Cement Extenders Mechanisms & Chemistry

2021-04-23Drilling Manual
https://www.drillingmanual.com/2021/04/cement-extenders-mechanisms-chemistry.html

As mentioned in Cementing Additives article, cement extenders are used to reduce cement
slurry density & increase slurry yield ( Check also: oil well cement properties). The most
common cement extenders chemicals are:

 Clays
 Sodium silicates
 Pozzolans
 Lightweight particles

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Clay minerals are hydrous aluminum silicates of the phyllosilicate group (Hurlbut, 1971), in
which the silica tetrahedra are arranged in sheets. Such minerals have platy or flaky shape and
one prominent cleavage. Magnesium or iron can partially substitute for aluminum in the crystal
lattice, and alkalis or alkaline earth may also be present as essential components.

Bentonite

The most frequently used clay-based cement extenders is bentonite, also known as “gel,”.
Bentonite has the unusual property of expanding to several times its original volume when
placed in water, resulting in higher fluid viscosity, gel strength, and solids-suspending ability.

Bentonite is added in concentrations up to 20% BWOC. Above 6%, the addition of a dispersant
is usually necessary to reduce the slurry viscosity and gel strength. The API/ISO recommends
that 5.3% additional water (BWOC) be added for each 1% bentonite for all classes of cement;
however, testing is necessary to determine the optimal water content with a particular cement.
As shown in Table 1, the slurry density decreases and the yield increases with bentonite
concentration; however, as shown in Fig. 1, there is a price to be paid in terms of compressive
strength. Cement permeability also increases with bentonite concentration; therefore, such
cement is less resistant to sulfate waters and corrosive fluids. However high concentrations of
bentonite tend to improve fluid-loss control.

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 Table 1. Effect of Bentonite on Cement-Slurry Properties

Figure 1. Effect of bentonite on compressive strength.

High concentrations of Ca2+ ion in the aqueous phase of a cement slurry inhibit the hydration of
bentonite. The extension efficiency of bentonite can be greatly enhanced if it is prehydrated in
the mix water before cement addition. A slurry containing 2% prehydrated bentonite BWOC is
equivalent to one containing 8% dryblended bentonite (Table 3-4). Complete hydration of a
good-quality bentonite occurs in about 30 min. The thickening times of prehydrated bentonite
slurries are generally the same as those of dry-blended slurries at the same density. It should
also be noted that prehydrating the bentonite does not appreciably change the final
compressive strength when compared to an equal density slurry prepared with dry-blended
bentonite.

According to API/ISO specifications, only pure, untreated bentonite should be used in well
cements. Beneficiating agents such as polyacrylamide, which improve the water absorption
capacity of low-grade bentonites, are prohibited. Such materials can interfere with the
performance of other cement additives and lead to unpredictable results (Grant et al., 1990).

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Attapulgite

Bentonite can be prehydrated in seawater or light brine, but the salt inhibits hydration and the
slurry yield is reduced. Bentonite is not effective as an extender in highly saline cement slurries.
Under such circumstances, another clay mineral, attapulgite, is frequently used (Smith and
Calvert, 1974).

Attapulgite, (Mg,Al)5Si8O22(OH)4 • 4H2O, also known as “salt-gel,” occurs as fibrous needles.

When dispersed in water, the attapulgite needles associate with one another and provide
viscosity. Unlike bentonite, attapulgite does not improve fluid-loss control. Attapulgite has been
banned in some countries because the fibrous needles are similar to those of asbestos
(Bensted, 2001). However, granular forms of attapulgite are available that are still permitted in
many locations.

Cement Extenders – Sodium silicates

Silicate extenders react with lime or calcium chloride in the cement to form a calcium silicate
gel. The gel structure provides sufficient viscosity to allow adding extra mix water without
excessive free-water separation. Sodium silicates are available in solid or liquid form. A major
advantage of the silicates is their efficiency, which minimizes storage and handling. However,
because of their tendency to accelerate, they tend to reduce the effectiveness of other additives,
retarders, and fluid-loss agents in particular.

Solid Sodium Silicate

The solid sodium silicate is normally dry-blended with the cement. If it is added to fresh mix
water before slurry preparation, a gel may not form unless calcium chloride is also added. If a
gel does not form, the proper slurry extension will not occur. The recommended concentration
range of Na2SiO3 is 0.2% to 3.0% BWOC. These concentrations provide a slurry-density range
of from 14.5 to 11.0 lbm/gal [1.75 to1.35 g/cm3]. The typical properties and performance of
sodium metasilicate-extended cement systems are shown in Table 2.

