SPE 77867 The Effect of Key Cement Additives on the Mechanical Properties of Normal Density Oil and Gas

Well Cement Systems

Thomas Heinold, SPE, Robert L. Dillenbeck, SPE, Murray J. Rogers SPE, BJ Services Company

Copyright 2002, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the SPE Asia Pacific Oil and Gas Conference and Exhibition held in Melbourne, Australia, 810 October 2002. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

materials tested, but also the methodology used to achieve their data. In an effort to more closely scrutinize the effect each individual material has on the mechanical properties of the set cement, each additive is examined independently. Armed with this information, design engineers should be equipped to propose cement systems that produce effective long-term zonal isolation at the induced annular stresses of their own wells. Introduction In the process of oil and gas well drilling various types of cement systems are being placed into the annular space between the casing and the formation. The purpose of this cement is to structurally support the casing string and prevent casing corrosion, as well as to create a competent hydraulic seal for long-term zonal isolation during the entire operational life of the well. As mentioned by Ravi1, the cement should meet a wide range of short-term criteria such as free water, thickening time, filtrate loss, gelling, strength development, shrinkage, etc., as well as certain long-term requirements like resistance to chemical attack, thermal stability and mechanical integrity of the cement sheath. In todays oil and gas fields, it is common to find design engineers who understand that changes throughout the life of a well can significantly impact induced stresses on the annular cement sheath responsible for maintaining annular isolation. Changes in wellbore stresses can affect the mechanical integrity of the cement sheath and can be caused by a variety of different factors such as: - production rate changes - depleting reservoirs - formation compaction - workovers - stimulation treatments - pressure and temperature changes - secondary and tertiary recovery methods Models have been developed to quantify induced stresses on cement sheaths, and in most instances, if a failure occurs, the models tend to predict that failure will usually not occur under compressional stresses, but rather under tensile stresses2. This realization has led many engineers to conclude that the ultimate compressive strength of a cement system may not be the best indication of the durability of an annular cement seal

Abstract Recent advances in oil and gas cementing technology allow for the modeling and prediction of both compressive and tensile stresses upon an annular cement sheath, throughout the life of a well. Given the knowledge of the type and magnitude of stresses likely to be encountered in a specific location in a wells annulus gives designers target parameters for designing the mechanical properties necessary in the set cement to be able to sustain those stresses without failing. Such a mechanical failure in a cement sheath can cause a loss of annular isolation. However, the authors feel the ability to model these stresses is only one-half of the information necessary to design cement systems for long-term zonal isolation. While some good work has been done on certain lower density cement systems in an attempt to develop fit-forpurpose designs with improved tensile and flexural strengths, the authors have found that some wells requiring higher density cement systems, also need cements with enhanced mechanical properties. Towards this end, the authors have conducted mechanical properties research of several relatively common cement additives. These included organic materials as well as non-organic materials. For this study, these materials were added to oilfield cements with water contents averaging from 50 to 66 % by weight of cement (bwoc). Besides the more common unconfined compressive strength tests, the samples are also subjected to tensile and/or flexural strength testing. While the API has long ago established procedures for running unconfined compressive strength tests, there are currently no API standards in place covering the testing methodology for tensile and/or flexural strengths of oilfield cements. Accordingly, the authors present not only the mechanical properties achieved with the use of the various

