2014年2月4日星期二

Cement Slurries & Types of Cement

Water is added to dry cement to cause hydration and to make a pumpable slurry. To be used correctly, several properties must be known: the yield per unit (cubic feet per sack), the amount of water required (gallons per sack), and its density (pounds per gallon). Another important parameter is the cements “absolute volume”. This is the actual volume occupied by the material (the bulk volume includes the open spaces between the cement particles). For example, one sack (94 lbs) of cement has a bulk volume of 1 ft3, but if all the open spaces between the particles were removed, the absolute volume would be 0.478 ft3. With dry materials (cement and additives), the absolute volume is used along with the water requirements to determine the slurry. For example, the absolute volume of one sack of cement (0.478 ft3) plus the water volume (5.18 gal/sk or 0.693 ft3) yields a slurry volume of 1.171 ft3 (0.478 +0.693). For components that dissolve in water (sodium chloride, etc.), since they do not occupy as much space as the specific gravities would indicate, the absolute volume is determined from experimental data. Slurry density is also determined. Since one sack of cement weighs 94 lbs, and 0.693 ft3 of water weighs 43.2 lbs, when mixed they yield 137.2 lbs of slurry. The slurry’s density is then calculated by dividing slurry weight by slurry volume, 137.2 lbs / 1.171 ft3 equals 117.1 lbs/ft3 (15.7 ppg). Yield is converted to cubic feet per sack by using the constant 7.4805 (62.4 lbs/ft3 / 8.34 lbs/gal). Fly ash, a synthetic pozzolan, is another major constituent of cements. A fly ash/cement mixture is designated as the ratio of fly ash to cement (expressed as 50:50 or 60:40, etc.) with the total always equaling 100. The first number is the percentage of fly ash (74 lbs/sack), the second number is cement (94 lbs/sack). A sack of fly ash and a sack of cement have the same absolute volume. If other additives are included (gel, accelerators, retarders, etc.), the mixture is expressed as a percentage of weight of both cement and fly ash. The slurry is then expressed: 50:50:2% gel.

Examples of slurries include:

Cement slurry, a mixture of� cement, water, and assorted dry and liquid additives used in the� petroleum and other industries[2]
Soil/cement slurry, also called Controlled Low-Strength Material (CLSM), flowable fill, controlled density fill, flowable mortar, plastic soil-cement, K-Krete, and other names[3]
A mixture of� thickening agent, oxidizers, and water used to form a� gel explosive[citation needed]
A mixture of� pyroclastic material, rocky debris, and water produced in a� volcanic eruption and known as a� lahar
A mixture of� bentonite and water used to make� slurry walls
Coal slurry, a mixture of coal waste and water, or crushed coal and water[4]
A mixture of wood pulp and water used to make� paper
A mixture of animal waste, organic matter, and sometimes water known simply as “slurry” in� agricultural use, used as� fertilizer after ageing in a� slurry pit
Meat slurry, a mixture of finely ground meat and water, centrifugally dewatered and used as food
An abrasive substance used in� chemical-mechanical polishing
Slurry ice, a mixture of ice crystals, freezing point depressant, and water
A mixture of raw materials and water involved in the� rawmill manufacture of� Portland cement
A mixture of minerals, water, and additives used in the manufacture of� ceramics
A� bolus of chewed food mixed with saliva.

Cement Slurry Basics:� Cement slurry has been in use since ancient times and continues to be one of the most durable types of foundation materials used in construction around the world. Its basic mixture is a fine sand with cement and water added until the entire mixture is a thick, creamy batch of concrete that can be poured through a tube or down a chute, such as on the back of a concrete truck.

Aggregate:� Aggregate added to the mixture helps thicken it. While gravel can be used in concrete and is commonly seen in rough structures as a basic building block, it is more common for a fine type of sand to be used for slurry to keep the mixture as pourable as possible while still retaining some form of thickness. It also helps the concrete from cracking during the shrinking phase of the curing.

