Cement Additives

Almost all cement used in oil and gas wells is Portland cement. However, neat
cement is seldom used throughout a job since various additives are usually necessary
to modify the properties of either slurry or set cement. With basic cements (API Class
G or H) and the use of additives, cement slurries can be tailored for any specific
requirement.

Most additives in current use are free-flowing powders that are dry-blended with the
cement prior to its transportation to the well. When necessary, some powdered
additives can be dispersed in mixing water at the site. Liquid additives are more
commonly used offshore and in remote land locations where dry cement blending
and storage are a problem.

Properties that are modified by additives are shown below:

For the slurry:

 thickening time (acceleration, retardation)

 density (extenders, weight increase/reduction)
 friction during pumping
 fluid loss (by filtrate)
 lost-circulation resistance (whole slurry loss)

For set cement:

 compressive strength
 strength retrogression (loss with time)
 expansion/contraction

Accelerators
Cement-setting time is accelerated to reduce WOC time and to increase early
strength. This is desirable for surface pipe, in shallow (cooler) wells, and for setting
plugs.

General pressure recommendations are as follows:

pipe support and zonal isolation — 100 psi (690 kPa)

drilling out — 500 psi (3450 kPa)

perforating

—bullets — 500 psi (3450 kPa)

—hollow carrier or expendable jets — 2000 psi (13,800 kPa)

whipstock plug — 2500 psi (17,200 kPa) or greater (or harder than
formation)
The most common accelerators are calcium chloride, sodium silicate, sodium chloride
(low concentrations), seawater, hemihydrate forms of gypsum, and ammonium
chloride. Table 1 shows typical amounts used per sack.

Type Amount used per sack (% by

weight)

Accelerators

Calcium Chloride (CaCl2) (flake, powder, an 2-4

hydrous)

Sodium Chloride (NaCl) 3 - 10 (water)

1.5 - 5 (cement)

Hemihydrate forms of 20 - 100

Gypsum (plaster of Paris)

Sodium Silicate (Na2SiO3)w 1 - 7.5

Cements with dispersants and reduced water 0.5 - 1.0

Sea Water

Retarders

Calcium-Sodium Lignosulfonate 0.1 - 1.0

Calcium Lignosulfonate 0.1 to 1.0

Calcium Lignosulfonate 0.1 to 2.5

plus organic acid

CMHEC 0.1 to 1.5

Saturated Salt 15 to 17 lb/sk

Table 1. Commonly used accelerators and retarders. (Source: Halliburton
Services).

Retarders
Cement-thickening time is slowed primarily to allow the slurry to be pumped and
displaced into position before setting. Retarder additives include calcium
lignosulfonate, organic blends, carboxymethylhydroxyethyl cellulose (CMHEC), borax,
sodium chloride (in high concentrations), and most fluid-loss agents
(see Table 1).Thickening time is a function of both temperature and pressure, and
these effects must be predicted before additives are selected
Type Amount used per sack (% by weight)

Accelerators

Calcium Chloride (CaCl2) (flake, 2-4

powder, an hydrous)

Sodium Chloride (NaCl) 3 - 10 (water)

1.5 - 5 (cement)

Hemihydrate forms of Gypsum (plaster 20 - 100

of Paris)

Sodium Silicate (Na2SiO3) 1 - 7.5

Cements with dispersants and reduced 0.5 - 1.0

water

Sea Water —

Retarders

Calcium-Sodium Lignosulfonate 0.1 - 1.0

Calcium Lignosulfonate 0.1 to 1.0

Calcium Lignosulfonate plus organic 0.1 to 2.5

acid

CMHEC 0.1 to 1.5

Saturated Salt 15 to 17 lb/sk

Table 1: Commonly used accelerators and retarders. (Source: Halliburton

Services).

Thickening time can also be shortened by interruption of pumping (loss of agitation).

API tests may be done in this manner to simulate actual interruptions during
squeezing.