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over the life of a well. Instead, many are now attempting to develop more elastic cement systems that are specifically designed to withstand the induced stresses anticipated for a specific well. However, as most researchers skilled in the art of oilfield cementing can attest, the task of trying to design a complex cement system for fit-for-purpose applications can be a real challenge. Many, if not most, of the more common cementing admixtures used in todays cementing systems can have a multitude of primary and secondary effects on the performance of both the slurry, as well as the final, hydrated cement. Given the realization that as an industry, much more attention must now be placed on the mechanical properties of the set cement than has been given in the past, most researchers are looking beyond compressive strengths to cement attributes such as the flexural and tensile strength. In our industry, new materials are being developed and evaluated in an attempt to expand the elasticity and tensile failure resistance of specialized cementing systems to allow for better long-term zonal isolation at the anticipated induced stresses throughout the life of a well. In many instances these new systems are of a medium or low density in order to try to reduce the hydrated cements Youngs Modulus, and hence to reduce induced stress for a given set of wellbore changes. While this strategy can be successful, the authors recognize that it may not be applicable in all instances. Many fields throughout the world still require cementing systems of higher density. These higher cement densities may be required for reasons such as pressure maintenance/well control or for maintaining hole stability. Given this need for more normal density cement systems with improved resistance to induced annular stresses, the authors have become aware through laboratory testing and field applications, that some very common cement additives can impact the flexural and tensile strengths of these systems in a multitude of ways. Therefore, the decision was reached that in order to develop cement systems with enhanced flexural and tensile strength properties, it would behoove them to first understand the impact of commonly used cementing additives on these set cement properties. It was felt that such an understanding would then allow for making better choices of basic cementing additives, such that these additives could act more synergistically with other purpose designed materials to yield a system with better elastic properties. A review of the available literature led the authors to the conclusion that much of the cement tensile strength testing done to date had been performed at relatively low temperatures or were derived from assumptions about certain relationships between flexural and tensile strength3,4. Due to the size and shape of the molds used to cure cement specimens for tensile strength tests, they typically will not fit in high pressure, high temperature (HTHP) curing chambers. Therefore, the authors discovered that even though most induced stress models calculate induced stress values in compressional and tensile components, much of the higher temperature testing of cement mechanical properties involved testing the cement flexural strengths only. The authors believe this was the case because the molds to cure cement test

specimens for flexural strength would typically fit in the HTHP curing chamber. In order to explore any possible correlation between flexural and tensile strengths in normal density cements at multiple temperatures, the authors made the decision to use specially made molds that would allow for the curing of tensile strength cement test samples inside HTHP curing chambers. Materials The cement used for this investigation was a monogrammed API Class G cement. Cements marked by the API monogram are manufactured within certain parameters and have specified chemical and physical characteristics. To investigate the effect various cement additives have on the mechanical properties of set cement, seven cementing additives commonly used in oil and gas well cementing were chosen for evaluation at 100F and 200F. Following is a short description of these materials, their applications and typical additive concentrations. a) Polyvinyl Alcohol (PVA)5 is a white, powdered, synthetic polymer, manufactured by the hydrolysis of polyvinyl acetate. It is readily cold water-soluble. This additive, dependant on its hydrolysis, is typically used at temperatures up to 300F with concentrations commonly ranging from 0.2 to 2.0 % bwoc. The film forming properties of this material can contribute to a reduction in permeability by limiting the inner particle flow within the cement matrix. Because of its adhesive properties, it is also considered to enhance bonding between cement and casing/wellbore. b) Silica Fume (SF)6 is a by-product of silicon metal, or ferrosilicon alloy production and consists primarily of amorphous silicon dioxide. When added to Portland cement, the silicon dioxide in the SF reacts with calcium hydroxide to form calcium silicate hydrate gel. This reaction will contribute to compressive strength improvement, as well as a reduction in the permeability of the cement matrix. The additive is typically used in temperatures of up to 400F with concentrations commonly ranging from 1.5 to 15.0 % bwoc. When used in conjunction with suitable fluid loss control additives, it can improve antigas migration properties. It is also used to enhance compressive strength, improve free fluid control as well as CO2 resistance of oil and gas well cement systems. c) Metakaolin (HRM) is a white, amorphous, aluminosilicate and is produced through the calcination of the clay mineral kaolin. Metakaolin is a highly reactive pozzolan with a high specific surface area. When added to Portland cement, it reacts aggressively with calcium hydroxide, a normal cement hydration by-product, which makes it very suitable as a cementing material. This additive is typically used over a temperature range from 32F to 180F in concentrations ranging usually from 1.0 to 25.0 % bwoc. It contributes to the improvement of various properties of oil and gas well cements, such as permeability,