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 Table 2 Typical Performance of Class G Cement Systems Containing Sodium Metasilicate

Liquid Sodium Silicate

The liquid sodium silicate, (also called water glass), is added to the mix water before slurry
mixing. If calcium chloride is to be included in cement systems mixed with fresh water, it must
be added to the mix water before the sodium silicate to obtain sufficient extending properties. In
the case of slurries mixed with seawater, sodium silicate will interact with the divalent cations in
the seawater to achieve slurry extension. The normal concentration range is 0.2 to 0.6 gal/sk.
Typical performance data are presented in Table 3.

Table 3 Effect of Liquid Sodium Silicate on the Performance of Class G Cement Slurries Mixed with Fresh
Water

Cement Extenders – Pozzolans

Pozzolans are perhaps the most important group of cement extenders. They are defined in
accordance with ASTM International designation C-219-55 as follows: A siliceous or siliceous
and aluminous material, which in itself possesses little or no cementitious value, but will, in

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finely divided form and in the presence of moisture, chemically react with calcium hydroxide at
ordinary temperatures to form compounds possessing cementitious properties.”

Thus, pozzolans not only extend Portland cement systems, but also contribute to the
compressive strength of the set product.

There are two types of pozzolans:

 Natural pozzolans, which include volcanic ashes and diatomaceous earth, and

 Artificial pozzolans, such as certain fly ashes.

When one 94-lbm sack of cement hydrates, about 20 to 23 lbm of free Ca(OH)2 are liberated.
By itself, Ca(OH)2 contributes little to the strength of the set cement and is fairly soluble; thus, it
can be eventually dissolved and removed by water contacting the cement. This contributes to a
weakening of the set cement. When a pozzolan is present, the silica combines with the free
Ca(OH)2 to form a stable cementitious compound (secondary C-S-H) that is very durable.

At typical cement densities, the water permeability of set pozzolan/cement systems is usually
less than 0.001 mD. The low permeability of the set cement, as well as the decrease of free
Ca(OH)2 content, resists the encroachment of sulfate water and other corrosive fluids. Should
corrosive waters manage to enter the set pozzolanic cement, damage is further prevented by
another mechanism. Zeolites in the pozzolan act as ion exchange agents and help prevent
deterioration.

Mixing Pozzolan Cements

There are two notation systems commonly used for mixing pozzolan cements.

 The first is a bulk/volume ratio. A 1:1 ratio indicates 1 ft3 of pozzolan and 1 ft3 of
cement. The first figure always indicates the volume of pozzolan, and the second
indicates the volume of cement. This system is used primarily with very light pozzolans.

 The second mixing system is the most widely used. It is based on the “equivalent sack.”
A sack of Portland cement has an absolute volume of approximately 3.59 gal. In other
words, when mixed with water, one sack of cement will increase the volume of the mix
by about 3.59 gal. An equivalent sack is the weight of pozzolan that also has an absolute
volume of 3.59 gallons. Different pozzolans have different equivalent sack weights. The
ratio for mixtures based upon equivalent sacks is designated as 25:75, 50:50, 75:25, or
whatever ratio is desired. The term 25:75 indicates 1⁄4 eq sk of pozzolan and 3⁄4 eq sk
of Portland cement.

The weights of other cement extender additives (except salt) are calculated as a percentage by
weight of the pozzolan/ cement equivalent sack. Salt is always calculated as a percentage of
the mix-water volume.

As an example, an equivalent sack of one typical fly ash is 74 lbm. A 50:50 blend would require
37 lbm of fly ash and 47 lbm of Portland cement. Thus, 84 lbm of this blend would displace 3.59
gal. Additive concentrations would then be calculated as a percentage of an 84-lbm equivalent
sack, not the usual 94-lbm sack of Portland cement. A more detailed discussion of pozzolanic
slurry calculations is presented in Appendix C.

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Diatomaceous earth

Diatomaceous earth is composed of the siliceous skeletons of diatoms deposited from either
fresh water or seawater. The main constituent of diatomaceous earth is opal, an amorphous
form of hydrous silica containing up to 10% water. For use as a pozzolanic extender,
diatomaceous earth is ground to a fineness approaching that of Portland cement; consequently,
it has a large surface area and a high water demand. Diatomaceous earth imparts slurry
properties similar to those of bentonite slurries; however, it does not increase the slurry viscosity
to such a high degree. In addition, because of its pozzolanic activity, set cements containing
diatomaceous earth are stronger than their bentonitic counterparts. The principal disadvantage
of diatomaceous earth is its cost. Typical slurry properties and performance of diatomaceous
earth slurries are shown in Table 4.

