OPTIMIZATION AND CONTROL OF A CONTINUOUS POLYMERIZATION REACTOR

This work studies the optimization and control of a styrene polymerization reactor. The proposed strategy deals with the case where, because of market conditions and equipment deterioration, the optimal operating point of the continuous reactor is modified significantly along the operation time and the control system has to search for this optimum point, besides keeping the reactor system stable at any possible point. The approach considered here consists of three layers: the Real Time Optimization (RTO), the Model Predictive Control (MPC) and a Target Calculation (TC) that coordinates the communication between the two other layers and guarantees the stability of the whole structure. The proposed algorithm is simulated with the phenomenological model of a styrene polymerization reactor, which has been widely used as a benchmark for process control. The complete optimization structure for the styrene process including disturbances rejection is developed. The simulation results show the robustness of the proposed strategy and the capability to deal with disturbances while the economic objective is optimized.

Optimization and control of a continuous polymerization reactor

This work studies the optimization and control of a styrene polymerization reactor. The proposed strategy deals with the case where, because of market conditions and equipment deterioration, the optimal operating point of the continuous reactor is modified significantly along the operation time and the control system has to search for this optimum point, besides keeping the reactor system stable at any possible point. The approach considered here consists of three layers: the Real Time Optimization (RTO), the Model Predictive Control (MPC) and a Target Calculation (TC) that coordinates the communication between the two other layers and guarantees the stability of the whole structure. The proposed algorithm is simulated with the phenomenological model of a styrene polymerization reactor, which has been widely used as a benchmark for process control. The complete optimization structure for the styrene process including disturbances rejection is developed. The simulation results show the robustness of the proposed strategy and the capability to deal with disturbances while the economic objective is optimized.

Polymerization kinetics and reactivity of alternative initiators systems for use in light-activated dental resins

Objectives. The purpose of this study was to evaluate the reactivity and polymerization kinetics behavior of a model dental adhesive resin with water-soluble initiator systems. Methods. A monomer blend based on Bis-GMA, TEGDMA and HEMA was used as a model dental adhesive resin, which was polymerized using a thioxanthone type (QTX) as a photoinitiator. Binary and ternary photoinitiator systems were formulated using 1 mol% of each initiator. The co-initiators used in this study were ethyl 4-dimethylaminobenzoate (EDAB), diphenyliodonium hexafluorophosphate (DPIHFP), 1,3-diethyl-2-thiobarbituric acid (BARB), p-toluenesulfinic acid and sodium salt hydrate (SULF). Absorption spectra of the initiators were measured using a UV-Vis spectrophotometer, and the photon absorption energy (PAE) was calculated. The binary system camphorquinone (CQ)/amine was used as a reference group (control). Twelve groups were tested in triplicate. Fourier-transform infrared spectroscopy (FTIR) was used to investigate the polymerization reaction during the photoactivation period to obtain the degree of conversion (DC) and maximum polymerization rate (R-p(max)) profile of the model resin. Results. In the analyzed absorption profiles, the absorption spectrum of QTX is almost entirely localized in the UV region, whereas that of CQ is in the visible range. With respect to binary systems, CQ + EDAB exhibited higher DC and R-p(max) values. In formulations that contained ternary initiator systems, the group CQ + QTX + EDAB was the only one of the investigated experimental groups that exhibited an R-p(max) value greater than that of CQ + EDAB. The groups QTX + EDAB + DPIHFP and QTX + DPIHFP + SULF exhibited values similar to those of CQ + EDAB with respect to the final DC; however, they also exhibited lower reactivity. Significance. Water-soluble initiator systems should be considered as alternatives to the widely used CQ/amine system in dentin adhesive formulations. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Use of Gas Diffusion Electrode for the In Situ Generation of Hydrogen Peroxide in an Electrochemical Flow-By Reactor

Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at -2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at -1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/ (L min); energy consumption = 30.1 kWh/kg).

