Influência da vermiculita expandida na resistência à compressão e reologia de pastas cimentantes de poços de petróleo

Several problems related to the loss of hydraulic seal in oilwells, causing gas migration and/or contamination of the production zone by water, have been reported. The loss of the hydraulic seal is a consequence of cracks which can be occasioned either by the invasion of gas during the wait on cement or by the expansion of the casing causing the fracture of the cement sheath. In case of the pressure of the formation is higher than the pressure in the annulus, gas can migrate into the slurry and form microannulus, which are channels where gas migrates after the cement is set. Cracks can be also occasioned by the fracture of the cement sheath when it does not withstand the thermal and dynamic loads. In reservoirs where the oil is heavy, steam water injection operation is required in order to get the oil flowing. This operation increases the temperature of the casing, and then it expands and causes the fracture of the cement sheath in the annulus. When the failures on the cement are detected, remedial cementing is required, which raise costs caused by the interventions. Once the use of cement in the construction civil sector is older than its use in the petroleum sector, it is common to bring technologies and solutions from the civil construction and apply them on the petroleum area. In this context, vermiculite, a mineral-clay widely encountered in Brazil, has been used, on its exfoliated form, in the civil construction, especially on the manufacture of lights and fireproof concretes with excellent thermal and acoustical properties. It has already been reported in scientific journals, studies of the addition of exfoliated vermiculite in Portland cements revealing good properties related to oilwell cementing operations. Thus, this study aimed to study the rheological behavior, thickening time, stability and compressive strength of the slurries made of Portland cement and exfoliated vermiculite in 5 different compositions, at room temperature and heated. The results showed that the compressive strength decreased with the addition of exfoliated vermiculite, however the values are still allowed for oiwell cementing operations. The thickening time of the slurry with no exfoliated vermiculite was 120 min and the thickening time of the slurry with 12 % of exfoliated vermiculite was 98 min. The stability and the rheological behavior of the slurries revealed that the exfoliated vermiculite absorbed water and therefore increased the viscosity of the slurries, even though increasing the factor cement-water. The stability experiment carried out at 133 ºF showed that, there was neither sedimentation nor reduction of the volume of the cement for the slurry with 12 % of exfoliated vermiculite. Thus, the addition of exfoliated vermiculite accelerates the set time of the cement and gives it a small shrinkage during the wait on cement, which are important to prevent gas migration

Dispersion and optimization of a calcium sulfoaluminate mortar prepared with superplasticizer

Calcium sulfoaluminate (CSA) cements/mortars are receiving increasing attention since their manufacture produces less CO2 than ordinary Portland cement (OPC) (up to 22% of decrease depending on its composition). These systems are complex and there are many parameters affecting their hydration mechanism, such as water-to-cement (w/c) ratio, type and amount of sulfate source, and so on. Low w/c ratios, within certain limits, may reduce the porosity and consequently, improve the mechanical strengths. However, it is accompanied by an increasing of viscosity and lack of both workability and homogeneity, with the consequent negative effect on the mechanical properties. The dispersion of the particles through the adsorption of the right amount and type of additives, such as superplasticizers, is a key point to improve the workability of mortars allowing both the preparation of homogeneous mixtures and the reduction of the amount of mixing water. This work deals with the preparation and optimization of homogeneous CSA-mortars with improved mechanical strengths. The optimum amount of superplasticizer was optimized through rheological measurements. The effect of different amounts of the superplasticizer on the viscosity of the mortars, its hydration mechanism and corresponding mechanical properties has been studied and will be discussed.