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THE EFFECT OF KEY CEMENT ADDITIVES ON THE MECHANICAL PROPERTIES OF NORMAL DENSITY OIL AND GAS WELL CEMENT SYSTEMS

compressive strength development, flexural and tensile strength, gas control and sulfate resistance. d) Wollastonite is a white calcium-silicate powder and is sometimes referred to as a naturally occurring mineral fiber. It is less reactive than HRM but will produce a range of benefits when added to Portland cement. This additive can typically be used over a wide temperature range from 32F to 400F in concentrations ranging usually from 10.0 to 50.0 % bwoc. Similar to HRM it can contribute to the improvement of various properties of oil and gas well cements, such as permeability, compressive strength development, flexural and tensile strength, gas control and sulfate resistance. e) Styrene Butadiene Latex6 is a milky suspension of small spherical particles and is normally stabilized with a surfactant package to improve freeze/thaw resistance and prevent coagulation when added to Portland cement. This additive can typically be used in temperatures up to 400F with concentrations ranging usually from 0.5 to 4 gal/sk. It is considered that the film forming properties of a latex modified cement system can lead to a reduction in permeability, increased tensile strength, better fluid loss control, enhanced bonding between cement and casing/wellbore and improved acid resistance. f) Hydroxyethyl cellulose (HEC)5 is a white, powdered, water-soluble polymer. Manufactured in wide range of grades, these principally differ in molecular weight. This additive can typically be used at temperatures in excess of 300F with concentrations commonly ranging from 0.1 to 1.0- % bwoc. HEC-based materials are used to enhance the fluid loss control properties of various cement systems and are effective over a broad range of well conditions. g) Sodium Metasilicate (SMS)6 is a white, water-soluble powder, which is produced through the fusing of silica (sand) with sodium carbonate at 1,400C. When added to Portland cement, silicates will react with lime to form calcium silicate gel. The resulting gel structure can provide enough viscosity to allow for the usage of large quantities of mixwater without compromising slurry stability due to the separation of excessive freewater. The additive is typically used in temperatures of up to 200F with concentrations normally ranging from 0.1 to 4.0 % bwoc. This additive is commonly used to provide an economical low-density slurry system with good free water control and enhanced compressive strength development. Testing Methodology All slurries presented in this paper were prepared and cured according to the API RP 10B7 document, using the previously mentioned Class G cement. All systems were mixed at 15.0 ppg containing only one individual additive per test. The authors felt that by omitting other cementing additives, such as retarders, dispersants and fluid loss control, which are used to optimise slurry systems, they could better gauge the effect each individual additive has on the mechanical properties of

the set cement. The exemption to the above were slurries that contained latex. All latex slurries were mixed at 16.0 ppg in order to generate a stable cement slurry. Initial testing had shown that by using a 15.0-ppg system, considerable settling occurred. No stabilizer additive was used. This was done to eliminate any positive or negative impact an additional chemical may have on the overall strength for each individual specimen. All slurries were mixed at room temperature in either one of the following orders. 1) fresh water + defoamer +dry blended cement 2) freshwater + defoamer + latex + cement The different mechanisms of cement sheath failure due to the impact of various mechanical stresses in a downhole environment were until recently not fully understood. As already mentioned in the introduction, in the past, very little attention had been paid to the importance of these properties for the mechanical integrity of various cement systems to ensure good long-term zonal isolation. The American Petroleum Institute (API) currently has no testing procedures in place to determine flexural or tensile strength of oilfield cement systems under simulated downhole conditions. Historically, most cement testing was governed by procedures in API RP 10B and concentrated on the properties of cement slurries prior to setting. Such tests included thickening time, fluid loss, rheology and free water. Until a few years ago, the only test carried out on the set cement was a compressive strength test under unconfined conditions. Typically, rules of thumb were applied for required minimum values and compressive strength as high as possible was usually considered better. However, for many years now, our colleagues in the construction industry have carried out destructive strength tests to determine the flexural and tensile properties of concrete. Utilising this expertise, many laboratories are currently using equipment and procedures as specified by the American Society for Testing and Materials (ASTM)8,9. In order to measure the mechanical properties of the set cement, all slurries were cured under simulated downhole conditions in a standard HPHT curing chamber. For several days (72 hrs), each specimen was exposed to a constant pressure of 3,000 psi and temperatures of 100F or 200F, respectively. After the curing period had expired, samples were cooled down over a period of 1 hour and 30 minutes and then slowly de-pressurized. During this period, all samples remained under water. All specimens for flexural, tensile and compressive strength tests were cured simultaneously, with molds in a vertical orientation, in the same curing chamber throughout the testing process. Flexural strength testing was performed on specimens measuring approximately 1.6 x 1.6 x 6.3 in. utilising a threepoint bend fixture in a Gilson Co. HM 138 strength tester, as illustrated in Figure 1. It should be noted that the rectangular shaped cement sample is placed in the fixture, with the two end supports pulling downwards, while the middle support pulls upwards. The exerted force is gradually increased until mechanical failure of the specimen occurs.

