Cement Manufacture and Chemistry

Cement is manufactured with materials and methods that have changed little over
the last 160 years. Joseph Aspdin, a builder from Leeds, UK, was granted a patent in
1924 for "a cement of superior quality resembling Portland stone." Asp-din's cement
was prepared by sintering fixed proportions of calcareous materials (limestone, chalk,
seashells, etc.) with aluminosilicates (clays) in a kiln at temperatures of 1425 to
15350 C. The resulting material, which is called clinker, is then cooled and ground
with gypsum to form Portland cement. Gypsum is added to prevent flash set. In
addition to the basic raw materials cited above, other materials such as sand,
bauxite, iron oxide, etc., may be used in the kiln feed to adjust the elemental ratios in
the resulting clinker.

Portland Cement Components

The principal components of common Portland cement are
50% tricalcium silicate/C3S* (3CaO SiO2)
25% dicalcium silicate/C2S* (2CaO SiO2)
10% tricalcium aluminate/C3A* (3CaO Al2O3)
10% tetracalcium aluminoferrite/C4AF* (4CaO Al2O3 Fe2O3) 5% other
oxides
* C3S, C2S, C3A, and C4AF are commonly used abbreviated notations for the
cement components.
The relative amounts of the above compounds may be varied depending on the
intended application of the cement. The component having the greatest effect on the
overall strength of Portland cement is C3S; it is also responsible for the early strength
(1 to 28 days) of the set mass. C3S is the slow-reacting component that accounts for
the gradual gain in strength of the cement which occurs over an extended period of
time. Of the above components, C3A shows the fastest rate of hydration. The initial
set and thickening time of cement, as well as the sensitivity of the set cement to
sulfate-containing waters, are influenced by the concentration of this component.
C4AF is the low heat of hydration compound in cement; the addition of Fe 2O3 to the
kiln feet favors the production of C4AF at the expense of C3A in the clinker. This
procedure is commonly followed in the production of medium sulfate resistant (MSR
3 to 8% C3A) and high sulfate resistant (HSR up to 3% C3A) cements. A
description of the manufacture and composition of cement may be found on pages 3
to 5 of the Halliburton Cementing Tables.

Hydration of Cement
Cement is composed principally of a blend of anhydrous metallic oxides. The addition
of water to this material converts these compounds to their hydrated form. After a
period of time, the hydrates form an interlocking crystalline structure which is
responsible for the set cement's strength and impermeability. The formation of this
structure, as the cement hydrates, is shown schematically and actually (by scanning
electron micrograph) in Figure 1 (The setting of portland cement ).

Figure 1

Water in excess of that required for cement to set is necessary for formation of slurry
(a suspension of solids in a continuous liquid medium) and gives the slurry its
required mobility. Removal of the excess water by filtration results in loss of slurry
mobility and in deposition of the wetted cement solids as filter cake.
The amount of water required for a given slurry depends on the type of cement and
the amount and type of additives used. For example, the water requirements for API
class "G" cement slurry, containing varying amounts of bentonite are as follows:

% bentonite

water requirement in U.S. gals/94 lb. Sack

5.0

6.3

7.6

If the amount of water is correct for a given system, the slurry will have acceptable
fluidity and will not show excessive solids-settling or free-water breakout. Water
requirements for cement and most of the commonly used additives can be found in
service company publications (e.g. Halliburton cementing tables (1981)).

Temperature Effects
As is true of most chemical reactions, the hydration of cement is accelerated by
increased temperature. Figure 2 (The effect of temperature and pressure on Portland
cement thickening time ( after Bearden, 1959)) shows the effect of temperature on
the thickening time of various cement slurries. The reaction of cement with water

begins when they are first mixed.

Figure 2

As the reaction proceeds, but before the system achieves sufficient set to have
measurable strength, the slurry shows an increase in viscosity. When the slurry
reaches a viscosity equivalent to 100 poise, it is said to be no longer pumpable. The
length of time required to achieve this viscosity under a given set of conditions is
referred to as the thickening time.

API Cement Types

Service company literature, such as Halliburton Cementing Tables , describes the
various API cement types. Section 2 of API Spec 10 describes not only the various API
cement types but the chemical ( API Table 2 .1) and physical requirements ( API Table
2 .2) for each. Note that not all countries use the API classification system. RHC
(Rapid Hardening Portland Cement) and HSC (High Strength Portland Cement), for
example, ar two non-U.S. cement classifications that correspond roughly to API class
C cement.

The API classifications and their general applications are summarized as follows: for
operations outside the United States, the predominant API Classes are A and G
(Smith, 1987).
API Class A cement also referred to in the United States as "construction cement"
or "common cement" may normally be used, mixed neat, from surface to a depth
of 6000 ft (1830 m) if no special properties are required. This cement is widely
available and its performance can be modified by the use of additives (see the
Halliburton Cementing Tables, Section 230, Blue Subsection II). Additive response and
product uniformity of Class A cement are generally inferior to those of
API Class G cement.
API class B cement is intended for use from surface to 6,000 ft depth, where
conditions require moderate to high sulfate resistance, while API class C is used this
same depth range where early high strength is needed.
API Class D cement is intended for use from 10,000 to 14, 000 ft. depth, under
conditions for moderate to high pressure and temperature. It is available in both
moderately and highly sulfate - resistant types.
API Class E is intended for use from 10,000 to 14,000 ft. depth, for conditions of high
temperature and pressure, and is available in both moderately and highly sulfate
resistant types.
API Class F is for use in the 10,000 to 16,000 ft. depth range, under conditions of
extremely high temperatures and pressures, and is available in both moderately and
highly sulfate -resistant types.
API Class G is intended for use in neat slurries from the surface to a depth of 8000 ft
(2438 m). This cement is available in both moderately sulfate-resistant and highly
sulfate-resistant forms and may be modified by additives for use in a wide range of
well depths pressures and temperatures. Specific formulations and resulting
properties of Class G slurries are found in section 230 of the Halliburton Cementing
Tables, (Subsection IV ).
API Class H cement is similar in form and application to class G, but is usually more
coarsely ground.
Most oil well-cementing operations worldwide use slurries based on API Classes A, G,
H, and C (high-early-strength cement). API Classes D, E, and F are intended for hightemperature applications, and each contains an organic set retarder added by the
manufacturer. Classes D, E, and F are not widely distributed, and in some instances
the set retarder is not compatible with materials added on-site.
API Class J cement is specifically intended for high-temperature applications; it does
not set at BHSTs less than 230 F (110 C), and does not require the addition of silica
to protect the set mass from high-temperature degradation. Class J is not widely
available.