Table 4. Effect of Diatomaceous Earth on the Performance of Class A Cement Systems

Fly ashes

Fly ash is the residue from power plants that burn pulverized coal (Davis et al., 1937). The ash
is suspended in flue gases as fused particles that solidify into a roughly spherical shape. The
ash is very finely divided, with a surface area roughly approximating that of Portland cements.
The major constituent of fly ash is a glass chiefly composed of silica and alumina with some iron
oxide, lime, alkalis, and magnesia. Quartz, mullite, hematite, and magnetite, as well as some
combustible matter, are also found. The composition and properties of fly ash can vary widely
depending upon the source of the coal and the efficiency of the power plant; accordingly, the
specific gravities of fly ashes can vary from about 2.0 to 2.7 (Hewlett, 2001).

According to ASTM International specifications, three types of fly ash are recognized: Types N,
F, and C. As shown in Table 5, the distinction is made on chemical grounds. Types N and F are
normally produced from burning anthracite or bituminous coals. Type C fly ashes, made from
lignite or subbituminous coals, are less siliceous, and some contain more than 10% lime; as a
result, many of them are cementitious and do not fit the strict definition of a pozzolanic material.
In well cementing, Type F fly ash is used most frequently.

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 Table 5. Chemical Requirements for Fly Ashes

Normally, 2% bentonite is added to Type F fly ash/ Portland cement systems to improve the
slurry properties and prevent the development of free water. In Table 6, slurry data for different
ratios of Type F fly ash and cement are presented with various water contents.

Table 6. Properties of Fly Ash/Class H Cement Systems

The use of Type C fly ashes as extenders for well cements is relatively new. Because of the
significant amount of lime in such fly ashes, the rheological effects must be carefully monitored.
In addition, Type C ashes vary widely depending upon the source, and special slurry
preparation guidelines are required for each.

Some Type C fly ashes are sufficiently cementitious to be used as the principal component of a
well cement. Such systems have been developed for application in shallow wells having
circulating temperatures up to 120°F [49°C]. Compressive strength development is often more
rapid than that observed with conventional Portland cement systems.

Commercial lightweight cements

Commercial oilwell cements, such as TXI Lightweight‡, are special formulations composed of
interground Portland cement clinker and lightweight siliceous aggregates; consequently, some
pozzolanic activity occurs. They are convenient and time-saving for the service company. The
particle-size distribution is finer than in Portland cements, and the normal slurry density range is
from 11.9 to 13.7 lbm/gal [1.43 to 1.64 g/cm3].

Silica

Three forms of finely divided cement extender silica are used in well cements: α-quartz,

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condensed silica fume, and colloidal silica dispersions. Silica as α-quartz is used most
frequently for the prevention of strength retrogression when Portland cement systems are
placed in thermal wells. Two particle sizes are routinely used: silica sand, with an average
particle size of about 100 μm, and silica flour, with an average particle size of about 15 μm.
Other sizes of crystalline silica are used in special cement systems with controlled particle-size
distributions. Because of cost, these materials are rarely used for slurry extension alone.

Condensed silica fume (also called microsilica) is a byproduct of the production of silicon,
ferrosilicon, and other silicon alloys. The individual particles are glassy, amorphous
microspheres. The mean particle size is usually between 0.1 μm and 0.2 μm, about 50 to 100
times finer than Portland cement or fly ash; consequently, the surface area is extremely high
(15,000 to 25,000 m2 /kg).

Condensed silica fume is highly reactive and, because of its fineness and purity, is a very
effective pozzolanic material (Parker, 1985). Its high degree of pozzolanic activity has led to the
introduction of low-density cement systems with a higher rate of compressive strength
development (Carathers and Crook, 1987). The high surface area of condensed silica fume
increases the amount of water required to prepare a pumpable slurry; therefore, slurries with
densities as low as 11.0 lbm/gal [1.32 g/cm3] have little or no free water. The normal
concentration of this material is about 15% BWOC; however, up to 28% BWOC is possible.