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Tensile strength testing was performed using briquette mold specimens that are commonly referred to as Dog Bones. Using fundamentally the same testing machine as for flexural strength testing, the differently shaped sample fixture should be noted in Figure 2. With a gradual increase in exerted force, the upper half of the fixture is pulling the cement sample slowly upwards, until mechanical failure of the specimen occurs. As mentioned in the introduction, these curing molds were specifically manufactured to enable the authors to cure cement specimens under temperature and pressure. Compressive strength of the specimens was obtained through destructive crush tests on specimens measuring 2 x 2 x 2 in. Results The mechanical strength data of the various slurry systems are graphically presented in Figures 3 through 9. In order to allow for easier comparison of the gathered information for each individual additive, data for both test temperatures is plotted in one single graph. The plots are representations of flexural, tensile and compressive strength for various additive concentrations at 100F and 200F respectively. Finally Tables 1 through 4 are tabular summaries of the data used to produce the above mentioned graphs. Discussion Before launching into a more detailed discussion of the recorded results, the authors would like to point out a few issues related to the chosen testing methodology. As mentioned previously, the majority of slurries tested were mixed at 15.0 ppg. The authors acknowledge the fact that these systems were not optimised and might not be utilised in this form to cement a wellbore. However, since the goal was to investigate the effectiveness of individual additives, the use of other common cementing admixtures such as dispersants, retarders or fluid loss control may have masked the effects of the materials under investigation. Because of the substantial water requirements of such materials like silica fume and metakaolin, and a desire to investigate the effects of the chosen additives over a relatively wide range of concentrations, the decision was made to lower the density slightly to compensate for these higher water requirements. In the course of researching this paper, the authors also decided to maintain a constant cement density rather than a constant cement to water ratio. Through an optimisation of the water to cement ratio, higher ultimate mechanical strength properties may have been possible. However, keeping the density rather then the water to cement ratio constant allowed us a better representation of actual field operational practices. As already mentioned, there is currently no specialised testing equipment and procedures available to determine flexural and tensile properties of oil and gas well cements in our industry. Therefore, all testing was carried out under unconfined atmospheric conditions using standard ASTM equipment. The authors acknowledge that the cooling and depressurisation of the test specimens could have induced additional stresses that the cement otherwise would not be

exposed to in the wellbore environment. Although this may have had a profound effect on the final result, at this time, the authors have no means of measuring how this may have influenced our test results presented in this paper. Since cement most likely would fail in tension and many mathematical simulators will only take tensile stresses into consideration, the authors decided to focus their data evaluation solely on the tensile strength properties of the set cement. Flexural and compressive strength data was used in an attempt to investigate possible relationships between flexural, tensile and compressive strength, as discussed in various parts of literature.3,4, However, although these relationships may exist in neat cement slurries and certain specialised cement systems, to this end the authors could not verify this with absolute certainty. While evaluating the data presented in this work, the authors noted that the additives under investigation could be placed in three distinct groups based purely on their effects on the tensile strength properties of the set cement. The first group, which is represented by Metakaolin, did not appear to contribute to any enhancement in the tensile strength of the set cement at 100F or 200F. With increasing additive loadings, a larger reduction in tensile strength could be observed. As can be seen in Tables 1 and 3, the tensile strength at 100F and 200F exhibited a reduction of approximately 73% and 42%, respectively. This trend was somewhat surprising to the authors, since much of the available literature and previous test results typically demonstrated a beneficial effect of HRM on the flexural and tensile properties of the set cement. However, more recent testing seems to indicate that HRM may not be as beneficial at higher temperatures than previously thought. Although further testing is required, the authors believe that this could be attributed to possible changes in the calcination temperature of the raw kaolin clay, variations in the particle size distribution of the metakaolin and substantial differences in the various testing methods. It should be pointed out that at the higher additive loading (15% and 20% bwoc), viscosity increased considerably. For additive concentrations above 15% bwoc, a cement dispersant should be used to produce a slurry system with good rheological properties. However, as mentioned earlier this was not done to prevent possible interaction between the different additives. A second group of additives containing silica fume and latex, as shown in Figures 4 and 9 as well as Tables 1 through 4, indicate a non-uniform trend when exposed to different temperatures. Silica fume appeared to improve tensile strength at lower temperatures but exhibited a detrimental effect on tensile strength when cured at 200F. However latex slurries seemed to reverse this trend with an improved performance at 200F but an apparent reduction in tensile strength at 100F. The third group containing additives such as HEC, Wollastonite, SMS and PVA exhibit improved tensile strength trends at both temperatures. The tensile strength for PVA and HEC appeared to be relatively flat as shown in Figures 3 and 7 as well as Tables 1 through 4. However, optimum additive concentrations could be established for both materials at either temperature. As documented in Figures 6 and 8 and Tables 1