Forms:� Cement slurries rely on forms to create the molds necessary for structures. Boards are normally used along with sheets of plywood and rebar to reinforce the inside of the foundation where the concrete will be poured as well as the outside.

Underwater:� An interesting thing about slurry is that it can be poured even in underwater settings, as is evident in many ancient harbors around the world. As a homeowner you can use cement slurry even if you live in a humid area or are expecting rainstorms. Once concrete mixes with water, a chemical process of curing begins that more water cannot affect once the surface is set up.

Notes: To formulate the cement slurry for a particular operation the cementing programme should be used as the basis. The slurry design is primarily the responsibility of the Well Fluids Chemist for those OpCos that have a Production Chemistry function. If absent, the slurry design is usually left to the Service Company holding the contract for cementing services. In the latter case the Drilling Engineer will have to be more closely involved in and take responsibility for the design process than in the in-house formulation case. The considerations that come into play in the design and testing process are detailed below.

slurry_transportBasic requirements primary cementations: Apart from the cementing programme providing the basic conditions and requirements for the slurry design, samples of all ingredients to be used on-site should be available at the Production Chemistry laboratory for at least the final confirmatory testing stage. The ingredients include: Cement, representatively sampled from the bulk silo’s or the sacks stock on site, Mix water to be used. If transport restrictions make it impossible for the mix water sample to reach the laboratory in time, the chloride and calcium content should be reported to enable the chemist to simulate water quality as close as possible to the actual one, Additives: Accelerator, retarder, extender, weighting agent, etc. All additives identified for the job should be sampled as soon as is practical.

The importance of representative sampling and use in testing cannot be overemphasised. Cement, although satisfying all API requirements, still will show variations in setting characteristics and response to additives. The quality of the latter may vary from batch to batch and synergistic/incompatibility effects have to be established. The mix water may contain compounds that affect setting time such as tannins or chlorides.

Slurry design: The cement slurry should be designed to meet the requirements for properties and characteristics specified in the programme as described below. The quality and supply of mix water are of prime importance in the cementing programme and in the selection of additives. Presence of contaminants in the water may have a significant, often adverse, effect on slurry properties and therefore should be flagged and accounted for in the design. In general fresh water is preferred for onshore operations. In offshore operations where salt-intolerant additives need to be used fresh or drill water has to be supplied from shore. In offshore operations, the mix water of choice obviously is sea water. It has the advantage of (slightly) accelerating the setting of cement (reducing WOC time) and improving compressive strength by as much as 20%. A significantly higher tendency of foaming is the penalty the operator is paying for the use of sea water. For cementing operations through salt formations saturated brines used to be required to mix slurries. This does impose severe restrictions on the use of additives, particularly fluid loss controllers, which are salt-intolerant. Mimicking the composition of the formation salts generally is recommended to improve chances of a satisfactory job by avoiding washouts. However, if the salts have a high magnesium content mix water may give rise to ‘flash setting’. In those cases the mix water should be prepared leaving out magnesium altogether and saturate with sodium chloride instead. Salt cements suffer from retarded setting and poor response of fluid loss additives. NAM has abandoned the use of salt-saturated cements in favour of a 10% sodium chloride brine to avoid the problems outlined above and to arrive at a more stable and flexible slurry.

Slurry design in secondary cementing: In secondary cementing, slurry volumes are usually relatively small compared to primary jobs requiring 150 m3 or more. As a consequence, pumping time for plugs and squeezes are short and the thickening time required can be kept to a minimum. Because of the small volume, plug cementing is also prone to heavy contamination. For the cement to achieve its purpose contamination should be avoided. Conditioning mud to a low rheology/gel, density contrast and spotting highly viscous pills/setting a bridge plug will all help to reduce contamination.