An increase in water volume increases the thickening time of unretarded cement

(Classes A, C, G, and H). With retarded cements (Classes D, E, and F), however,
increased water or solids may decrease thickening time by reducing the
concentration of retarder.

The thickening time of a slurry under realistic conditions must be established to

ensure adequate pumping time for slurry placement.

Excessive thickening time must be avoided to prevent:

 delays in resuming drilling operations

 settling and separation of slurry components
  formation of free-water pockets
 loss of hydrostatic head and gas cutting

Density-Reducing Additives
Slurry density may be reduced with extenders such as bentonite, pozzolan,
diatomaceous earth, and anhydrous sodium metasilicate. Table 1 shows typical
additive concentrations.

Low-density slurry is frequently preferred, to decrease the likelihood of breaking down

the formation and causing lost circulation. In addition, low-density slurries cost less
per cubic foot because yield per sack is increased.

Density decrease results in large part from increased water content. Extenders, with
their high surface area to "tie up" water, permit water addition without separation.
Cement strength is reduced approximately in proportion to water-content increase.
However, we shall see later that high strength is not always required.

Type Amount used per sack

(% by weight)

Density reducers/extenders

Bentonite 2 to 16

Attapulgite 1/2 to 4

Diatomaceous Earth (Diacel D) 10, 20, 30 or 40

Pozzolan, Artificial (fly ash) 74 lb/sk

Natural hydrocarbons:

Gilsonite 1 to 50 lb/sk

Coal 5 to 50 lb/sk

Pozzolan-Bentonite Cement Variable

Sodium Silicate 1 to 7.5 lb/sk

Expanded Perlite 5 to 20 lb/sk

Hollow Spheres Variable

Density increasers

Sand 5 to 25

Barites 10 to 108

Ilmenite (iron-titanium oxide) 5 to 100

Hematite 4 to 104

Salt 5 to 16

Friction Reducers 0.05 to 1.75

Table 1: Materials used to vary slurry density.( Source: Halliburton Services).

For years, bentonite has been the most commonly used additive for filler-type
cement. In addition to its effect on density, yield, and cost, bentonite increases
viscosity and gel strength, which reduces settling of high-density particles (e.g.,
weight material, cement), or floating of low-density particles (e.g., perlites, pozzolan,
gilsonite, crushed coal, hollow spheres). Bentonite also reduces API fluid loss.
However, cements containing bentonite are more permeable and have lowered
sulfite resistance.

Pozzolans increase slurry viscosity and provide low permeability. Sodium meta-silicate
provides a very low density slurry with early compressive strength; this material and
calcined shale-cement (a special cement, not an extender) are becoming popular,
particularly in offshore applications.

Very light slurries (less than 8 lb./gal.) have been made using hollow spheres. These
new cements are useful in underpressured, hot geothermal wells and other special
applications.

Density-Increasing Additives
High density cement sluries are often necessary to offset the high pressures that are
frequietly encontered in deep or abnormally pressured fromations. Density may be
increased with weight material such as sand, barite, hematite or ilmenite, and/or salt
dissolved in the mix water, as shown in Table 1.

Type Amount used per sack

(% by weight)

Density reducers/extenders

Bentonite 2 to 16

Attapulgite 1/2 to 4

Diatomaceous Earth (Diacel D) 10, 20, 30 or 40

Pozzolan, Artificial (fly ash) 74 lb/sk

Natural hydrocarbons:

Gilsonite 1 to 50 lb/sk

Coal 5 to 50 lb/sk
Pozzolan-Bentonite Cement Variable

Sodium Silicate 1 to 7.5 lb/sk

Expanded Perlite 5 to 20 lb/sk

Hollow Spheres Variable

Density increasers

Sand 5 to 25

Barites 10 to 108

Ilmenite (iron-titanium oxide) 5 to 100

Hematite 4 to 104

Salt 5 to 16

Friction Reducers 0.05 to 1.75

Table 1: Materials used to vary slurry density.( Source: Halliburton Services).

Available densities and effects on compressive strength are shown in Table 2.

