cost of portland cement (PC) by raising its production cost, the
quality of the PC
The fineness of the portland cement (PC) is determined by its per-
meability to air (Using Blaine air permeability apparatus)
3. The specific gravity of the portland cement (PC) is critical to the
portland cement concrete mix design (~3.15)

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4. There is a requirement for the soundness of portland cement (PC)
paste, i.e., the PC and water (with admixtures), which refers to the
ability of the paste to retain its volume through the curing process
— a standard met by testing with the use of an autoclave expansion
apparatus – per ASTM C150 should be <0.8%:

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 5. Portland cement (PC) is required to meet strength requirements us-
ing compressive (as well as a now-obsolete tensile) strength tests.
a) The strength of portland cement (PC) is determined by meas-
uring the strength of mortar made with Ottawa standard sand

b) There are different strength requirements for the different

types of portland cement (PC) and at different curing intervals.
ASTM C150 specifies minimum compressive strength of mor-
tar cubes for different cement types

Prior to determining the strength of portland cement, its (Initial and Final Set
time (indicating the normal consistency of the cement) should be deter-
mined using either Vicat or Gillmore Penetrometer:

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 Tests for Initial and Final Set

• penetration of weighted needle

Vicat

Gillmore

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 6.11 Admixtures for Concrete

Commonly used to improve properties of fresh and hardened

concrete
Types of admixtures
1. Air entrainer
2. Water reducer
3. Retarder
4. Hydration controller
5. Accelerator
6. Specialty admixtures

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E. Admixtures Mixed in the Portland Cement (PC) Paste
1. Air entraining agents, comparable to soapy materials or detergents,
produce evenly distributed air bubbles throughout the portland ce-
ment (PC) paste

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a) The primary benefit of air entrainment is resistance to the ef-
fects of repeated cycles of freezing and thawing of water ab-
sorbed by the hardened portland cement concrete (PCC); the
entrained air provides room for the expanding water as it
freezes
b) The secondary benefit of air entrainment is improving the
workability of the freshly mixed concrete without requiring
added mix water
c) Another benefit of using air entrainment is water-tightness of
the portland cement concrete
d) Yet another benefit of air entrainment is resistance to de-icing
agents or chemicals sulfates, and alkalis
e) The only demerit of using air entrainment is a 20 % reduction
in the strength of the concrete — some of said loss in strength
being mitigated by the lower w/c ratio

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2. Water reducers diminish the need for added mix water intended to
improve workability of the freshly mixed concrete by diminishing
the static electricity binding portland cement (PC) grains

Effects of using different water reducers on slump or wetness of

portland cement concrete (PCC):

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(a) Slump of PCC without any water reducer
(b) Slump of PCC with conventional water
reducer
(c) Slump of PCC with mid-range water reducer
(d) Slump of PCC with high-range water reducer
(super-plasticizer)

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(a) Slump of PCC without any water reducer
(b) Slump of PCC with conventional water
reducer
(c) Slump of PCC with mid-range water reducer
(d) Slump of PCC with high-range water reducer
(superplasticizer)

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2.1 Superplasticizers or high-range water reducers are polycarboxylate
ethers that improve the viscoelasticity of the freshly mixed concrete
considerable over a short period, thus improving the flow of the
concrete
3. Retarders delay the hardening of the concrete to compensate for
hot weather so as to allow:
a) More time to place and finish the portland cement concrete (PCC)
b) Reduction in heat of hydration build-up rapidly — to prevent
expansion and cracking

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4. Hydration control admixtures allow a delay in the onset of hydra-
tion with the use of a stabilizer component for up to three days; an
activator component allows for hydration to start. Different acidic
compounds help ready-mix plants to delay the start of transporta-
tion of the mixed concrete
5. Accelerators, such as calcium chloride (CaCl2) help speed up hy-
dration of the portland cement (PC) and, thus, hardening portland
cement concrete (PCC); this would help race against upcoming frost,
reduce curing time, harden the concrete so traffic can flow over it
sooner, or plug up hydraulic leaks

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7. Other admixtures help protect against corrosion (of metals),
shrinkage, permeability, etc. Still others help improve the mobility
of the portland cement concrete (PCC) through pumps and hoses.
There are coloring agents, fungicides and insecticides, and other
specific admixtures to meet specific needs.
A word about admixtures:
In some cases, it is advisable to restrict the use of certain admixtures,
per recommendation of the American Concrete Institute (ACI), or not
use altogether, per recommendation of the Portland Cement Associa-
tion (PCA).
In general, it is possible to not use most admixtures by choosing the
proper type of portland cement (PC), other ingredients of portland ce-
ment concrete (PCC) carefully, and modifying the PCC mix according to
prevailing conditions more meticulously.

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F. Mix Water Used Produce Portland Cement Concrete (PCC)
In general, the water used should be potable water. Sometimes, it is
possible to use underground water that has not been treated.

H. Sustainability and Environmental Effects of Manufacturing and Using

Portland Cement (PC)
1. Portland cement (PC) itself is not recyclable, reducing the need for
fresh PC manufacture; however, portland cement concrete (PCC) is
highly recyclable — as filler for future PCC; therefore, any consider-
ation for certification of PC under Leadership in Energy and Envi-
ronment Design (LEED) standards, sanctioned by the U.S. Green
Building Council (USGBC), has to be linked to similar considerations
for portland cement concrete (PCC)
2. As stated above, hydrogen sulfide (H2S) trapped in the limestone

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 (CaCO3), is released in the manufacture of portland cement (PC),
and such releases of the highly toxic H2S must be contained
3. The manufacture of portland cement (PC) is energy intensive; thus,
choice of fuels used in producing the heat for the kiln that produces
the clinker is important environmental factors

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