Plug cementing: In the case of plug setting the most important properties are thickening time and (early) compressive strength. The latter is of special interest for kick-off to be able to ‘steer’ the bottom-hole assembly (BHA) in the desired direction. Use of a cement with high early strength characteristics (API Class C) may be advantageous, although this will add a logistical complication. However, as in most operations cement is handled and stored in bulk facilities a stock of sacked cement could be considered for this purpose. Moreover the volumes are relatively small and thus the amount of cement set aside is minimal. Taking the example of a kick-off plug in 0.3397 m (13.375 inch) casing for side-tracking through a milled window 150 m cement would require some 300 sacks of cement. If ultimate strength is not adequate, silica sand or hematite can improve strength, particularly at elevated temperatures. As plug volumes are small, requiring only 10-15 minutes to be made up, mixing ‘on the fly’ may result in inconsistent properties for a relative large part of the slurry. It is therefore recommended to prepare plug cement slurries by batch blending.

Squeeze cementing: In this mode of cementing fluid loss and thickening time are the pre-dominant characteristics. Filtrate loss of small slurry volumes squeezed in perforation tunnels or through channels in a failed primary cementation. will severely affect ‘penetration’. Therefore the slurry must be designed for minimum fluid loss. In some cases it may be advantageous for a wholesome cement slurry to invade a zone to be sealed. This will require the use of ultra micro-fine cement with particle sizes below ‘pore-throat’. Long thickening times will be pre-ordained by hesitation squeezes, which may take as much as 6 hours to displace the requisite slurry volume. Mobility of the cement slurry is a further characteristic that needs to be adapted to suit the squeeze mode. In many cases high mobility combined with a low fluid loss are most conducive to achieving satisfactory results. As for plugs the small volume and tailoring of the cement slurry are best carried out in batch blending.

