Desgaste corrosivo-cavitativo-erosivo de um aço-carbono em meio aquoso com frações de sal (NaCl), CO2 e particulados sólidos (SiO2)

A batch of eighty-four coupons of low carbon steel were investigated at laboratory conditions under a corrosive, cavitative-corrosive (CO2) and corrosive-erosive (SiO2 + CO2) in an aqueous salt solution and two levels of temperature. The following measurements were made on Vickers (HV0,05, HV0,10, HV0,20) Microhardness tests at three levels of subsurface layer. A turbulent flow collided on the cylindrical sample, with and without mechanical stirring and gas bubbling, with and without fluid contamination by solid particles of SiO2, at two temperatures. Surface Roughness and Waviness, under two conditions "as received, after machining" and "after worn out", as well as gravimetric and electrochemical parameter were measured on the two opposite generatrices of each cylindrical sample, on the flow upstream (0°) and downstream (180°) by Profilometry, Mass Variation and Linear Polarization Resistance (LPR). The results of the Microhardness and Surface Texture of all coupons were subjected to statistical comparison, using the software Statgraphics® Centurion XVI, 95% statistical certainty, and significant differences were observed in some arrays of measurements. The corrosive wear rate measured by LPR and mass variation shown to be sensitive to the presence of bubbles and hydrodynamic fluctuations inside the cell, considering the temperature and contamination of corrosive fluid by solid particles. The main results of visual inspection relative to some topologies of the surface damages involving different mechanisms that were seen to give explanation for some fluctuations in wear rates of the steel experimentally investigated

Estudo da eficácia do tensoativo sorbitano tween 80 veiculado em nanoemulsão contendo óleo de soja, como inibidor de corrosão

Nowadays, the use of chemicals that satisfactorily meet the needs of different sectors of the chemical industry is linked to the consumption of biodegradable materials. In this context, this work contemplated biotechnological aspects with the objective of developing a more environmentally-friendly corrosion inhibitor. In order to achieve this goal, nanoemulsion-type systems (NE) were obtained by varying the amount of Tween 80 (9 to 85 ppm) a sortitan surfactant named polyoxyethylene (20) monooleate. This NE-system was analyzed using phase diagrams in which the percentage of the oil phase (commercial soybean oil, codenamed as OS) was kept constant. By changing the amount of Tween 80, several polar NE-OS derived systems (O/W-type nanoemulsion) were obtained and characterized through light scattering, conductivity and pH, and further subjected to electrochemical studies. The interfacial behavior of these NE-OS derived systems (codenamed NE-OS1, S2, S3, S4 and S5) as corrosion inhibitors on carbon steel AISI 1020 in saline media (NaCl 3.5%) were evaluated by measurement of Open Circuit Potential (OCP), Polarization Curves (Tafel extrapolation method) and Electrochemical Impedance Spectroscopy (EIS). The analyzed NE-OS1 and NE-OS2 systems were found to be mixed inhibitors with quantitative efficacy (98.6% - 99.7%) for concentrations of Tween 80 ranging between 9 and 85 ppm. According to the EIS technique, maximum corrosion efficiency was observed for some tested NE-OS samples. Additionaly to the electrochemical studies, Analysis of Variance (ANOVA) and Principal Component Analysis (PCA) were used, characterization of the nanoemulsion tested systems and adsorption studies, respectively, which confirmed the results observed in the experimental analyses using diluted NE-OS samples in lower concentrations of Tween 80 (0.5 1.75 ppm)

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

Nitretação em plasma com gaiola catódica: investigação do mecanismo e estudo comparativo com a nitretação em plasma de tensão contínua

The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Avaliação por pig de perfilagem de danos superfciais nos materiais das paredes de dutos de petróleo

The modern technology of materials and structural integrity of pipelines requests the use of inspection tools named inspection pigs to detect, localize and measure the length, width and depth dimensions of the thickness losses of walls of buried and underwater pipelines in service. These tools run them internally, performing and recording measurements, with performance that varies according to the pig s technology. It has been developed recently an instrumented pig technology, called feller pig. This work aims to indicate factors that influence the feller pig technology performance in the detection and in the accuracy of measurement of the length, width and depth dimensions of the thickness losses on the internal surface of an oil pipeline wall under normal conditions of oil pipe inspection with pig. In this work, is made a collection of factors and an analyses of the technology based on the available literature, as well as an experiment to observe the technology and the factors operating. In the experiment, a feeler pig is used in a pipeline built in carbon steel and in operation that flows petroleum, in witch are observed areas with internal thickness losses occurred naturally. Some of these areas and their dimensions taken by automated ultra-sound scanner are compared with the ones indicated by the feller pig. Based on the data collection, on the analysis and on the experiment, the influence of factors object of this research is discussed. It is concluded that, among these, there are factors related to pipe fabrication tolerances, to wear of pig components, to internal adhesive wear of pipeline, to other pipeline damages and to technology characteristics. Finally, actions are suggested to know better, improve and define the applicability of this technology

