An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. This work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersive X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Mechanical properties of the set cements were not compromised by the retarder.
This study evaluates the degradation of six different elastomeric polymers used for O-rings: EPDM, FEPM, type I-and II-FKM, FFKM, and FSR, in five different simulated geothermal environments at 300°C: 1) non-aerated steam/cooling cycles, 2) aerated steam/cooling cycles, 3)water-based drilling fluid, 4) CO 2 -rich geo-brine fluid, and, 5) heat-cool water quenching cycles.The factors assessed included the extent of oxidation, changes in thermal behavior, microdefects, permeation of ionic species from the test environments into the O-rings, silicate-related scale-deposition, and changes in the O-rings' inverse tensile compliance.The reliability of the O-ring to maintain its integrity depended on the elastomeric polymer composition and the exposure environment. FSR disintegrated while EPDM was oxidized only to some degree in all the environments, FKM withstood heat-water quenching but underwent chemical degradation, FEPM survived in all the environments with the exception of heat-water quenching where it underwent severe oxidation-induced degradation, and FFKM displayed outstanding compatibility with all the tested environments. The paper discusses the degradation mechanisms of the polymers under the aforementioned conditions.
The short-term resistance to sulfuric acid at 90°C of four calcium aluminate cement (CAC)-fly ash class F (FAF) blends activated with sodium metasilicate (thermal shock resistant cements (TSRCs)), cured at 300°C, was compared to that of a calcium phosphate cement (CPC) (CAC-FAF blend activated with sodium hexametaphosphate) and a Portland cement class G/silica blend. The mechanical properties and compositions of the acid-exposed samples were evaluated by measuring their compressive strength and by means of x-ray diffraction, μEDX (energy-dispersive x-ray spectrometry), thermogravimetric and Fourier transform infrared analyses. All calcium-containing hydrates were sensitive to the conditions of acid exposure. In the TSRC blends, these hydrates included hydrogrossular, feldspar family minerals and zeolites; in CPC, feldspar minerals and phosphate phases; and in the class G/silica blend, portlandite and tobermorite.Crystalline calcium sulfates formed in the acid-exposed surfaces with the exception of the most aluminium-rich TSRC samples where only potassium(sodium) aluminium sulfate, alunite, was detected. This sample underwent the least changes in weight, compressive strength and had the lowest sulfur permeation into the sample core. Calcium sulfates precipitated on sample surfaces limited sulfur penetration into the core of calcium-rich TSRC, CPC and G/silica blends.
We studied the effectiveness of sodium silicate-activated Class F fly ash in improving the thermal shock resistance and in extending the onset of hydration of Secar #80 refractory cement. When the dry mix cement, consisting of Secar #80, Class F fly ash, and sodium silicate, came in contact with water, NaOH derived from the dissolution of sodium silicate preferentially reacted with Class F fly ash, rather than the #80, to dissociate silicate anions from Class F fly ash. Then, these dissociated silicate ions delayed significantly the hydration of #80 possessing a rapid setting behavior. We undertook a multiple heating -water cooling quenching-cycle test to evaluate the cement's resistance to thermal shock. In one cycle, we heated the 200C-autoclaved cement at 500C for 24 hours, and then the heated cement was rapidly immersed in water at 25C. This cycle was repeated five times. The phase composition of the autoclaved #80/Class F fly ash blend cements comprised four crystalline hydration products, boehmite, katoite, hydrogrossular, and hydroxysodalite, responsible for strengthening cement. After a test of 5-cycle heat-water quenching, we observed three crystalline phase-transformations in this autoclaved cement: boehmite -Al 2 O 3 , katoite calcite, and hydroxysodalite carbonated sodalite. Among those, the hydroxysodalite carbonated sodalite transformation not only played a pivotal role in densifying the cementitious structure and in sustaining the original compressive strength developed after autoclaving, but also offered an improved resistance of the #80 cement to thermal shock. In contrast, autoclaved Class G well cement with and without Class F fly ash and quartz flour failed this cycle test, generating multiple cracks in the cement. The major reason for such impairment was the hydration of lime derived from the dehydroxylation of portlandite formed in the autoclaved cement, causing its volume to expand.4
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