Light weight cement slurry: A cement slurry with gradient below 17 kPa/m (14.4 ppg) can be formulated by using a foam formulation, a Pozzolan or fly ash blend,
bentonite as extender (‘water binder’) or an inert filler (diatomaceous earth, glass spheres, etc.). All have their advantages and disadvantages which have to be weighed to make a choice.
  1. Foam cements can be prepared in the gradient range 10 to 15 kPaim by adjusting the ‘foam quality’, i.e. changing the air to liquid ratio. They have the advantage of a density gradient over the cement column. The foaming compound also imparts better gas shut-off characteristics because during the gelling stage the hydrostatic head remains constant, being derived mainly from the air pressure inside the foam bubbles. On the negative side foam cementing is a complicated process and therefore expensive to perform. It also may require application of back pressure on the annulus, particularly for the lower gradients to prevent expansion and unloading. This will partly negate the low gradient of foam cement.
  2. Pozzolan or fly ash cement can be made into a stable slurry in the range of 14.5 to 17.0 kPa/m (12.3 to 14.5 ppg). Pozzolan (a volcanic material) or fly ash (from coal-burning power stations) is mostly blended with API Class B Portland cement in 1:1 weight ratio yielding a light-weight cement with a grain density of 2820 kglm3 (bulk density 1185 kg/m3 or 74lbm/cuft = 1 sack). When fly-ash is used, or in some Pozzolan blends, bentonite is added at 2% by weight of blend to increase slurry stability, particularly at high W/C ratio. Pozzolan cement has the advantages of being a ‘one-sack’ product, which is easier on the logistics and the capability of yielding a slurry with a low consistency, favouring turbulent conditions even at moderate displacement rates. As slurry yields are considerably higher material costs for a given volume are generally lower compared to ordinary cements. However it develops lower strength than Portland cement under the same curing conditions and has a longer transition (gelling) time than neat cement slurries. Also higher a strength retrogression counts as a disadvantage.
  3. Condensed silica fume (or micro silica) is a highly reactive pozzolanic material on account of its extremely large surface area and therefore more effective than Pozzolan or fly ash. Addition of up to 28% bwoc of this material is possible, although in most cases only half of this concentration is used to formulate a slurry with a gradient of 12.9 kPa/m (11.0 ppg). It is credited with good fluid loss control properties by reduction of the cement filter cake permeability.
  4. Waterglass (Sodium meta silicate) is also used as extender in cement slurries in concentrations up to 3% bwoc, resulting in a gradient of 12.9 kPa/m (11.0 ppg). Econolite is Halliburton’s brand name for sodium meta silicate. The reaction between silicate and (free) lime from the cement base generates a gel, which permits use of much higher water/cement ratios while retaining good slurry stability (i.e. without excessive free water).
  5. Bentonite extension allows lower gradients to be made with regular API cements at higher water/cement ratios, up to 1 m3/tonne, corresponding to a gradient of 14.5 kPa/m (12.3 ppg), at the expense of a considerably lower strength, particularly at elevated temperatures and longer transition times. Bentonite can be pre-blended with e.g. API Class G cement at 8% by weight of cement (bwoc) or added to the mix water for slurry formulation at some 2% bwoc. The latter procedure is much preferred over the dry route as segregation during transfers and difficulties inherent to the blending of relatively small quantities in a large matrix often result in a less homogeneous product. As with Pozzolan cements lower material costs are one of the main attractions.
  6. Inert flllers dry-blended with Class G cement to a ratio of 40% bwoc allow slurry gradients as low as 12.5 kPa/m (10.6 ppg) to be made. However at this low densities not much strength will develop and curing times are rather long. Filler cements should not be used for applications where set cement is load bearing. They are well suited for use in curing lost circulation.
  7. Use of glass spheres as filler should be treated with caution as the spheres are liable to collapse under pressure, resulting in a much denser cement than designed for. Mechanical degradation (e.g. in pumps) also leads to this undesirable situation. Hollow glass spheres, e.g. microspheres have a much higher mechanical strength and therefore retain most of the density reduction under pressure. Microspheres can be used in admixture to Portland cement up to a fairly high ratio of 1:1. The slurry gradient at this ratio is 9.3 kPa/m (7.9 ppg) at atmospheric pressure, increasing to 11.5 kPa/m (9.8 ppg) at 3000 psi. Special brands of glass spheres have much thicker membranes and therefore will stand pressures up to 69 MPa (10000 psi).
  8. Silica sand or flour (quartz) addition also will lower gradients, although its main purposes are increasing compressive strength and reduction of strength retrogression in high temperature applications (cementing steam injectors and producers).
High density cement formulations: When slurry densities are required in excess of those that can be formulated with neat oil well cement weighting materials such as barite, hematite and ilmenite can be used. Addition of these materials does have significant effects on other properties of the slurry, sometimes excessively so. Solids content and resultant rheology are the characteristics most affected, often needing addition of more chemicals, to render a pumpable slurry.
  1. Barite can be used up to a gradient of 20.5 kPa/m (17.4 ppg), which requires some 0.67 tonnes to be added to each tonne of cement. As barite also has a relatively high water requirement of 0.2 kg/kg the efficiency of increasing gradients with barites becomes progressively less and also less economical.
