Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Comportamento magnético de compósitos de matriz polimérica com adição de ferritas

Polymer matrix composites offer advantages for many applications due their combination of properties, which includes low density, high specific strength and modulus of elasticity and corrosion resistance. However, the application of non-destructive techniques using magnetic sensors for the evaluation these materials is not possible since the materials are non-magnetizable. Ferrites are materials with excellent magnetic properties, chemical stability and corrosion resistance. Due to these properties, these materials are promising for the development of polymer composites with magnetic properties. In this work, glass fiber / epoxy circular plates were produced with 10 wt% of cobalt or barium ferrite particles. The cobalt ferrite was synthesized by the Pechini method. The commercial barium ferrite was subjected to a milling process to study the effect of particle size on the magnetic properties of the material. The characterization of the ferrites was carried out by x-ray diffraction (XRD), field emission gun scanning electron microscopy (FEG-SEM) and vibrating sample magnetometry (VSM). Circular notches of 1, 5 and 10 mm diameter were introduced in the composite plates using a drill bit for the non-destructive evaluation by the technique of magnetic flux leakage (MFL). The results indicated that the magnetic signals measured in plates with barium ferrite without milling and cobalt ferrite showed good correlation with the presence of notches. The milling process for 12 h and 20 h did not contribute to improve the identification of smaller size notches (1 mm). However, the smaller particle size produced smoother magnetic curves, with fewer discontinuities and improved signal-to-noise ratio. In summary, the results suggest that the proposed approach has great potential for the detection of damage in polymer composites structures

Avaliação do efeito da adição de resíduo de borracha de pneu e brita calcária na formulação de compósitos cimentíceos

Researches have shown that the introduction of rubber in concrete improves the features of its deformability, as well as contributes to environmental disposal of waste generated in the tire retreading process. Furthermore, there is a high availability of limestone within RN and CE country. Ignorance about this stone, does not allow its wide use as aggregate, leaving, this abundant supply idle. A composite of limestone gravel, with proportions of tire rubber waste which could be used as concrete would be an alternative to concrete for low applications. Therefore, this research aims to evaluate the characteristics of concrete containing limestone gravel and proportions of little aggregate replacement (sand) by tire rubber waste. To this goal, the material components of the concrete were characterized, concrete specimens with limestone gravel were made, from the dash 1.0: 2.5: 3.5, varying the water/cement ratio, and inserting a commercial plasticizer, without a proportion of residue, known as reference. From this, concrete with and without the presence of the additive in the same proportions were chosen, as well as these with the use of granite gravel, for being the most used. Selected the references, to these, replacements of little aggregate (sand) were added replaced by rubber waste from the tire retreading process, treated with 1M NaOH in proportions from 5.0 to 20.0 % by mass, cured and exposed to the semiarid environment. The results indicate the possibility of using limestone gravel in the concrete composition with workability correction using plasticizer. There was a decrease in the mechanical properties of the concrete with increments of waste rubber, but there is an improvement in toughness and deformability of the composite, which makes it interesting for the construction of non-structural concrete floors, as well as, the rubber waste delayed the hardening process, continuing to gain resistance after 28 days

Efeito de adições poliméricas na aderência de pastas de cimento a tubos metálicos após ciclagem térmica

Thermal recovery methods, especially steam injection, have been used to produce heavy oils. However, these methods imply that the metallic casing-cement sheath interface is submitted to thermal cycling. As a consequence, cracking may develop due to the thermal expansion mismatch of such materials, which allows the flow of oil and gas through the cement sheath, with environmental and economical consequences. It is therefore important to anticipate interfacial discontinuities that may arise upon Thermal recovery. The present study reports a simple alternative method to measure the shear strength of casing-sheath interfaces using pushthrough geometry, applied to polymer-containing hardened cement slurries. Polyurethane and recycled tire rubber were added to Portland-bases slurries to improve the fracture energy of intrinsically brittle cement. Samples consisting of metallic casing sections surrounded by hardened polymer-cement composites were prepared and mechanically tested. The effect of thermal cycles was investigated to simulate temperature conditions encountered in steam injection recovery. The results showed that the addition of polyurethane significantly improved the shear strength of the casing-sheath interface. The strength values obtained adding 10% BWOC of polyurethane to a Portland-base slurry more than doubled with respect to that of polyurethane-free slurries. Therefore, the use of polyurethane significantly contributes to reduce the damage caused by thermal cycling to cement sheath, improving the safety conditions of oil wells and the recovery of heavy oils