Synthesis of active Belite-Alite-Ye'elimite clinker (BAY)

Ordinary Portland cement (OPC) is an environmentally contentious material, as for every ton of OPC produced, on average, 0.97 tons of CO2 are released. Ye'elimite-rich cements are considered as eco-cements because their manufacturing process releases less CO2 into the atmosphere than OPC; this is due to the low calcite demand. Belite-Alite-Ye’elimite (BAY) cements are promising eco-friendly building materials as OPC substitutes at a large scale. The reaction of alite and ye´elimite with water should develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. However, they develop lower mechanical strengths at early-medium ages than OPC. It is known that the presence of different polymorphs of ye'elimite and belite affects the hydration due to the different reactivity of those phases. Thus, a solution to this problem may be well the activation of BAY clinkers by preparing them with 'H-belite and pseudo-cubic-ye'elimite, jointly with alite. The aim of this work is the preparation and characterization of active-BAY clinkers which contain high percentages of coexisting 'H-belite and pseudo-cubic-ye'elimite, jointly with alite to develop, in a future step, comparable mechanical strengths to OPC. The parameters evolved in the preparation of the clinker have been optimized, including the selection of raw materials (mineralizers and activators) and clinkering conditions. Finally, the clinker was characterized through laboratory X-ray powder diffraction, in combination with the Rietveld methodology, and scanning electron microscopy.

Synthesis and behavior of Belite-Alite-Ye’elimite (BAY) cement

Ye’elimite based cements have been studied since 70’s years in China, due to the irrelevant characteristics from a hydraulic and environmental point of view. One of them is the reduced fuel consumption, related to the lower temperature reaction required for this kind of cement production as compared to Ordinary Portland Cement (OPC), another characteristic is the reduced requirement of carbonates as a typical raw material, compared to OPC, with the consequent reduction in CO2 releases (~22%)from combustion. Thus, Belite-Ye’elimite-Ferrite (BYF) cements have been developed as potential OPC substitutes. BYF cements contain belite as main phase (>50 wt%) and ye´elimite as the second content phase (~30 wt%). However, an important technological problem is associated to them, related to the low mechanical strengths developed at intermediate hydration ages (3, 7 and 28 days). One of the proposed solutions to this problem is the activation of BYF clinkers by preparing clinkers with high percentage of coexisting alite and ye'elimite. These clinkers are known Belite-Alite-Ye’elimite (BAY) cements. Their manufacture would produce ~15% less CO2 than OPC. Alite is the main component of OPC and is responsible for early mechanical strengths. The reaction of alite and ye´elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. Moreover, the high alkalinity of BAY cement pastes/mortars/concretes may facilitate the use of supplementary cementitious materials with pozzolanic activity which also contributes to decrease the CO2 footprint of these ecocements. The main objective of this work was the design and optimization of all the parameters evolved in the preparation of a BAY eco-cement that develop higher mechanical strengths than BYF cements. These parameters include the selection of the raw materials (lime, gypsum, kaolin and sand), milling, clinkering conditions (temperature, and holding time), and clinker characterization The addition of fly ash has also been studied. All BAY clinker and pastes (at different hydration ages) were mineralogically characterized through laboratory X-ray powder diffraction (LXRPD) in combination with the Rietveld methodology to obtain the full phase assemblage including Amorphous and Crystalline non-quantified, ACn, contents. The pastes were also characterized through rheological measurements, thermal analyses (TA), scanning electronic microscopy (SEM) and nuclear magnetic resonance (NMR). The compressive strengths were also measured at different hydration times and compared to BYF.

In-situ Molibdenum X-ray powder diffraction study of the early hydration of cementitious systems on a humidity chamber

The durability of cement-based construction materials depends on the environmental conditions during their service life. A further factor is the microstructure of the cement bulk, established by formation of cement hydrates. The development of the phases and microstructure under given conditions is responsible of the high strength of cementitious materials. The investigation on the early hydration behavior of cements and cementing systems has been for a long time a very important area of research: understanding the chemical reactions that lead to hardening is fundamental for the prediction of performances and durability of the materials. The production of 1 ton of Ordinary Portland Cement, OPC, releases into the atmosphere ~0.97 tons of CO2. This implies that the overall CO2 emissions from the cement industry are 6% of all anthropogenic carbon dioxide. An alternative to reduce the CO2 footprint consists on the development of eco-cements composed by less calcite demanding phases, such as belite and ye'elimite. That is the case of Belite-Ye’elimite cements (BY). Since the reactivity of belite is not quick enough, these materials develop low mechanical strengths at intermediate hydration ages. A possible solution to this problem goes through the production of cements which jointly contain alite with the two previously mentioned phases, named as Belite-Alite-Ye’elimite (BAY) cements. The reaction of alite and ye'elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later values. The final goal is to understand the hydration mechanisms of a variety of cementing systems (OPC, BAY and pure phases) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, in-situ laboratory humidity chambers with Molybdenum X-ray Powder diffraction are employed. In the first 2h of hydration, reaction degree (α) of ye'elimite had been decreased for superplasticizer.