  2. Hematite is used for gradients up to 25 kPa/m (21.3 ppg). The material requirement for this gradient is some 0.65 tonne/tonne. Apart from its higher grain density hematite has also the attraction of a much lower water demand of 0.02 kg/kg.
  3. Ilmenite is used like hematite for gradients up to 25 kPa/m. The advantage over hematite is that this mineral does not require any water by itself. Both hematite and ilmenite are claimed to cause abrasive damage to hardware and casing/liner on account of the higher hardness on Mohs’ scale of 6 compared to barite’s 3.3. However tests of abrasiveness of solids-laden fluids have not shown a significant higher result for hematite/ilmenite compared to barite.
Cement Rheology Note: The rheology of a cement slurry is one of the most important characteristics for its impact on pumping and displacement. As explained earlier we have adopted the Power Law relationship between shear stress and shear rate as it most closely models the pseudo-plastic flow behaviour under dynamic (flow) and static conditions. To characterise pseudo-plastic flow the term consistency rather than viscosity is more often used to quantify internal friction (shear stress-rate relationship). The rheological characteristics are largely determined by the water cement ratio and the surface area of the cement particles. An ordinary API oil-well cement slurry with a water/cement ratio of 0.44 m3/tonne will therefore have a much higher consistency than for instance a Pozzolan cement at 0.95 m3/tonne. In many cases the intrinsic consistency of the cement slurry will cause unacceptably high equivalent circulation densities and does not favour turbulent conditions to be established during displacement.
Note: In completion of most wells, the contractor, his superintendents or tool pushers have little to say about the easing string design, setting points or the cementing of the casing. However, the past several years have seen an increase in the amount of well drilling done on a complete “turnkey” basis. The techniques and materials used in cementing operations vary from area to area and in some cases, from well to well in the same field. So much has been written on cementing that only the basic techniques and equipment can be noted here.
Types Of Cement Used In Oil Wells
Conditions and Required Properties: Cement that is used in oil wells today is subjected to a wide range of conditions. These conditions range from 15 oor lower in arctic wells to deep wells having temperatures in excess of 500 oF. The use of single type cementing material to fit these wide variations of temperature and pressure is impractical; therefore, it is necessary that different types of cements be manufactured or that suitable admixtures be developed to meet these variable conditions. The first property of a cement slurry that should be considered is that which is commonly referred to as the pumping time or thickening time. A cementing slurry must remain fluid for a sufficient length of time to allow it to be pumped down the casing and up the annular space behind the pipe. A suitable cement should possess an adequate safety factor in case of unavoidable shut down while pumping the cement slurry. Secondly, the cement, after having been properly placed in the well, must set in a reasonable period of time and should develop sufficient strength to allow continuation of normal drilling operations are resumed will vary with the operator, but a figure of 500 psi compressive strength is generally accepted by the industry as being adequate. According to work by R. F. Farris, the minimum strength required to support pipe on a primary casing cement job is 8 psi tensile strength or approximately 100 psi compressive strength.
Astm Types: There are two major classification systems for cements. The first cement classification was developed by the American Society for Testing Materials (ASTM) and covered five types of portland cement, primarily for construction usage: Type I for use in general concrete construction when special properties specified for Types II, III, IV and V are not required. Note: Type I is usually referred to as “common” cement. Type II for use in general concrete construction exposed to moderate sulfate action, or when moderate heat of hydration is required. Note: Type II is usually referred to as “high early.” Type III for use when high early strength is require. Type III cement is not commonly used in oil wells. Type IV for use when low heat of hydration is require. Type IV cement is not commonly used in oil wells. Type V for use when high sulfate resistance is require. Type V cement is not commonly used in oil wells.
API Specifications: With the advent of drilling of deeper oil wells it became apparent that the ASTM classification for cement would not meet the conditions necessary for the cementing of these deeper wells. This necessitated the formulation of an API (American Petroleum Institute) Specification for Oil-Well Cements. The are classified in API Spec 10 as follows: A well cement which has been manufactured and supplied according to this specification may be mixed and placed in the field using water ratios or additives at the user’s discretion. It is not intended that manufacturing compliance with this specification be based on such field conditions.
Classes and Grades: Well cement shall be specified in the following Classes (A, B, C, D, E, F, G and H) and Grades (O, MSR and HSR).
Class A: This product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have been shown to meet the requirements of ASTM C 465. This product is intended for use when special properties are not required. Available only in ordinary (O) Grade (similar to ASTM C 150, Type I).
