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Thermal Shock-resistant Cement

Description: 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 200 and #61616;C-autoclaved cement at 500 and #61616;C for 24 hours, and then the heated cement was rapidly immersed in water at 25 and #61616;C. 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 and #61614; and #61543;-Al2O3, katoite and #61614; calcite, and hydroxysodalite and #61614; carbonated sodalite. Among those, the hydroxysodalite and #61614; 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 ...
Date: February 1, 2012
Creator: T., Sugama; Pyatina, T. & Gill, S.
Partner: UNT Libraries Government Documents Department

Effect of MgO Additive on Volumetric Expansion of Self-Degradable Cements

Description: We identified hard-burned magnesium oxide (MgO) as a suitable expansive additive for improving the plugging performance of self-degradable, temporary sodium silicate-activated slag/Class C fly ash (SSASC) blend cement sealers into rock fractures in Enhanced Geothermal Systems (EGSs). MgO extended the volumetric expansion of sealers during their exposure to a hydrothermal environment at 200 C under pressures, ranging from 300 to 1500 psi. A great expansion ratc of 19.3% was observed by adding 3.0 wt% MgO under 300 psi pressure, thus promising to plug thoroughly inner fracture. When the pressure was increased from 300 psi to 1500 psi, the expansion rate of cement markedly reduced, corresponding to the formaLion of crack-free specimens and the improvement of compressive strength. However, with 3.0 wt% MgO, the specimens still engendered the generation of numerous visual cracks, although they were prepared under a high pressure of 1500 psi. The effective content of MgO in minimizing and eliminating the generation of cracks was 2.0 wt%, which provided a moderate expansion of {ge} 0.5%. The compressive strength of 2.0 wt% MgO specimens made under a pressure of 300 psi rose {approx} 1.7-fold to 4816 psi with an increasing pressure to 1500 psi. The in-situ growth of brucite crystal formed by the hydrothermal hydration of MgO was responsive for such an expansion of the SSASC cement; meanwhile. two crystalline hydrothermal reaction products, 1.1 nm tobermorite and calcium silicate hydrated, contributed to the development of the sealer's compressive strength. Thus, the increasing pressure seems to suppress and control a growth rate of brucite crystal in response to a lower extension of expansion. Furthermore, all MgO-conlaining SSASC sealers possessed the water-catalyzed self-degradable properties.
Date: September 30, 2011
Creator: T., Sugama; Warren, J. & Butcher, T.
Partner: UNT Libraries Government Documents Department

Effect of Sodium Carboxymethyl Celluloses on Water-catalyzed Self-degradation of 200-degree C-heated Alkali-Activated Cement

Description: We investigated the usefulness of sodium carboxymethyl celluloses (CMC) in promoting self-degradation of 200°C-heated sodium silicate-activated slag/Class C fly ash cementitious material after contact with water. CMC emitted two major volatile compounds, CO2 and acetic acid, creating a porous structure in cement. CMC also reacted with NaOH from sodium silicate to form three water-insensitive solid reaction products, disodium glycolate salt, sodium glucosidic salt, and sodium bicarbonate. Other water-sensitive solid reaction products, such as sodium polysilicate and sodium carbonate, were derived from hydrolysates of sodium silicate. Dissolution of these products upon contact with water generated heat that promoted cement’s self-degradation. Thus, CMC of high molecular weight rendered two important features to the water-catalyzed self-degradation of heated cement: One was the high heat energy generated in exothermic reactions in cement; the other was the introduction of extensive porosity into cement.
Date: May 1, 2012
Creator: T., Sugama & Pyatina, T.
Partner: UNT Libraries Government Documents Department

Temporary Cementitious Sealers in Enhanced Geothermal Systems

Description: Unlike conventional hydrothennal geothermal technology that utilizes hot water as the energy conversion resources tapped from natural hydrothermal reservoir located at {approx}10 km below the ground surface, Enhanced Geothermal System (EGS) must create a hydrothermal reservoir in a hot rock stratum at temperatures {ge}200 C, present in {approx}5 km deep underground by employing hydraulic fracturing. This is the process of initiating and propagating a fracture as well as opening pre-existing fractures in a rock layer. In this operation, a considerable attention is paid to the pre-existing fractures and pressure-generated ones made in the underground foundation during drilling and logging. These fractures in terms of lost circulation zones often cause the wastage of a substantial amount of the circulated water-based drilling fluid or mud. Thus, such lost circulation zones must be plugged by sealing materials, so that the drilling operation can resume and continue. Next, one important consideration is the fact that the sealers must be disintegrated by highly pressured water to reopen the plugged fractures and to promote the propagation of reopened fractures. In response to this need, the objective of this phase I project in FYs 2009-2011 was to develop temporary cementitious fracture sealing materials possessing self-degradable properties generating when {ge} 200 C-heated scalers came in contact with water. At BNL, we formulated two types of non-Portland cementitious systems using inexpensive industrial by-products with pozzolanic properties, such as granulated blast-furnace slag from the steel industries, and fly ashes from coal-combustion power plants. These byproducts were activated by sodium silicate to initiate their pozzolanic reactions, and to create a cemetitious structure. One developed system was sodium silicate alkali-activated slag/Class C fly ash (AASC); the other was sodium silicate alkali-activated slag/Class F fly ash (AASF) as the binder of temper-try sealers. Two specific additives without sodium silicate as alkaline additive were ...
Date: December 31, 2011
Creator: T., Sugama; Pyatina, T.; Butcher, T.; Brothers, L. & Bour, D.
Partner: UNT Libraries Government Documents Department