Material Spec. Gravity Max. Effect on

(lb./gal) Density compressive
strength

Ottawa Sand 2.63 18 None

Barite 4.25 19 Reduce

Coarse Barite 4.00 20 None

Hematite 5.02 20 None

Ilmenite 4.45 20 None

Dispersant 17.5 Increase

Salt 18 Reduce

Table 2: Densities of weight materials and their effect on compressive strength.

A density of 22 lb/gal can be obtained with hematite or ilmenite plus friction-reducing
additives. Fine barite requires a large amount of water, which reduces compressive
strength and retards thickening time.

Slurry weighted with solids must have adequate viscosity and gel strength to carry
and suspend high-specific-gravity solids. In addition, some additives (e.g., fluid-loss
agents, retarders, water) tend to significantly thin or thicken a slurry.

High slurry densities (up to 17.5 lb/gal) may be obtained by (1) using heavy additives
and/or (2) adding dispersants to achieve pumpability at lower-than-normal
water/cement ratios. The latter is more expensive, but it yields the highest
compressive strength.

Pretesting of such high-density slurries should include measurement of density,

thickening time, compressive strength, settling, free water, and viscosity.

Density-Increasing Additives
High density cement sluries are often necessary to offset the high pressures that are
frequietly encontered in deep or abnormally pressured fromations. Density may be
increased with weight material such as sand, barite, hematite or ilmenite, and/or salt
dissolved in the mix water, as shown in Table 1.

Type Amount used per sack

(% by weight)

Density reducers/extenders

Bentonite 2 to 16

Attapulgite 1/2 to 4

Diatomaceous Earth (Diacel D) 10, 20, 30 or 40

Pozzolan, Artificial (fly ash) 74 lb/sk

Natural hydrocarbons:

Gilsonite 1 to 50 lb/sk

Coal 5 to 50 lb/sk

Pozzolan-Bentonite Cement Variable

Sodium Silicate 1 to 7.5 lb/sk

Expanded Perlite 5 to 20 lb/sk

Hollow Spheres Variable

Density increasers
Sand 5 to 25

Barites 10 to 108

Ilmenite (iron-titanium oxide) 5 to 100

Hematite 4 to 104

Salt 5 to 16

Friction Reducers 0.05 to 1.75

Table 1: Materials used to vary slurry density.( Source: Halliburton Services).

Available densities and effects on compressive strength are shown in Table 2.

Material Spec. Gravity Max. Effect on

(lb./gal) Density compressive
strength

Ottawa Sand 2.63 18 None

Barite 4.25 19 Reduce

Coarse Barite 4.00 20 None

Hematite 5.02 20 None

Ilmenite 4.45 20 None

Dispersant 17.5 Increase

Salt 18 Reduce

Table 2: Densities of weight materials and their effect on compressive strength.

A density of 22 lb/gal can be obtained with hematite or ilmenite plus friction-reducing

additives. Fine barite requires a large amount of water, which reduces compressive
strength and retards thickening time.

Slurry weighted with solids must have adequate viscosity and gel strength to carry
and suspend high-specific-gravity solids. In addition, some additives (e.g., fluid-loss
agents, retarders, water) tend to significantly thin or thicken a slurry.

High slurry densities (up to 17.5 lb/gal) may be obtained by (1) using heavy additives
and/or (2) adding dispersants to achieve pumpability at lower-than-normal
water/cement ratios. The latter is more expensive, but it yields the highest
compressive strength.

Pretesting of such high-density slurries should include measurement of density,

thickening time, compressive strength, settling, free water, and viscosity.

Filtration-Control Additives
Fluid loss, or the premature escape of mix water from the slurry before chemical
reaction occurs, can cause many downhole problems, including

differential sticking of casing and decentralization

formation damage by filtrate (if not controlled by mud cake)

loss of pumpability

cement bridging above gas zones and gas cutting from hydrostatic pressure
loss

improper or premature dehydration during squeezing

Filtration-control additives in present use and their recommended concentrations are

listed in Table 1.