The fineness of condensed silica fume also promotes improved fluid-loss control, perhaps by
reducing the permeability of the initial cement filtercake (Mueller and Dillenbeck, 1991). For this
reason, it is also used for the prevention of annular fluid migration (Grinrod et al., 1988;
Golapudi et al., 1993). In addition, it is used as a source of silica in thermal cement systems
(Grabowski and Gillot, 1989; Noik et al., 1998). High retarder concentrations are often required
owing to the high specific surface area of silica fume.

Colloidal silica dispersions are aqueous sols of pure amorphous silica and traces of sodium
hydroxide. Like microsilica, colloidal silica particles are spherical; however, the particle size is
about one order of magnitude smaller (0.05 μm). Therefore, the surface area of colloidal silica is
about 500,000 m2 /kg. The primary applications of colloidal silica are to prepare low-density
cement systems and to prevent annular fluid migration (Bjordal et al., 1993).

Cement Extenders Lightweight particles

Lightweight particle extenders reduce the slurry density because they are lighter than the
cement particles. Such extenders include expanded perlite, powdered coal, gilsonite, and either
glass or ceramic microspheres. Most extenders in this category are inert with respect to the
cement.

Expanded perlite

Perlite is a crushed volcanic glass that expands when heated to the point of incipient fusion
(Lea, 1971). The expanded perlite product generally has a bulk density of 7.75 lbm/ft3, which
allows the preparation of competent cement slurries with densities as low as 12.0 lbm/gal [1.44
g/cm3]. A small quantity of bentonite (2% to 4% BWOC) is added to prevent the segregation of
the perlite particles from the slurry.

Expanded perlite contains both open and closed pores. Under hydrostatic pressure, the open

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pores fill with water, and some of the closed pores are crushed; as a result, the perlite becomes
more dense. To maintain density control, the use of perlite is confined to shallow wells.

To prepare an expanded perlite slurry that will have a given density downhole, it is necessary to
mix a lower density slurry at the surface. At 3,000 psi [20.7 MPa], the specific gravity of
expanded perlite is 2.40. Table 7 shows some typical slurry designs (check also cement
design guidelines) and illustrates how the slurry density increases between atmospheric
pressure and 3,000 psi [20.7 MPa]. Owing to the density variability, perlite is rarely used today.

Table 7. Properties of Cement Systems Containing Expanded Perlite and Bentonite†

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Cement Extenders – Gilsonite

Gilsonite is a naturally occurring asphaltite mineral, found primarily in northeastern Utah. The
specific gravity of gilsonite is 1.05. The water requirement for gilsonite is low, about 2 gal/ft3;
thus, it is possible to prepare low-density cement systems with relatively high compressive
strength (Slagle and Carter, 1959). Up to 50 lbm of gilsonite can be used per sack of Portland
cement to achieve slurry densities as low as 12.0 lbm/gal [1.44 g/cm3]. However, mixing
difficulties may occur at such high concentrations. Bentonite is often included in the slurry to
keep the gilsonite particles evenly dispersed.

Cement Extender Gilsonite is a black, angular solid, normally supplied as a ground material with
a wide particle-size distribution (up to 0.6 cm). It is often used to prevent lost circulation.
Gilsonite has a melting point of 385°F [196°C]. Some softening occurs above 240°F [116°C],
and the particles may tend to fuse. As a result, gilsonite is not recommended for use in wells
with bottomhole static temperatures above 300°F [149°C].

Powdered coal

The performance of powdered coal as an extender is very similar to that of gilsonite. Its specific
gravity is slightly greater (1.30). Like gilsonite, it is coarsely ground (50% of particles between 6
and 12 mesh) and is often used to prevent lost circulation. Unlike gilsonite, the melting point of
powdered coal is high—1,000°F [538°C]. Therefore, powdered coal can be used in thermal well
environments. Between 12.5 and 25 lbm of powdered coal are normally added per sack of
cement to prepare slurries with densities as low as 11.9 lbm/gal [1.43 g/cm3]. Bentonite is often
added to such slurries to prevent the coal from segregating. Table 8 illustrates typical slurry
designs for powdered coal systems.

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 Table 8. Physical Properties of Class A Cement Slurries Containing Powdered Coal and Bentonite

Microspheres Cement Extenders

Microspheres are small gas-filled beads with specific gravities normally between 0.2 and 0.9.
Such low specific gravities allow the preparation of high-strength, low-permeability cements with
densities as low as 7.5 lbm/gal [1.02 g/cm3] without the need for nitrogen. Two types of
microspheres are available: glass and ceramic.