Self-decomposable Fibrous Bridging Additives for Temporary Cementitious Fracture Sealers in EGS Wells

Description: This study evaluates compatibility of a self-degradable temporary fracture sealer with the drilling mud and plugging and self-degrading performance of different fibers to be used in combination with the sealer. The sodium silicate-activated slag/Class C fly ash (SSASC) cementitious sealer must plug fractures at 85oC to allow continuous well drilling and it must degrade and leave the fractures open for water at later times when exposed to temperatures above 200oC. The sealer showed good compatibility with the mud. Even the blend of 80/20 vol.% of sealer/mud reached a compressive strength of more than 2000 psi set as one of the material criteria, mostly due to the additional activation of the slag and Class C fly ash by the alkaline ingredient present in the drilling fluid. In contrast, the drilling fluid was detrimental to the compressive strength development in conventional Class G well cement, so that it failed to meet this criterion. Among several organic fibers tested both polyvinyl alcohol (PVA)-and nylon-based fibers showed adequate plugging of the sealer in slot nozzles of 1-in. wide x 6-in. long x 0.08 in. and 0.24 in. high under pressures up to 700 psi. PVA fibers displayed better compressive toughness and self-degrading properties than nylon. The compressive toughness of sealers made by adding 1.0 wt% 6 mm-length PVA and 0.5 wt% 19 mm-length PVA was 9.5-fold higher than that of a non-bridged sealer. One factor governing the development of such high toughness was an excellent adherence of PVA to the SSASC cement. The alkali-catalyzed self-decomposition of PVA at 200°C led to the morphological transformation of the material from a fibrous structure to a microscale flake-like structure that helped the desirable conversion of the sealer into small fragments. In contrast, nylon’s decomposition provided a reticular network structure in the self-degraded sealer resulting in bigger fragments ...
Date: November 1, 2012
Creator: T., Sugama; Pyatina, T.; Gill, S.; Kisslinger, K.; Iverson, B. & Bour, D.
Partner: UNT Libraries Government Documents Department

Corrosion-resistant Foamed Cements for Carbon Steels

Description: The cementitious material consisting of Secar #80, Class F fly ash, and sodium silicate designed as an alternative thermal-shock resistant cement for the Enhanced Geothermal System (EGS) wells was treated with cocamidopropyl dimethylamine oxide-based compound as foaming agent (FA) to prepare numerous air bubble-dispersed low density cement slurries of and #61603;1.3 g/cm3. Then, the foamed slurry was modified with acrylic emulsion (AE) as corrosion inhibitor. We detailed the positive effects of the acrylic polymer (AP) in this emulsion on the five different properties of the foamed cement: 1) The hydrothermal stability of the AP in 200 and #61616;C-autoclaved cements; 2) the hydrolysis-hydration reactions of the slurry at 85 and #61616;C; 3) the composition of crystalline phases assembled and the microstructure developed in autoclaved cements; 4) the mechanical behaviors of the autoclaved cements; and, 5) the corrosion mitigation of carbon steel (CS) by the polymer. For the first property, the hydrothermal-catalyzed acid-base interactions between the AP and cement resulted in Ca-or Na-complexed carboxylate derivatives, which led to the improvement of thermal stability of the AP. This interaction also stimulated the cement hydration reactions, enhancing the total heat evolved during cement’s curing. Addition of AP did not alter any of the crystalline phase compositions responsible for the strength of the cement. Furthermore, the AP-modified cement developed the porous microstructure with numerous defect-free cavities of disconnected voids. These effects together contributed to the improvement of compressive-strength and –toughness of the cured cement. AP modification of the cement also offered an improved protection of CS against brine-caused corrosion. There were three major factors governing the corrosion protection: 1) Reducing the extents of infiltration and transportation of corrosive electrolytes through the cement layer deposited on the underlying CS surfaces; 2) inhibiting the cathodic reactions at the corrosion site of CS; 3) extending the coverage of ...
Date: December 1, 2012
Creator: T., Sugama; Gill, S.; Pyatina, T., Muraca, A.; Keese, R.; Khan, A. & Bour, D.
Partner: UNT Libraries Government Documents Department