Remoción del barrillo dentario después de la preparación del espacio para el poste: requisito u omisión

El pronóstico a largo plazo de una pieza dental tratada endodónticamente depende de una adecuada rehabilitación definitiva que evitará la recontaminación del sistema del conducto radicular, permitiendo a su vez restituir de forma efectiva su función y estética en boca. La colocación de postes dentro del conducto radicular está indicada cuando el sustrato dental residual es muy limitado, permitiendo al especialista reconstruir la estructura dentaria para que la restauración futura pueda ser retenida. Diversos estudios concluyen que los postes de fibra de vidrio son una de las mejores alternativas para establecer un anclaje seguro entre la pieza dental y la restauración, los cuales son retenidos en el interior del conducto radicular mediante cementos resinosos en combinación con sistemas adhesivos. Este anclaje puede modificarse por diversos factores que pueden ser dependientes del operador como la elección de protocolos químiomecánicos en la terapia endodóntica y al momento de la preparación del espacio para el poste, o independientes del operador, como la anatomía del conducto radicular, formación de la capa barrillo dentinario durante la desobturación, el sustrato de adhesión, mecanismos endógenos y comportamiento de los materiales. Por lo tanto el presente estudio plantea una revisión de las variables a las que se enfrenta el especialista para obtener una adecuada retención del poste al conducto radicular por medio de cementos adhesivos, proponiendo diversos protocolos de irrigación y dispositivos coadyuvantes basados en evidencia científica que ayudaran a neutralizar los efectos adversos que el operador puede controlar.

Influence of adhesive system on quartz fiber post dislocation resistance in endodontically treated teeth

Aim: To evaluate the dislocation resistance of the quartz fiber post/cement/dentin interface after different adhesion strategies. Methods: Forty bovine lower central incisors were selected and prepared with K-files using the step-back technique, and irrigated with 3 mL of distilled water preceding the use of each instrument. Prepared teeth were stored at 37ºC and 100% humidity for 7 days. The roots were prepared and randomized into 4 groups. The quartz fiber post was cemented with an adhesion strategy according to the following groups: GBisCem- BISCEM; GOneStep±C&B- One Step ± C&B; GAllBond±C&B- AllBond3 ± C&B; GAllBondSE±C&B- AllBondSE ±C&B with a quartz fiber post. Cross-sectional root slices of 0.7 mm were produced and stored for 24 h at 37° C before being submitted to push-out bond strength. Results: The mean and standard deviation values of dislocation resistance were GBisCem: 1.12 (± 0.23) MPa, GOneStep±C&B: 0.81 (± 0.31) MPa, GAllBond±C&B: 0.98 (± 0.14) MPa, and GAllBondSE±C&B: 1.57 (± 0.04) MPa. GAllBondSE±C&B showed significantly higher values of dislocation resistance than the other groups. Conclusions: Based on this study design, it may be concluded that adhesion strategies showed different results of quartz post dislocation resistance. Simplified adhesive system with sodium benzene sulphinate incorporation provided superior dislocation resistance.