Class B: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have been shown to meet the requirements of ASTM C 465. This product is intended for use when conditions require moderate or high sulfate-resistance. Available in both moderate (MSR) and high sulfateresistance (HSR) Grades (similar to ASTM C 150, Type II).
Class C: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as in interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have been shown to meet the requirements of ASTM C 465. This product is intended for use when conditions require early strength. Available in ordinary (O), moderate sulfate-resistance (MSR) and high sulfateresistant (HSR) Grades (similar to ASTM C 150, Type III).
Class D: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have shown to meet the requirements of ASTM C 465. Further, at the option of the manufacturer, suitable set modifying agents* may be interground or blended during manufacture. This product is intended for use under conditions of high temperatures and pressures. Available in moderate sulfate-resistant (MSR) and high sulfate-resistant (HSR) Grades.
Class E: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have been shown to meet the requirements of ASTM C 465. Further, at the option of the manufacturer, suitable set modifying agents* may be interground or blended during manufacture. This product is intended for use under conditions of high temperatures and high pressures. Available in moderate sulfate-resistance (MSR) and high sulfate-resistant (HRS) Grades.
Class F: The product obtained by grinding Portland cement clinker, consisting of essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. At the option of the manufacturer, processing additions* may be used in the manufacture of the cement, provided such materials in the amounts used have been shown to meet the requirements of ASTM C 465. Further, at the option of the manufacturer, suitable set-modifying agents* may be interground or blended during manufacture. This product is intended for use under conditions of extremely high temperatures and pressures. Available in moderate sulfate-resistant (MSR) and high sulfate-resistant (MSR) Grades.
Class G: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates usually containing one or more of the forms of calcium sulfate as an interground addition. No additions other than calcium sulfate or water, or both, shall be interground or blended with clinker during manufacture of Class G well cement. This product is intended for use as a basic well cement. Available in moderate sulfate-resistant (MSR) and high sulfate-resistant (HRS) Grades.
Class H: The product obtained by grinding Portland cement clinker, consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an interground addition. No additions other than calcium sulfate or water, or both, shall be interground or blended with the clinker during manufacture of Class H well cement. This product is intended for use as a basic well cement. Available in moderate sulfate-resistant (MSR) and high sulfate-resistant (HSR) Grades. The placement of any cement composition depends primarily on temperature rather than depth. The API testing schedules for standardization purposes have been developed after many years of study and industry cooperation. This is an average and extrapolative data should be used with caution as it may not meet your well conditions. Instrumentation is available to measure bottom hole circulating temperature very easily in today’s field operations before each cement job. These schedules in Table T1-1 represent average temperatures at various depths along the Gulf Coast and may not correspond to temperatures at the same depths in other areas.
Cement Slurries
Water is added to dry cement to cause hydration and to make a pumpable slurry. To be used correctly, several properties must be known: the yield per unit (cubic feet per sack), the amount of water required (gallons per sack), and its density (pounds per gallon)
Another important parameter is the cements “absolute volume”. This is the actual volume occupied by the material (the bulk volume includes the open spaces between the cement particles). For example, one sack (94 lbs) of cement has a bulk volume of 1 ft3, but if all the open spaces between the particles were removed, the absolute volume would be 0.478 ft3.
With dry materials (cement and additives), the absolute volume is used along with the water requirements to determine the slurry. For example, the absolute volume of one sack of cement (0.478 ft3) plus the water volume (5.18 gal/sk or 0.693 ft3) yields a slurry volume of 1.171 ft3 (0.478 +0.693).
For components that dissolve in water (sodium chloride, etc.), since they do not occupy as much space as the specific gravities would indicate, the absolute volume is determined from experimental data.
Slurry density is also determined. Since one sack of cement weighs 94 lbs, and 0.693 ft3 of water weighs 43.2 lbs, when mixed they yield 137.2 lbs of slurry. The slurry’s density is then calculated by dividing slurry weight by slurry volume, 137.2 lbs / 1.171 ft3 equals 117.1 lbs/ft3 (15.7 ppg).
Yield is converted to cubic feet per sack by using the constant 7.4805 (62.4 lbs/ft3 / 8.34 lbs/gal). Fly ash, a synthetic pozzolan, is another major constituent of cements. A fly ash/cement mixture is designated as the ratio of fly ash to cement (expressed as 50:50 or 60:40, etc.) with the total always equaling 100. The first number is the percentage of fly ash (74 lbs/sack), the second number is cement (94 lbs/sack). A sack of fly ash and a sack of cement have the same absolute volume.
If other additives are included (gel, accelerators, retarders, etc.), the mixture is expressed as a percentage of weight of both cement and fly ash. The slurry is then expressed: 50:50:2% gel

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