Type Amount used per sack

(% by weight)

Fluid-loss additives 0.5-1.5%

Organic polymers (cellulose),

form micelles

Organic plymers (dispersants), 0.5 - 1.25%

size distribution and form
micelles

Carboxymethyl hydroxyethyl 0.3 - 1.0%

cellulose, from micelles

Latex additives, form films 1.0 gal/sk

Bentonite cement with 12-16% gel

dispersant
Table 1: Materials to reduce filtrate loss, friction.

These materials function by forming micelles or films, and/or by improving particle-

size distribution, which holds liquids.

A neat Class G or H slurry has an API 30-minute filter loss of over 1000 ml. Figure 1
shows the effectiveness of high-molecular-weight synthetic polymer in reducing filter
loss.

Figure 1

Friction Reducers
Friction reducers or dispersants are commonly used to lower viscosity, yield point and
gel strength of the slurry to reduce friction in pipe, and thus allow turbulent flow to
occur at reduced pump rates. For example, to achieve turbulent flow with 7 5/8 in.
casing in a 8 5/8 in. hole requires a rate of over 600 gal/min. With 0.5, 0.75, and 1.0%
friction reducing additives (FRA), the required rate is only 530, 300, and 210 gal/min,
respectively. These additives also permit slurries to be mixed at lower water/cement
ratios so that higher densities may be achieved.

Some common dispersants are alkylaryl sulfonate, polyphosphate, lignosulfonate,

salt, and organic acid. Table 1 shows typical concentrations. Turbulent-flow additives
tend to cause settling and excessive free water. These effects should be tested in the
lab prior to field use.

Type Amount used per sack

(% by weight)
Friction reducers/
dispersants

Polymer: blend 0.5 to 0.3 lb/sk

Polymer: long chain 0.5 to 1.5 lb/sk

Calcium lignosulfonate 0.5 to 1.5 lb/sk

(organic acid)

Sodium Chloride 1 to 16 lb/sk

Organic acid 0.1 to 0.3 lb/sk

Table 1: Materials to reduce filtrate loss, friction.

Lost-Circulation Materials
"Lost circulation" or "lost returns" refers to the loss to formation voids of either whole
drilling fluid or cement slurry used during the course of drilling or completing a well.
It should not be confused with volume decrease caused by filtration.

Drilling fluids or slurries are usually lost to either natural or induced formation
fractures. These fluids may also be lost through highly permeable formations — those
starting at about 5 darcies for drilling fluid with a maximum particle size of 0.002 in.
(300 mesh). Cement, with its larger particle size (neat cement has 2.6 to 18%
particles larger than 200 mesh) is less susceptible to loss in permeable formations.

The best time to treat the formation to reduce such fracture or formation
permeability is during drilling, when high concentrations of bridging materials and
various types of plugs (pills) may be utilized.

During primary cementing, concentrations of such materials must be carefully

controlled to avoid bridging the casing or liner-borehole annulus, or plugging
downhole equipment such as bottom wiper plugs, small-diameter stage tools, and
float equipment.

Types of lost-circulation additives available for cement are blocky-granular materials

(walnut shells, gilsonite, crushed coal, perlite-expanded and perlite-semiexpanded)
which form bridges, and laminated materials (cellophane flakes) which form flake-
type mats. In laboratory studies, granular material was found to be best suited for
bridging fractures ( Figure 1 ,
 Figure 1

the performance of LCM materials in sealing simulated

Type Generic Type Volumes used, typical range

material name particle

Granular Gilsonite Graded 5-50 lb/sk

Perlite Expanded 1/2-1 cu ft/sk

Walnut Graded 1-5 lb/sk

shells

Coal Graded 1-10 lb/sk

Lamellated Cellophane Flakes 1/8-2 lb/sk

Fibrous Nylon Short 1/8-1/4 lb/sk

fibers

Table 1: Ranges of lost-circulation material (LCM) volumes used per sack.

Fibrous materials (such as nylon fibers) are used in drilling fluid for sealing large
openings but are not normally used in cement because they tend to plug surface and
downhole cementing equipment. Also, most other fibrous materials contain organic
chemicals that can seriously retard cement-thickening time.