Antimicrobial and bond strength properties of a dental adhesive containing zinc oxide nanoparticles

Aim: To assess the effect of adding zinc oxide nanoparticles to dental adhesives on their anti-microbial and bond strength properties. Methods: 45 human premolars were cut at the cement enamel junction (CEJ) and the crowns were sliced into buccal and lingual halves. The specimens were classified into three groups, etched with 37% phosphoric acid for 15 s and rinsed for 30 s. Single Bond, Single Bond+5% zinc oxide and Single Bond+10% zinc oxide were used in the first, second and third groups. A cylinder of Z250 composite was bonded and cured for 40 s. For anti-bacterial testing, 10 samples of each group were assessed by direct contact test; 10 μL of bacterial suspension was transferred into tubes containing adhesives and incubated for one hour; 300 μL of brain heart infusion (BHI) broth was added to each tube and after 12 h, 50 μL of bacteria and broth were spread on blood agar plates and incubated for 24 h. Results: The colony count decreased significantly in the second and third groups compared to the first. Conclusions: Incorporation of zinc oxide nanoparticles into dental adhesives increases their anti-microbial properties without affecting their bond strength.

Mechanical behaviour at high temperature of alkali-activated aluminosilicates (geopolymers)

This study was designed to determine the effect of temperature on the mechanical strength (in both in vivo and post-exposure trials) of two alkaline cements (without OPC): (a) 100% fly ash (FA) and (b) 85% FA + 15% bauxite, the activated alkaline solution used was 85% 10-M NaOH + 15% sodium silicate. A Type I 42.5 R Portland cement was used as a control. Two series of trials were conducted: (i) in vivo trials in which bending and compressive strength, fracture toughness and modulus of elasticity were determined at different temperatures; and (ii) post-firing trials, assessing residual bending and compres-sive strength after a 1-h exposure to high temperatures and subsequent cooling. The findings showed that from 25 to 600 C, irrespective of the type of test (in vivo or post-firing), compressive mechanical strength rose, with the specimens exhibiting elastic behaviour and consequently brittle failure. At tem-peratures of over 600 C, behaviour differed depending on the type of test: (i) in the in vivo trials the high temperature induced pseudo-plastic strain and a decline in mechanical strength that did not necessarily entail specimen failure; (ii) in the post-firing trials, compressive strength rose.

Desenvolvimento de pastas cimentantes utilizando cimentos portland compostos para cimentação de poços petrolíferos

The Compound Portland cements are commonly used in construction, among them stand out the CPII-Z, CPII-F and CPIV. These types of cement have limited application on oil well cementing, having its compositional characteristics focused specifically to construction, as cement for use in oil wells has greater complexity and properties covering the specific needs for each well to be coated. For operations of oil wells cementing are used Portland cements designed specifically for this purpose. The American Petroleum Institute (API) classifies cements into classes designated by letters A to J. In the petroleum industry, often it is used Class G cement, which is cement that meets all requirements needed for cement from classes A to E. According to the scenario described above, this paper aims to present a credible alternative to apply the compound cements in the oil industry due to the large availability of this cement in relation to oil well cements. The cements were micro structurally characterized by XRF, XRD and SEM tests, both in its anhydrous and hydrated state. Later technological tests were conducted to determine the limits set by the NBR 9831. Among the compound cements studied, the CPII-Z showed satisfactory properties for use in primary and secondary operations of oil wells up to 1200 meters cementing

Influência da adição de cinza do bagaço de cana calcinada em sistemas de pastas para cimentação de poços petrolíferos