Kinetic and thermodynamic investigation of Arthrospira (Spirulina) platensis fed-batch cultivation in a tubular photobioreactor using urea as nitrogen source

BACKGROUND: Fed-batch culture allows the cultivation of Arthrospira platensis using urea as nitrogen source. Tubular photobioreactors substantially increase cell growth, but the successful use of this cheap nitrogen source requires a knowledge of the kinetic and thermodynamic parameters of the process. This work aims at identifying the effect of two independent variables, temperature (T) and urea daily molar flow-rate (U), on cell growth, biomass composition and thermodynamic parameters involved in this photosynthetic cultivation. RESULTS: The optimal values obtained were T = 32 degrees C and U = 1.16 mmol L-1 d-1, under which the maximum cell concentration was 4186 +/- 39 mg L-1, cell productivity 541 +/- 5 mg L-1 d-1 and yield of biomass on nitrogen 14.3 +/- 0.1 mg mg-1. Applying an Arrhenius-type approach, the thermodynamic parameters of growth (?H* = 98.2 kJ mol-1; ?S* = - 0.020 kJ mol-1 K-1; ?G* = 104.1 kJ mol-1) and its thermal inactivation (Delta H-D(0) =168.9 kJ mol-1; Delta S-D(0) = 0.459 kJ mol-1 K-1; Delta G(D)(0) =31.98 kJ mol-1) were estimated. CONCLUSIONS: To maximize cell growth T and U were simultaneously optimized. Biomass lipid content was not influenced by the experimental conditions, while protein content was dependent on both independent variables. Using urea as nitrogen source prevented the inhibitory effect already observed with ammonium salts. Copyright (c) 2012 Society of Chemical Industry

Phenol degradation in an anaerobic fluidized bed reactor packed with low density support materials

The objective of this research was to study phenol degradation in anaerobic fluidized bed reactors (AFBR) packed with polymeric particulate supports (polystyrene - PS, polyethylene terephthalate - PET, and polyvinyl chloride - PVC). The reactors were operated with a hydraulic retention time (HRT) of 24 h. The influent phenol concentration in the AFBR varied from 100 to 400 mg L-1, resulting in phenol removal efficiencies of similar to 100%. The formation of extracellular polymeric substances yielded better results with the PVC particles; however, deformations in these particles proved detrimental to reactor operation. PS was found to be the best support for biomass attachment in an AFBR for phenol removal. The AFBR loaded with PS was operated to analyze the performance and stability for phenol removal at feed concentrations ranging from 50 to 500 mg L-1. The phenol removal efficiency ranged from 90-100%.

A comparative study between crack analysis and a mechanical test for assessing the polymerization stress of restorative composites

Objectives. To verify the hypothesis that crack analysis and a mechanical test would rank a series of composites in a similar order with respect to polymerization stress. Also, both tests would show similar relationships between stress and composite elastic modulus and/or shrinkage. Methods. Soda-lime glass discs (2-mm thick) with a central perforation (3.5-mm diameter) received four Vickers indentations 500 mu m from the cavity margin. The indent cracks were measured (500x) prior and 10 min after the cavity was restored with one of six materials (Kalore/KL, Gradia/GR, Ice/IC, Wave/WV, Majesty Flow/MF, and Majesty Posterior/MP). Stresses at the indent site were calculated based on glass fracture toughness and increase in crack length. Stress at the bonded interface was calculated using the equation for an internally pressurized cylinder. The mechanical test used a universal testing machine and glass rods (5-mm diameter) as substrate. An extensometer monitored specimen height (2 mm). Nominal stress was calculated dividing the maximum shrinkage force by the specimen cross-sectional area. Composite elastic modulus was determined by nanoindentation and post-gel shrinkage was measured using strain gages. Data were subjected to one-way ANOVA/Tukey or Kruskal-Wallis/Mann-Whitney tests (alpha: 5%). Results. Both tests grouped the composites in three statistical subsets, with small differences in overlapping between the intermediate subset (MF, WV) and the highest (MP, IC) or the lowest stress materials (KL, GR). Higher stresses were developed by composites with high modulus and/or high shrinkage. Significance. Crack analysis demonstrated to be as effective as the mechanical test to rank composites regarding polymerization stress. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Arthrospira (Spirulina) platensis cultivation in tubular photobioreactor: Use of no-cost CO2 from ethanol fermentation