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THE EFFECT OF KEY CEMENT ADDITIVES ON THE MECHANICAL PROPERTIES OF NORMAL DENSITY OIL AND GAS WELL CEMENT SYSTEMS

through 4, SMS and Wollastonite yield interesting trends. In the case of SMS, the percentage improvement trend in tensile strength is almost identical both at 100F and 200F. Tensile strength in both cases peaks at 0.75% bwoc and tapers off quite quickly when the additive loading is increased to 1.0% bwoc. These results may indicate a possible independence from the chosen curing temperatures. Wollastonite, in contrast, exhibits a progressive improvement in tensile strength under both temperatures, when additive loadings are increased. Conclusions From the investigation and the results discussed in this paper the authors would like to present the following conclusions: 1. Not all additives, when used individually in Portland cement, appear to contribute to an enhancement of flexural and tensile strength properties of cement systems with higher density. 2. Additives known to improve flexural and tensile strength properties in low to medium density systems may not be as beneficial in higher density systems. Alternatively, enhanced mechanical properties at lower density may have been the result of a combination of various additives. 3. Caution should be exercised when trying to apply blanket rules - of - thumb about the relationships between flexural, tensile and compressive strength. Although they may apply for neat cement systems or some specific slurry designs, we could not verify these relationships with any certainty in the data presented here. 4. The authors were able to identify an optimum loading for various additives in this investigation, beyond which no additional benefits could be observed or conversely, a reduction in tensile and flexural strength occurred. 5. Caution should be exercised when trying to apply one additive over a wide range of temperatures. Our data appears to indicate that some additives, although beneficial at lower temperatures, may have detrimental effects on the mechanical integrity of cement at higher temperatures and vise versa. 6. Currently, available testing methods using ASTM equipment is not adequate and may influence overall testing results. The process whereby API curing of cements and ASTM testing is blended together may be problematic. The current curing procedure of cooling down the specimens from the test temperature and the following de-pressurisation may induce additional stresses that could cause stress cracking and influence the ultimate test result. 7. Further improvements in the modeling and prediction of downhole stresses during the life of a well are

8.

necessary to establish a better definition of good mechanical properties of set cement. Assuming that the information presented in this paper can be substantiated through future testing, the authors believe that combinations of materials like HEC, Wollastonite, PVA, etc. and their optimisation in a cement slurry can provide systems with excellent mechanical properties.

Nomenclature API - American Petroleum Institute ASTM - American Society for Testing and Materials bwoc - By Weight of Cement gal/sk - Gallons per Sack HEC - Hydroxyethylcellulose HPHT - High Pressure High Temperature HRM - High Reactivity Metakaolin PPG - Pounds per Gallon PVA - Polyvinylalcohol SF - Silica Fume SMS - Sodium Metasilicate Acknowledgements The authors would like to acknowledge the assistance in gathering the test data of Mr. Scott Bray of BJ Services Company. Finally the authors would like to thank Mrs. Doris Porter of BJ Services Company for her assistance in reviewing this paper and also the management of BJ Services Company for their permission to prepare and present this paper. References
1. Kris Ravi et al: Improve the Economics of Oil and Gas Wells by Reducing the Risk of Cement Failure, paper 74497 presented at the 2002 IADC/SPE Drilling Conference, Dallas, February 26-28. K.J. Goodwin and R.J. Crook: Cement Sheath Stress Failure, paper SPE 20453 presented at the 1992 SPE Latin American and Caribbean Engineering Conference, Buenos Aires, March 25-28. S. Le Roy-Delage et al: New Cement Systems for Durable Zonal Isolation, paper IADC/SPE 59132 presented at the 2000 IADC/SPE Drilling Conference, New Orleans, February 23-25. G. Di Lullo and P. Rae: Cements for Long Term Isolation Design Optimization by Computer Modeling and Prediction, paper SPE 62745 presented at the 2000 IADC/SPE Asia Pacific Drilling Technology, Kuala Lumpur, September 11-13. Robert L. Davidson: Handbook of Water-Soluable Gums and Resins, McGraw Hill Book Company, New York, NY (1980) 12-1. Erik B. Nelson: Well Cementing, Elsevier Science BV, Amsterdam, The Netherlands, (1990) 3-10. API Recommended Practice 10B, Specification for Materials and Testing for Well Cements, 22nd Edition, December 1997. ASTM C 348-86, Standard Test Method for Flexural Strength of Hydraulic Cement Mortars, Volume 04.01, Philadelphia (1986). ASTM C 190-85, Tensile Strength of Hydraulic Cement Mortars,Volume 04.01, Philadelphia (1986).