Ranges of lost-circulation material (LCM) values used per sack are listed in Table 1.

Salt
Salt has many different properties. In addition to its uses as a dispersant and in slurry
densification, it may be used as a cementing additive in the following ways:

• Bonding to Salt Formations Saturated-salt slurries are the best overall choice
for cementing across salt zones because they do not dissolve the salt zone
and thus give a better formation-to-cement bond.

• Protecting Clay and Shale Formations Small amounts of sodium chloride

(NaCl) and potassium chloride (KCl) help protect clay and shale formations
that are otherwise susceptible to crumbling and sloughing.

• Acceleration Use of salt may be used as an accelerator. KCl in small amounts

also promotes early-strength development.

• Retardation Saturated salt is an effective retarder in circulating

temperatures up to about 23° to 260° F (100 to 127° C)

• Expansion Salt can be used to cause linear expansion of cement to occur

long after the cement has set. This effect is minor but beneficial in obtaining a
better formation-to-cement bond.

Compressive-Strength Stabilizers
Four variables — composition, temperature, pressure, and time — affect compressive
strength. However, at high temperatures, cement compositions may retrogress (lose
strength) after reaching a high value and never attain the strength reached at lower
curing temperatures ( The effect of curing: Figure 1 , pressure and Figure 2 ,
temperature on cement strength.
 Figure 1

The high temperatures cause strength retrogression).

 Figure 2

This strength retrogression is accompanied by increased cement permeability, e.g., a

neat retarded cement with 0.02+ md permeability at 290° F (143° C) after three days
may have 8+ md at 320° F (160° C) after seven days.

Retarded cement (used in high-temperature applications) and high-water-content

cement seem particularly subject to strength retrogression. For cement types used in
deep and/or hot wells, the phenomenon begins at around 260° F (127° C), and
becomes severe at 290° F (143° C).

Silica flour in high percentages inhibits strength retrogression and produces

compressive strength far in excess of that of neat cement. Silica flour also reduces
permeability of set cement; for instance, its addition to cement cured at 350° F (177°
C) reduces permeability to less than 0.001 md.

Usually 30 to 40% silica flour is used. Silica sand ground to 200 mesh reacts with
cement in the same way as fine-ground 325-mesh silica flour. Sand is used when high
density is desired, and flour when low density is adequate. The different densities are
achieved because of the different water requirements of the sand and the flour.
Compositions containing silica sand or flour can be retarded effectively for high-
temperature wells.
Natural pozzolans and fly ash produce a strong material with silica-stabilized cements
up to 450° F (232° C). At a temperature of 600° F (315° C), fly ash and, to a lesser
degree, natural pozzolans can cause cement to weaken and become more
permeable.

Other Additives
Other additives are materials that do not fit readily into classifications. They are
usually compatible with classified additives, and include the following:

Radioactive tracers are added to serve as markers that can be detected by

logging devices. Radioactive tracers include iodine 131 (8-day half-life),
scandium 46 (85-day half-life), liquid iridium 192 (74-day half-life), and sand
for squeeze work.

Anti foam agents are available in dry or liquid form to combat air
entrainment. They are used routinely in many cements to facilitate mixing.
Some additives can cause excessive air entrainment, making it difficult to
achieve the desired slurry density without the addition of anti foam agents.

Dyes are occasionally employed as an aid to determine the effectiveness of

mud displacement during cementing operations.

Mud decontaminants neutralize certain mud-treating chemicals that could

have a detrimental effect on the cement. They are used primarily in openhole
plug-back and liner jobs, squeeze jobs, and tail-in primary casing jobs.

Gypsum additives, which create thixotropic properties in cement slurry, help

combat lost circulation through rapid gel-strength development. Viscosity
increases and slurry gelling is induced when shear rate is reduced. Gypsum
additives decrease cement mobility and thus its setting time. In addition,
these additives have expansion properties to improve bonding in set cement.