Round II Cement

Basic Cement

Cement is basically a calcareous material with some clay containing Iron and some
aluminium oxides.
These basic ingredients can be blended together in either a wet or dry process and then fired
in a rotary kiln. During the firning process, the chemical reactions give rise to clinker like
material. This material is added to gypsum to give cement.
Clinker then contains the four compounds Tri calcium silicate, Dicalcium silicate, tricalcium
Aluminate and tetracalcium Aluminoferrite..

Cement Hydration.
The subject is not fully understood but the general theory is that when water is added to
cement there is a rapid heat eveolution. This lasts a short period of time after which there is
a sharp fall in heat evolution. There then follows a dormant period after which there is a
second heat evolution after which the cement begins to set. The dormant period can last
many hours and this is when the cement is pumped.

Heat

Time

The process is believced to be one of osmotic pressure. When water is added, it reacts
quickly with the C3A or prmarily C3S grains in the cement and a gel coating is quickly
formed around the cement grains (initial heat given out). This coating then prevents further
reactions (dormant period). During the dormant period, OH and Ca ions diffuse through the
gel membrane and are exchanged for water ions diffusing in through the membrane. This
process increases pressure within the gelled grain. This pressure increases until the gel
coating is ruptured (marking the end of the dormant period). When this happens spikes of
cement are thrown out of the structure to form a rigid structure.

It is the nature of this structure that give the strength (rule of thumb more cement, higher
strength). The inclusion of a large amount of water means that there is a lot of porosity and
little strength.

Basic Slurry Properties.

Water/Cement Ratio
The strength of the structure formed and the associated porosity is very dependent on the
water/cement ratio. High the water content, the weaker the cement.
The minimum amount of water is defined as that that gives a slurry with a consistency of
<30 bc. (slurry approx. 0.88 psi/ft). These cements are difficult to pump and need to be
heavily dispersed. (kick off plugs)
Maximum water content is that content that can suspend all of the cmeent particles. As a
sule of thumb, the free water level should not be more than 3.5 ml from a 250 ml sample.
 Round II Cement

Slurry Density
This is driven mainly by the water/cement ratio used. High cement ratios will give a slurry
that is heavy and difficult to pump unless it is heavily dispersed. You want at least 0.3 psi/ft
more weight then the mud in use (especially if deviated). The density can be lowered by
addition of extenders or light materials such as pozzolan and is increased by inert materials
such as heamatite.

Fluid Loss Control

Variations in the water content of the cement can lead to problems. The final set strength
and density is dependent on the amount of water present. If not enough water is present
then it is unpumpable and hydration cannot take place properly. If water is lost from the
slurry then the cement can de-hydrate and flash set or turn into an umpumpable gel.
Additionally loss of water carrier cement fines to the formation where it can cause damage.

Fluid loss is even more important in squeezing operations where a thin filter cake is formed,
but premature de-hydration is not required. An uncontrolled slurry has a fluid loss between
800 and 1000 ml/30 minutes, a slurry for a casing job has a fluid loss between 100 and 200
ml/30 mins. For a squeeze job the fluid loss should be less then 100 ml. Fluid loss additives
work by viscosifying the water phase or by binding cement particles in the filter cake.

Rheology.
This is important in oreder to determine the displacement efficiency. A viscous cement may
also mean a large back pressure and the danger of fracturing the formation. Additives that
effect rheology can also act as a retarder.

Thickening time.
Normally in a lab this is the time for the rheology to reach 100 bc consistency. This must be
more than the placement time. Thickening time can be affected by both pressure but
primarily temeprature and the type of cement.
Vital information here is the BHCT and the BHST. A squeeze job, for instance will take place
at low flowrates and so the BHST is more improtant. In a casing job, the BHCT is more
important.

Basic Set Cement Properties.

Strength.
At temperatures below 230 deg F, cement contimues to hydrate for up a year. However at
temperature above 230 deg F, the maximum strength is reached early and then the cement
losses it’s strength from then on. With high temperatures, chemicla changes within the
cement structure leave the set cement more porous and permeable which is then
suscepetible to attack from the elements. The slurry can be stabilised with Silica and will
chemically prevent the formation of this weak porous structure.Poratland cement with 20%
lime can react badly. Pozzo has the advantage that there is no free lime, but the lime is taken
up in the cement structure.

Cement doesn’t need to have the compressive strength of rock but needs to have the
strength to:-
1. Support the casing.
2. Withstand the shock of drilling out.
3. Withstand a LOT pressure and frac applied
4. Withstand the pressure assocuaited with a kick.
 Round II Cement

500 psi compressive strength is generally enough, though for a kick off plug this needs to be
higher son that kicking off is easier.

Isolation properties.
Isolation is a property of low permeability and cement bond strength. It is a function of
water content.

Additives

Accelerators
During the manufacturing process, a cement can be made to set faster by increasing the
grain size or C3A content. You can reduce the water/cement ration but this can give
operational problems. Chemical additive such as CaCl 2 increase the ionic exchange during
the hydration of the cement. OH ions diffuse faster in a Ca ++ environment. This speeds up
hydration and hence the setting of the cement.
Accelerators include
 CaCl2 - very effective. Normally used in the range of 2 - 4% BWOC. Over 6% can cause
flash setting.
 NaCl Accelerator up to 10% BWOC. Anything over that and it may work as a retarder.
 Seawater - contains 25000 ppm NaCl and can be used as a slight accelerator.
 Gypsum. Difficult to use and can lead to complex chemical reactions.

Retarders
They work by either absorption onto onto cement grains or precipitation onto the grains
which temporarily halts hydration. During manufacture, the quantities of C3A can be
reduced.
 High contents of NaCl will retard but a fluid loss additive is required.
 Lignosulpanates also act as a strong dispersant. They are common in mud so watch for
mud contaimnation of cement. There can also be traces of ligno. in fresh water so that
needs to be checked as well.
 Cellulose derivatives - Primarily fluid loss agents (viscosify the water phase) but can also
act as thinners. Very often used in seawater to help with fluid loss control.
 Sugar and organic acids - very potent and care is needed.

Fluid Loss Additives

Achieved by either good particle size distribution, viscosifying the water phase and forming a binding
film in the filter cake with polymers. Genral rule of thumb is fluid loss will increase as the cement
density decreases. A good dispersant is also required to give a good filter cake.
 Cellulose derivatives - Primarily a viscosifier and can retard. They are also temeprature dependant.
 Polymers - They just bind the filter cake.

Disperants
Many products have a dispersant as a secondary function. Often retardants disperse as well.
Dispersants neutralise the attractive forces between particles to allow easier pumping. A
well dispersed slurry will allow for higher cement/water ratios to be pumped to allow for
good strength. A well dispersed slurry will allow for good fluid loss control.

Extenders
These are used to decrease weight of slurry or to increase the yield in a surface. The down
side is decreased strength.
Water based extenders min MW 0.65 psi/ft.
Clay types include bentonite which when hydrated takes on a lot of water. The bentonite
should be hydrated for at least 2 hours before using in the cement job.
 Round II Cement

Chemical Based.
Normally silica based. They can react with lime to form a gel. This gel structure will allow
for a lot of water to be taken up. They can, however be sensitive to retarder concentration.

Lighter aggregates as extenders.

Pozzolans, either natural or as slag/fly ash can be used. These cements give good resistance
to sulphate attack (no free lime). They are often good at high temperatures. They can come
as 50:50 mixtures with Portland cement.

Weighting Agents.
Inert solids such as heamatite and magnox. Barytes however will need more water so
strength will decrease. Sea water can be used as a mix water but there is the problem with
retarding.