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SPE 77867

Figure 1

Figure 2

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THE EFFECT OF KEY CEMENT ADDITIVES ON THE MECHANICAL PROPERTIES OF NORMAL DENSITY OIL AND GAS WELL CEMENT SYSTEMS

Figure 3

Effect of PVA on Mechanical Properties of 15.0 ppg Class G

3,000 Strength (psi) 2,500 2,000 1,500 1,000 500 0 0 0.5 1 1.5 2 Additive (% bwoc)
Flexural 100 F Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F

Flexural 100 F Tensile 200 F

Figure 4

Flexural 200 F Compressive 100 F

Tensile 100 F Compressive 200 F

Effect of Silica Fume on Mechanical Properties of 15.0 ppg Class G

3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 2.5 Additive (% bwoc) Flexural 100 F Tensile 200 F 5

Strength (psi)

Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F Flexural 100 F

Flexural 200 F Compressive 100 F

Tensile 100 F Compressive 200 F

T. HEINOLD, R. DILLENBECK, M. ROGERS

SPE 77867

Figure 5

Effect of Metakaolin on Mechanical Properties of 15.0 ppg Class G

3,500 3,000 Strength (psi) 2,500 2,000 1,500 1,000 500 0 0 5 10 15 20 Additive (% bwoc) Flexural 100 F Tensile 200 F
Figure 6
Flexural 200 F Flexural 100 F Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F

Flexural 200 F Compressive 100 F

Tensile 100 F Compressive 200 F

Effect of Wollastonite on Mechanical Properties of 15.0 ppg Class G

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 5 10 15 20 Additive (% bwoc) Flexural 100 F Tensile 200 F Flexural 200 F Compressive 100 F

Strength (psi)

Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F Flexural 100 F

Tensile 100 F Compressive 200 F

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THE EFFECT OF KEY CEMENT ADDITIVES ON THE MECHANICAL PROPERTIES OF NORMAL DENSITY OIL AND GAS WELL CEMENT SYSTEMS

Figure 7

Effect of HEC on Mechanical Properties of 15.0 ppg Class G

3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 0.5 Additive (% bwoc) Flexural 100 F Tensile 200 F 1

Strength (psi)

Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F Flexural 100 F

Flexural 200 F Compressive 100 F

Tensile 100 F Compressive 200 F

Figure 8

Effect of SMS on Mechanical Properties of 15.0 ppg Class G

3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 0.75 Additive (% bwoc) Flexural 100 F Tensile 200 F 1

Strength (psi)

Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F Flexural 100 F

Flexural 200 F Compressive 100 F

Tensile 100 F Compressive 200 F

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Figure 9

Effect of Latex on Mechanical Properties of 16.0 ppg Class G

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500 0 0 1 2 3 Additive (gal/sk) Flexural 100 F Tensile 200 F Flexural 200 F Compressive 100 F

Strength (psi)

Compressive 200 F Compressive 100 F Tensile 200 F Tensile 100 F Flexural 200 F Flexural 100 F

Tensile 100 F Compressive 200 F

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THE EFFECT OF KEY CEMENT ADDITIVES ON THE MECHANICAL PROPERTIES OF NORMAL DENSITY OIL AND GAS WELL CEMENT SYSTEMS