Cementing operation is one of the most important stages in the oil well drilling processes and has main function to form hydraulic seal between the various permeable zones traversed by the well. However, several problems may occur with the cement sheath, either during primary cementing or during the well production period. Cements low resistance can cause fissures in the cement sheath and compromise the mechanical integrity of the annular, resulting in contamination of groundwater and producing zones. Several researches show that biomass ash, in particular, those generated by the sugarcane industry have pozzolanic activity and can be added in the composition of the cementing slurries in diverse applications, providing improvements in mechanical properties, revenue and cement durability. Due to the importance of a low cost additive that increases the mechanical properties in a well cementing operations, this study aimed to potentiate the use of sugarcane bagasse ash as pozzolanic material, evaluate the mechanisms of action of this one on cement pastes properties and apply this material in systems slurries aimed to cementing a well with 800 m depth and geothermal gradient of 1.7 °F/100 ft, as much primary cementing operations as squeeze. To do this, the ash beneficiation methods were realized through the processes of grinding, sifting and reburning (calcination) and then characterization by X-ray fluorescence, XRD, TG / DTG, specific surface area, particle size distribution by laser diffraction and mass specific. Moreover, the ash pozzolanic activity added to the cement at concentrations of 0%, 20% and 40% BWOC was evaluated by pozzolanic activity index with lime and with Portland cement. The evaluation of the pozzolanic activity by XRD, TG / DTG and compressive strength confirmed the ash reactivity and indicated that the addition of 20% in the composition of cement slurries produces improvement 34% in the mechanical properties of the slurry cured. Cement slurries properties evaluated by rheological measurements, fluid loss, free fluid, slurry sedimentation, thickening time and sonic strength (UCA) were satisfactory and showed the viability of using the sugarcane ash in cement slurries composition for well cementing

Prevalencia del síndrome de cementación ósea en pacientes de artroplastia de cadera, Hospital Universitario Mayor Méderi 2014

Resumen Introducción: Con el fin de estimar la prevalencia del síndrome de cementación ósea (SICO) en pacientes llevados a artroplastia de cadera cementada en el Hospital Universitario Mayor Méderi 2014. Materiales y métodos: Se realizó un estudio observacional, descriptivo, de corte transversal, se evaluaron los registros de historia clínica de los pacientes llevados a artroplastia cementada de cadera desde enero a diciembre de 2014. Se estimó la prevalencia del número total de casos de SICO sobre el total de intervenidos y la mortalidad del número de muertes intraoperatorias sobre el total de pacientes que desarrollaron el SICO. Resultados: Se encontraron 102 pacientes llevados a artroplastia cementada de cadera; 73,5% de género femenino, la mediana de edad fue 82 años, la prevalencia de SICO fue de 0,96 x 100 procedimientos y la mortalidad de 7,14 x 100 eventos (1 caso), el evento más frecuentemente relacionado fue las Perdida sanguínea < 300ml (p.valor: 0,006), el resto de diferencias entre los factores de riesgo reconocidos no fueron estadísticamente significativas. Discusión Se encontró una baja frecuencia del evento, con una muerte relacionada, se requieren estudios prospectivos para explorar desenlaces en el tiempo para la presentación de SICO y factores de riesgo adicionales. Palabras clave: "Hipotensión/Diagnóstico", "Prevalencia", "Artroplastia de Reemplazo de Cadera/Efectos Adversos", "Cementos Óseos/Efectos Adversos", "Complicaciones Postoperatorias/Etiología" y "Complicaciones Postoperatorias/Inducido Químicamente"

Percutaneous vertebroplasty: a new animal model.

Background Context Percutaneous vertebroplasty (PVP) is a minimally invasive surgical procedure and is frequently performed in humans who need surgical treatment of vertebral fractures. PVP involves cement injection into the vertebral body, thereby providing rapid and significant pain relief. Purpose The testing of novel biomaterials depends on suitable animal models. The aim of this study was to develop a reproducible and safe model of PVP in sheep. Study Design This study used ex vivo and in vivo large animal model study (Merino sheep). Methods Ex vivo vertebroplasty was performed through a bilateral modified parapedicular access in 24 ovine lumbar hemivertebrae, divided into four groups (n=6). Cerament (Bone Support, Lund, Sweden) was the control material. In the experimental group, a novel composite was tested—Spine-Ghost—which consisted of an alpha-calcium sulfate matrix enriched with micrometric particles of mesoporous bioactive glass. All vertebrae were assessed by micro-computed tomography (micro-CT) and underwent mechanical testing. For the in vivo study, 16 sheep were randomly allocated into control and experimental groups (n=8), and underwent PVP using the same bone cements. All vertebrae were assessed postmortem by micro-CT, histology, and reverse transcription-polymerase chain reaction (rt-PCR). This work has been supported by the European Commission under the 7th Framework Programme for collaborative projects (600,000–650,000 USD). Results In the ex vivo model, the average defect volume was 1,275.46±219.29 mm3. Adequate defect filling with cement was observed. No mechanical failure was observed under loads which were higher than physiological. In the in vivo study, cardiorespiratory distress was observed in two animals, and one sheep presented mild neurologic deficits in the hind limbs before recovering. Conclusions The model of PVP is considered suitable for preclinical in vivo studies, mimicking clinical application. All sheep recovered and completed a 6-month implantation period. There was no evidence of cement leakage into the vertebral foramen in the postmortem examination.