The original application of microspheres was for primary cementing of conductor and surface
pipes, in which washouts and low formation fracturing pressures are common. However, they
are used much more extensively today, and in many cases microsphere cements have
eliminated the need for multistage cementing. Microspheres have also found use in special
cement systems with controlled particle-size distributions. A significant limitation of

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microspheres is their inability to withstand high hydrostatic pressure without being crushed;
thus, they cannot be used in deep wells. Microsphere cement systems require special care in
design and mixing, and these special procedures are briefly described below.

Glass microspheres are manufactured from borosilicate glass. Several grades are commercially
available, and the specific gravity varies from 0.12 to 0.80 (Smith et al., 1980). All grades have
roughly the same particle-size distribution (30–40 μm), and their pressure resistance is directly
related to specific gravity. Most grades of glass microspheres withstand pressures up to 5,000
psi [34.5 MPa]; however, the heavier grades with thicker walls will survive to 10,000 psi [68.9
MPa]. Glass microspheres are significantly more expensive than their ceramic counterparts;
thus, their use is relatively infrequent.

Ceramic microspheres, also called cenospheres, are derived from ash produced by coal-
burning power plants. Their composition is variable, but the principal constituents are silica and
alumina (Table 9) The material is mainly amorphous; however, small amounts of mullite are
sometimes detected by X-ray diffraction. They have low reactivity in a Portland cement matrix;
however, some pozzolanic behavior can occur at high curing temperatures (Drochon and
Maroy, 2000).

Table 9. Typical Chemical Composition of Cenospheres

The particle-size range is between 20 and 500 μm. The shell thickness is about 10% of the
particle radius. The composition of the gas inside is a mixture of CO2 and N2. The
microspheres are heavier than their glass counterparts, with a specific gravity of 0.6–0.9 and a
bulk density of 25 lbm/ft3; thus, a higher concentration is necessary to achieve low slurry
densities (Harms and Sutton, 1981).

As mentioned earlier, both glass and ceramic microspheres are susceptible to breakage and
collapse when exposed to high hydrostatic pressure; as a result, the density of the slurry
increases (Messenger, 1974). The pressure resistance of ceramic microspheres can vary widely
depending upon the source (Fig. 2). This increase can be predicted and as shown in Fig. 3, can
be taken into account in the design calculations. When the microspheres are crushed, the slurry
volume decreases and the packing volume fraction changes. This can lead to significantly
higher slurry viscosities. The use of ceramic microspheres is not recommended when
bottomhole pressures exceed 4,500 psi [31 MPa].

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 Figure 2. Percent crushing of two sources of cenospheres versus hydrostatic pressure.

Figure 3. Density of cenosphere-extended slurries versus pressure.

It is important to ensure that the extender microspheres do not separate from the cement
particles during the blending process. The microspheres must be thoroughly dryblended with
the cement and not premixed in the water. Any variation in the ratio of microspheres to cement
will result in erratic densities during mixing. The bulk volume of microspheres is high relative to
their specific gravity; therefore, when preparing blends, it is important to ensure that the capacity
of the blending equipment is adequate.

Microspheres extenders are compatible with any class of cement. Figure 4 illustrates the
amount of microspheres required to achieve slurry densities between 8.5 and 15.0 lbm/gal [1.02
and 1.80 g/cm3]. Mix water requirements are shown in Fig. 5 and slurry yields in Fig. 6. The
relationship between the density of ceramic microsphere system density and compressive
strength is illustrated in Table 10.

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 Figure 4. Typical cenosphere concentration requirements versus slurry density.

Figure 5. Water requirements for cenosphere-extended cement systems.

Figure 6. Yield of cenosphere-extended cement systems.

Table 10. Compressive-Strength Data for Cenosphere Extended Cement Systems Mixed with Class G
Cement + 1% Calcium Chloride†

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Nitrogen Cement Extenders

Foamed cement is a system in which nitrogen is incorporated directly into the slurry to obtain a
low-density cement. The system requires the use of specially formulated base cement slurries
to prepare a homogeneous system with high compressive strength and low permeability.
Incorporating nitrogen allows the preparation of competent cement systems with densities as
low as 7.0 lbm/gal [0.84 g/cm3]. The reader is referred to for a complete discussion of this
important technology.

Ref: Schlumberger Well Cementing, Erik B. Nelson and Dominique Guillot

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