11

Table 1 Mechanical Properties of 15.0 ppg Class G Cement at 100 F

Test Mixfluid PVA # % % bwoc 1 2 3 4 5 6 7 8 9* 10* 11 12 13 53.5 53.2 53.0 52.7 52.5 53.5 55.2 57.0 58.7 60.5 53.5 54.0 54.6 0 0.5 1 1.5 2 0 5 10 15 20 0 2.5 5 Metakaolin % bwoc Silica Fume % bwoc Flexural Strength psi 497 563 780 765 760 497 0 274 446 482 497 877 659 Tensile Strength psi 265 259 245 276 287 265 270 177 141 70 265 284 324 Compressive Strength psi 1,965 2,090 1,850 1,900 1,850 2,338 2,206 3,038 3,184 2,845 2,338 2,448 2,660 Change Flexural 0% 13% 57% 54% 53% 0% -100% -45% -10% -3% 0% 77% 33% Change Tensile 0% -2% -7% 4% 9% 0% 2% -33% -47% -73% 0% 7% 22%

* High Viscosity

Table 2 Mechanical Properties of 15.0 ppg Class G Cement at 100 F

Test Mixfluid # % 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 53.5 55.2 57.0 58.7 60.5 53.5 53.5 53.6 53.5 53.3 53.1 42.3 42.5 42.6 42.8 Wollastonite % bwoc 0 5 10 15 20 0 0.75 1 0 0.5 1 0 1 2 3 SMS % bwoc HEC % bwoc Latex gal/sk Flexural Strength psi 497 821 928 553 573 821 324 405 821 725 598 1,196 1,014 1,115 1,115 Tensile Strength psi 265 369 343 327 411 265 296 268 265 330 335 315 313 282 298 Compressive Strength psi 2,338 2,465 2,112 2,198 2,130 2,338 2,093 2,013 2,338 2,237 2,277 3,312 3,267 3,682 3,289 Change Flexural 0% 65% 87% 11% 15% 0% -60% -51% 0% -12% -27% 0% -15% -7% -7% Change Tensile 0% 39% 30% 23% 55% 0% 12% 1% 0% 25% 27% 0% -1% -11% -5%

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Table 3 Mechanical Properties of 15.0 ppg Class G Cement at 200 F

Test Mixfluid PVA # % % bwoc 1 2 3 4 5 6 7 8 9* 10* 11 12 13 53.5 53.2 53.0 52.7 52.5 53.5 55.2 57.0 58.7 60.5 53.5 54.0 54.6 0 0.5 1 1.5 2 0 5 10 15 20 0 2.5 5 Metakaolin % bwoc Silica Fume % bwoc Flexural Strength psi 203 846 892 0 0 203 122 61 41 0 203 0 0 Tensile Strength psi 335 327 380 307 284 335 318 223 177 194 335 220 194 Compressive Strength psi 2,728 2,737 2,899 2,481 1,897 2,728 2,945 2,431 2,053 2,484 2,728 2,665 3,109 Change Flexural 0% 318% 340% -100% -100% 0% -40% -70% -80% -100% 0% -100% -100% Change Tensile 0% -3% 13% -8% -15% 0% -5% -34% -47% -42% 0% -34% -42%

* High Viscosity

Table 4 Mechanical Properties of 15.0 ppg Class G Cement at 200 F

Test Mixfluid # % 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 53.5 55.2 57.0 58.7 60.5 53.5 53.5 53.6 53.5 53.3 53.1 42.3 42.5 42.6 42.8 Wollastonite % bwoc 0 5 10 15 20 0 0.75 1 0 0.5 1 0 1 2 3 SMS % bwoc HEC % bwoc Latex gal/sk Flexural Strength psi 203 319 365 750 664 203 0 0 203 1,176 1,191 203 1,287 725 1,044 Tensile Strength psi 335 397 383 403 450 335 377 321 335 434 391 495 538 529 549 Compressive Strength psi 2,728 3,960 3,480 3,056 3,154 2,728 3,424 3,044 2,728 3,214 3,306 3,726 3,685 3,445 3,220 Change Flexural 0% 58% 80% 270% 228% 0% -100% -100% 0% 480% 488% 0% 535% 258% 415% Change Tensile 0% 18% 14% 20% 34% 0% 13% -4% 0% 29% 17% 0% 9% 7% 11%