Peptide-based low molecular weight gelators for the preparation of self-assembled materials

Low molecular weight gelators (LMWGs) based on pseudo-peptides are here studied for the preparation of supramolecular materials. These compounds can self-assemble through non-covalent interactions such as hydrogen bonds and π-π stacking, forming fibres and gels. A wide variety of materials can be prepared starting from these building blocks, which can be tuned and functionalised depending on the application. In this work, derivatives of the three aromatic amino acids L-Phenylalanine, L-Tyrosine and L-DOPA (3,4-dihydroxiphenylalanine) were synthesised and tested as gelators for water or organic solvents. First, the optimal gelating conditions were studied for each compound, varying concentration, solvent and trigger. Then the materials were characterised in terms of mechanical properties and morphology. Water remediation from dye pollution was the first focus of this work. Organogels were studied as absorbent of dyes from contaminated water. Hydrogels functionalised with TiO2 nanoparticles and graphene platelets were proposed as efficient materials for the photo-degradation of dyes. An efficient method for the incorporation of graphene inside hydrogels using the gelator itself as dispersant was proposed. In these materials a high storage modulus coexists with good self-healing and biocompatibility. The incorporation of a mineral phase inside the gel matrix was then investigated, leading to the preparation of composite organic/inorganic materials. In a first study, the growth of calcium carbonate crystals was achieved inside the hydrogel, which preserved its structure after crystal formation. Then the self-assembled fibres made of LMWGs were used for the first time instead of the polymeric ones as reinforcement inside calcium phosphate cements (CPCs) for bone regeneration. Gel-to-crystal transitions occurring with time in a metastable gel were also examined. The formation of organic crystals in gels can be achieved in multicomponent systems, in which a second gelator constitutes the independent gel network. Finally, some compounds unable to gelate were tested as underwater adhesives.

Applied biomaterials from sustainable sources

If we look back in time at the history of humanity, we can state that our generation is living an era of outstanding efficiency and progress because of globalization and global competition, even if this is resulting in the rapid depletion of energy sources and raw materials. The environmental impact of non-biodegradable plastic wastes is of increasing global concern: nowadays, imagining a world without synthetic plastics seems impossible, though their large-scale production and their extensive use have only spread since the end of the World War II. In recent years, the demand for sustainable materials has increased significantly and, with a view to circular economy, research has also focused on the enhancement and subsequent reuse of waste materials produced by industrial processing, intensive farming and the agricultural sector. Plastic polymers have been the most practical and economical solution for decades due to their low cost, prompt availability and excellent optical, mechanical and barrier properties. Biodegradable polymers could replace them in many applications, thus reducing the problems of traditional plastics disposability and the dependence on petroleum. Natural biopolymers are in fact characterized by a high biocompatibility and biodegradability and have already prompted research in the field of regenerative medicine. During my PhD, my goal was to use natural polymers from sustainable sources as raw materials to produce biomaterials, which are materials designed to interface with biological systems to evaluate, support or replace any tissue, organ, or function of the body. I focused on the use of the most abundant biopolymers in nature to produce biomaterials in the form of films, scaffolds and cements. After a complete characterization, the materials were proposed for suitable applications in different fields, from tissue engineering to cosmetics and food packaging. Some of the obtained results were published on international scientific and peer-reviewed journals.