Desenvolvimento de um sistema para análise de integridade estrutural de equipamentos estáticos baseado em cad vps micro cracks e ultrassom

In general, the designs of equipment takes into account the effects and processes of deterioration it will undergo and arrives at an approximate useful life. However, changes in operational processes and parameters, the action of external agents, the kind of maintenance conducted, the means of monitoring, and natural and accidental occurrences completely modify the desired performance of the equipment. The discontinuities that occur in anisotropic materials often and due to different factors evolve from being subcritical to critical acquiring the status of defect and compromising the physical integrity of the equipment. Increasingly sophisticated technological means of detection, monitoring and assessment of these discontinuities are required to respond ever more rapidly to the requirements of industry. This paper therefore presents a VPS (Virtual Pipe System) computational tool which uses the results of ultrasonic tests on equipment, plotting the discontinuities found in models created in the CAD and CAE systems, and then simulates the behavior of these defects in the structure to give an instantaneous view of the final behavior. This paper also presents an alternative method of conventional ultrasonic testing which correlates the integrity of an overlay (carbon steel and stainless steel attached by welding) and the reflection of ultrasonic waves coming from the interface between the two metals, thus making it possible to identify cracks in the casing and a shift of the overlay

Análise topológica experimental por perfilometria cíclica indutiva de superficies de paredes estruturais

To enhance the maintenance practices, Oil and Gas Pipelines are inspected from the inside by automated systems called PIG (Pipeline Inspection Gauge). The inspection and mapping of defects, as dents and holes, in the internal wall of these pipelines are increasingly put into service toward an overall Structural Integrity Policy. The residual life of these structures must be determined such that minimize its probability of failure. For this reason, the investigation on the detection limits of some basic topological features constituted by peaks or valleys disposed along a smooth surface is of great value for determining the sensitivity of the measurements of defects from some combinations of circumferential, axial and radial extent. In this investigation, it was analyzed an inductive profilometric sensor to scan three races, radius r1, r2, r3, in a circular surface of low carbon steel, equipped with eight consecutive defects simulated by bulges and holes by orbit, equally spaced at p/4 rad. A test rig and a methodology for testing in laboratory were developed to evaluate the sensor response and identify their dead zones and jumps due to fluctuations as a function of topological features and scanning velocity, four speeds different. The results are presented, analyzed and suggestions are made toward a new conception of sensor topologies, more sensible to detect these type of damage morphologies

Estudos ecogenômicos e bioprospectivos de Shewanella ssp

Bacteria trom Shewanella and Geobacter ganera are the most studied iron-reducing microorganisms particularly due to their electron transport systems and contribution to some industrial and environmental problems, including steel corrosion, bioenergy and bioremediation of petroleum-impacted sites. The present study was focused in two ways: the first is an in silico comparative ecogenomic study of Shewanella spp. with sequenced genomes, and the second is an experimental metagenomic work to detect iron-reducing Shewanella through PCR-DGGE of a metabolic gene. The in silico study resulted in positive correIation between copy number of 16S rDNA and genome size in Shewanella spp., with clusters of rrn near lhe origin of replication. This way, the genus is inferred as opportunist. There are no compact genomes and their sequences length varied, ranging from 4306142 nt in S. amazonensis SB2B to 5935403 nt in S. woodyi ATCC 51908, without correIation to temperature range characteristic of each specie. Intragenomic 16S rDNA sequences possess little divergence, but reasonable to resuIt in different phyIogenetic trees, depending on the sequence that is chosen to compare. For moIecuIar detection of iron-reducing Shewanella, it is proposed the mtrB gene as new biomarker. because it codes to a fundamental protein at Fe (III)-reduction. The specific primers were designed and evaluated in silico and resulted in a fragment of 360 pb. In the second study, these primers were tested in a genomic sample from S. oneidensis MR-1, amplifying the expected region. After this successfuI resuIt, the primer set was used as a tool to assess the iron-reducing communities of ShewaneIla genus under an environmental stress, i.e. crude oil contamination in mangrove sediment in Rio Grande do Norte State (Brazil). The primers presented high specificity and the reactions performed resulted in one single band of ampIification in the metagenomic samples. The fingerprinting obtained at DGGE reveaIed temporal variation of Shewanella spp. in analyzed samples. The resuIts presented show the detection of a biotechnological important group of microorganisms, the iron-reducing Shewanella spp. using a metabolic gane as target. It is concluded there are eight or more 16S rDNA sequences in Shewanella genus, with little divergence among them that affects the phylogeny; the pair of primers designed to ampIify mtrB sequences is a viable alternative to detect iron-reducing ShewanelIa in metagenomic approaches; such bacteria are present in the mangrove sediment anaIyzed, with temporal variations in the samples. This is the first experimental study that screened the iron-reducing Shewanella genus in a metagenomic experiment of mangrove sediments subjected to oil contamination through a key metabolic gene