The present study aimed at evaluating the production of Arthrospira platensis in tubular photobioreactor using CO2 from ethanol fermentation. The results of these cultivations were compared to those obtained using CO2 from cylinder at different protocols of simultaneous ammonium sulfate and sodium nitrate feeding. Maximum cell concentration (X-m), cell productivity (P-x), nitrogen-to-cell conversion factor (Y-X/N), and biomass composition (total lipids and proteins) were selected as responses and evaluated by analysis of variance. The source of CO2 did not exert any significant statistical influence on these responses, which means that the flue gas from ethanol fermentation could successfully be used as a carbon source as well as to control the medium pH, thus contributing to reduce the greenhouse effect. The results taken as a whole demonstrated that the best combination of responses mean values (X-m = 4.543 g L-1; P-x = 0.460 g L-1 d(-1); Y-X/N = 15.6 g g(-1); total lipids = 8.39%; total proteins = 18.7%) was obtained using as nitrogen source a mixture of 25% NaNO3 and 75% (NH4)(2)SO4, both expressed as nitrogen. (C) 2011 Elsevier Ltd. All rights reserved.

A comparative evaluation of polymerization stress data obtained with four different mechanical testing systems

Objectives. The null hypothesis was that mechanical testing systems used to determine polymerization stress (sigma(pol)) would rank a series of composites similarly. Methods. Two series of composites were tested in the following systems: universal testing machine (UTM) using glass rods as bonding substrate, UTM/acrylic rods, "low compliance device", and single cantilever device ("Bioman"). One series had five experimental composites containing BisGMA:TEGDMA in equimolar concentrations and 60, 65, 70, 75 or 80 wt% of filler. The other series had five commercial composites: Filtek Z250 (3M ESPE), Filtek A110 (3M ESPE), Tetric Ceram (Ivoclar), Heliomolar (Ivoclar) and Point 4 (Kerr). Specimen geometry, dimensions and curing conditions were similar in all systems. sigma(pol) was monitored for 10 min. Volumetric shrinkage (VS) was measured in a mercury dilatometer and elastic modulus (E) was determined by three-point bending. Shrinkage rate was used as a measure of reaction kinetics. ANOVA/Tukey test was performed for each variable, separately for each series. Results. For the experimental composites, sigma(pol) decreased with filler content in all systems, following the variation in VS. For commercial materials, sigma(pol) did not vary in the UTM/acrylic system and showed very few similarities in rankings in the others tests system. Also, no clear relationships were observed between sigma(pol) and VS or E. Significance. The testing systems showed a good agreement for the experimental composites, but very few similarities for the commercial composites. Therefore, comparison of polymerization stress results from different devices must be done carefully. (c) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The influence of "C-factor" and light activation technique on polymerization contraction forces of resin composite

Objectives: This study evaluated the influence of the cavity configuration factor ("C-Factor") and light activation technique on polymerization contraction forces of a Bis-GMA-based composite resin (Charisma, Heraeus Kulzer). Material and Methods: Three different pairs of steel moving bases were connected to a universal testing machine (Emic DL 500): groups A and B - 2x2 mm (CF=0.33), groups C and D - 3x2 mm (CF=0.66), groups E and F - 6x2 mm (CF=1.5). After adjustment of the height between the pair of bases so that the resin had a volume of 12 mm(3) in all groups, the material was inserted and polymerized by two different methods: pulse delay (100 mW/cm(2) for 5 s, 40 s interval, 600 mW/cm(2) for 20 s) and continuous pulse (600 mW/cm(2) for 20 s). Each configuration was light cured with both techniques. Tensions generated during polymerization were recorded by 120 s. The values were expressed in curves (Force(N) x Time(s)) and averages compared by statistical analysis (ANOVA and Tukey's test, p<0.05). Results: For the 2x2 and 3x2 bases, with a reduced C-Factor, significant differences were found between the light curing methods. For 6x2 base, with high C-Factor, the light curing method did not influence the contraction forces of the composite resin. Conclusions: Pulse delay technique can determine less stress on tooth/restoration interface of adhesive restorations only when a reduced C-Factor is present.