Specialty Cements

These include such materials as these cements: pozzolan , resin or plastic , gypsum ,
diesel oil, expanding, calcium aluminate, latex, and permafrost. Although they do not
comprise the bulk of cements used in the petroleum industry, they have certain
properties that are useful in various applications. These are summarized as follows:

Specialty Cement
Type

Application

Pozzolan

High temp.; low weight requirements

Resin or Plastic

Selective plugging/squeezing operations

Gypsum

Temporary remedial work requiring rapid setting, high

strength

Diesel Oil

Control of water zones, lost circulation

Expanding

Special downhole conditions

Calcium Aluminate

Extreme high temperature (i.e., in-situ combination wells)

Latex

Improved bonding/filtration control requirements

Permafrost

Frozen environments

Formation of Cement Slurries

Cement slurries are usually prepared in the field with a jet mixer. The components
and operation of this continuous-mixing system are shown in Figure 1 (Jet mixing of
oilwell cement slurries ) Jet mixers are simple, dependable, and are not volumelimited.

Figure 1

Their principal disadvantage is an inability to closely control slurry density. Various

types of batch mixers utilizing either mechanical agitation or circulation are available
for mixing up to 100 bbl (16 m3) of cement slurry. This type of mixer can control
density within a range of 0.2 lb/gal. For some operations it is useful to prepare the
slurry with a jet mixer that discharges into a batch mixer, where final density
adjustments may be made before the slurry is pumped into the well. Recirculatingtype jet mixers can also prepare slurries with a more uniform density.

Neat Slurries
A suspension of cement in water, containing no other components, is called a neat
cement slurry. From the standpoints of ease of mixing and of economy, it would be
desirable to use such slurries extensively in oil well cementing. This is usually not
possible, however, since control of the properties of a neat slurry can be achieved
only by slight changes in liquid/solids ratio and by choice of API cement type. Table 1
, below, gives the preferred water/cement ratio for the various API cement types, as
well as the resulting slurry densities.

API Cement
Type

Recommended
Water/Cement Ratio
(gal/sack)

Slurry Density (lb/gal)

A&B

5.2

15.6

6.3

14.8

D&F

4.3

16.4

5.0

15.8

4.3

16.4

4.9

15.4

Table 1. Neat cement slurries

The range of densities of these slurries results from the different degrees of fineness
of the various types of API cement, which affect water requirement. Of the commonly
used API types, Class C is the most finely ground, Classes A and G are intermediate,
and Class H is the most coarsely ground. Slurries prepared with the finer grinds tend
to show slightly lower cement-slurry-filtration rates. The thickening time of neat
cement slurries may be estimated from the thickening-time requirements for the
various API cement classes given in Section 8, Table 8 .3, Schedules 1, 4, 5, 6, 8, and
9 of API Spec 10. API Classes A and C require a minimum thickening time of 90
minutes when tested according to Schedule 1 (final temperature 80 F [27 C]) and
Schedule 4 (final temperature 113 F [45 C]). API Classes G and H must indicate a
thickening time between 90 and 120 minutes when tested according to Schedule 5
(final temperature 125 F [52 C]). This information is useful for comparing the
relative reactivity of the various API classes; however, a thickening-time test under
simulated well conditions is an important part of most cementing jobs.
For most applications, sufficient control over slurry density, filtration rate, and
thickening time cannot be obtained simply by choosing the appropriate API cement
class; additives must be used to achieve slurry-property modification. Choice of the
proper API cement type (when a choice is possible) can make modification by the use
of additives easier.

Additive-Containing Slurries
Additives are necessary for the use of most oil well cements. This is not surprising If
one considers that Portland-type cements are designed primarily for construction
applications at surface conditions of temperature and pressure. For simplicity and
economy, it is good practice to minimize the number of additives, thereby facilitating
mixing and reducing the chances of undesirable interactions. Also, it is important to
utilize optimum concentrations of additives for each situation; for this reason, slurry
should be tested using on-site components and realistic procedures. The effects of a
variety of additives on the properties of oil well cement, according to Dwight K.
Smith, are given in Table 2 (Effects of additives on cement properties )

Table 2

Alteration of Rate of Set

Additives are used extensively to alter the rate of reaction between cement and mix
water. Acceleration of the reaction rate decreases the thickening time of the slurry
and thus the WOC time (time required for the cement to attain a compressive
strength of 500 psi [3450 kPa]). Retardation of the rate increases both thickening
time and WOC time. At shallow well depths temperatures are relatively low, pumping
times are short, and it is often necessary to accelerate the set of the cement to
reduce WOC time. This must be done within the constraint of retaining adequate
thickening times. For deep, hot wells slurries are usually retarded to attain sufficient
thickening time (plus a safety factor), but over-retardation must be avoided or WOC
time will be unduly prolonged.