Caracterização e aplicação de sistemas micelares e microemulsionados como inibidores de corrosão

Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers

Estudo do comportamento da sinterização de compactos de cavacos de um aço SAE 1050 obtidos sob alta pressão

From an economic standpoint, the powder metallurgy (P/M) is a technique widely used for the production of small parts. It is possible, through the P/M and prior comminution of solid waste such as ferrous chips, produce highly dense sintered parts and of interest to the automotive, electronics and aerospace industries. However, without prior comminution the chip, the production of bodies with a density equal to theoretical density by conventional sintering techniques require the use of additives or significantly higher temperatures than 1250ºC. An alternative route to the production of sintered bodies with high density compaction from ferrous chips (≤ 850 microns) and solid phase sintering is a compression technique under high pressure (HP). In this work, different compaction pressures to produce a sintered chip of SAE 1050 carbon steel were used. Specifically, the objective was to investigate them, the effect of high pressure compression in the behavior of densification of the sintered samples. Therefore, samples of the chips from the SAE 1050 carbon steel were uniaxially cold compacted at 500 and 2000 MPa, respectively. The green compacts obtained were sintered under carbon atmosphere at 1100 and 1200°C for 90 minutes. The heating rate used was 20°C/min. The starting materials and the sintered bodies were characterized by optical microscopy, SEM, XRD, density measurements (geometric: mass/volume, and pycnometry) and microhardness measurements Vickers and Rockwell hardness. The results showed that the compact produced under 2000 MPa presented relative density values between 93% and 100% of theoretical density and microhardness between 150 HV and 180 HV, respectively. In contrast, compressed under 500 MPa showed a very heterogeneous microstructure, density value below 80% of theoretical density and structural conditions of inadequate specimens for carrying out the hardness and microhardness measurements. The results indicate that use of the high pressure of ferrous chips compression is a promising route to improve the sinterability conditions of this type of material, because in addition to promoting greater compression of the starting material, the external tension acts together with surface tension, functioning as the motive power for sintering process. Additionally, extremely high pressures allow plastic deformation of the material, providing an intimate and extended contact of the particles and eliminating cracks and pores. This tends to reduce the time and / or temperature required for good sintering, avoiding excessive grain growth without the use of additives. Moreover, higher pressures lead to fracture the grains in fragile or ductile materials highly hardened, which provides a starting powder for sintering, thinner, without the risk of contamination present when previous methods are used comminution of the powder.

Nitretação em plasma com gaiola catódica: investigação do mecanismo e estudo comparativo com a nitretação em plasma de tensão contínua

The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Avaliação de heterociclo do tipo mesoiônico solubilizado em sistema microemulsionado para aplicação em dutos

The efficiency of inhibition to corrosion of steel AISI 1018 of surfactant coconut oil saponified (SCO) and heterocyclic type mesoionics (1,3,4-triazólio-2-tiolato) in systems microemulsionados (SCO-ME and SCO-ME-MI) Of type O/A (rich in water emulsion) region with the work of Winsor IV. The systems microemulsionados (SCO-ME and SCO-ME-MI) were evaluated with a corrosion inhibitor for use in saline 10,000 ppm of chloride enriched with carbon dioxide (CO2). The assessment of corrosion inhibitors were evaluated by the techniques of linear polarization resistance (LPR) and loss of weight (MW) in a cell instrumented given the gravity and electrochemical devices. The systems were shooting speed of less than 60 minutes and efficiency of inhibition [SCO-ME (91.25%) and SCO-ME-MI (98.54%)]

Avaliação de heterociclo do tipo mesoiônico solubilizado em sistema microemulsionado para aplicação em dutos

The efficiency of inhibition to corrosion of steel AISI 1018 of surfactant coconut oil saponified (SCO) and heterocyclic type mesoionics (1,3,4-triazólio-2-tiolato) in systems microemulsionados (SCO-ME and SCO-ME-MI) Of type O/A (rich in water emulsion) region with the work of Winsor IV. The systems microemulsionados (SCO-ME and SCO-ME-MI) were evaluated with a corrosion inhibitor for use in saline 10,000 ppm of chloride enriched with carbon dioxide (CO2). The assessment of corrosion inhibitors were evaluated by the techniques of linear polarization resistance (LPR) and loss of weight (MW) in a cell instrumented given the gravity and electrochemical devices. The systems were shooting speed of less than 60 minutes and efficiency of inhibition [SCO-ME (91.25%) and SCO-ME-MI (98.54%)]