Characterization of Immobilized Biomass by Amplified rDNA Restriction Analysis (ARDRA) in an Anaerobic Sequencing-Batch Biofilm Reactor (ASBBR) for the Treatment of Industrial Wastewater

The performance of an anaerobic sequencing-batch biofilm reactor (ASBBR-laboratory scale- 14L) containing biomass immobilized on coal was evaluated for the removal of elevated concentrations of sulfate (between 200 and 3,000 mg SO4-2.L-1) from industrial wastewater effluents. The ASBBR was shown to be efficient for removal of organic material (between 90% and 45%) and sulfate (between 95% and 85%). The microbiota adhering to the support medium was analyzed by amplified ribosomal DNA restriction analysis (ARDRA). The ARDRA profiles for the Bacteria and Archaea domains proved to be sensitive for the determination of microbial diversity and were consistent with the physical-chemical monitoring analysis of the reactor. At 3,000 mg SO4-2.L-1, there was a reduction in the microbial diversity of both domains and also in the removal efficiencies of organic material and sulfate.

Characterization of depolymerized residues from extremely low acid hydrolysis (ELA) of sugarcane bagasse cellulose: Effects of degree of polymerization, crystallinity and crystallite size on thermal decomposition

Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H2SO4 at 190, 210 and 225 degrees C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225 degrees C for 80,40 and 8 min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210 degrees C were similar to that of Avicel. (C) 2011 Elsevier B.V. All rights reserved.

Flow-injection spectrophotometric determination of captopril in pharmaceutical formulations using a new solid-phase reactor containing AgSCN immobilized in a polyurethane resin

A simple flow-injection analysis procedure was developed for determining captopril in pharmaceutical formulations employing a novel solid-phase reactor containing silver thiocyanate immobilized in a castor oil derivative polyurethane resin. The method was based on silver mercaptide formation between the captopril and Ag(I) in the solid-phase reactor. During such a reaction, the SCN- anion was released and reacted with Fe3+, which generated the FeSCN2+ complex that was continuously monitored at 480 nm. The analytical curve was linear in the captopril concentration range from 3.0 x 10(-4) mol L-1 to 1.1 x 10(-3) mol L-1 with a detection limit of 8.0 x 10(-5) mol L-1. Recoveries between 97.5% and 103% and a relative standard deviation of 2% for a solution containing 6.0 x 10(-4) mol L-1 captopril (n = 12) were obtained. The sample throughput was 40 h(-1) and the results obtained for captopril in pharmaceutical formulations using this procedure and those obtained using a pharmacopoeia procedure were in agreement at a 95% confidence level.

Fiber Post Cementation Strategies: Effect of Mechanical Cycling on Push-out Bond Strength and Cement Polymerization Stress

Purpose: To evaluate the effect of mechanical cycling and cementation strategies on the push-out bond strength between fiber posts and root dentin and the polymerization stresses produced using three resin cements. Materials and Methods: Eighty bovine mandibular teeth were sectioned to a length of 16 mm, prepared to 12 mm, and embedded in self-curing acrylic resin. The specimens were then distributed into 8 groups (n = 10): Gr1 - Scotchbond Multi Purpose + RelyX ARC; Gr2 - Scotchbond Multi Purpose + RelyX ARC + mechanical cycling; Gr3 - AdheSE + Multilink Automix; Gr4 - AdheSE + Multilink Automix + mechanical cycling; Gr5 - phosphoric acid + RelyX U100 (self-adhesive cement); Gr6 - phosphoric acid+ RelyX U100 + mechanical cycling; Gr7 - RelyX U100; Gr8 - RelyX U100 + mechanical cycling. The values obtained from the push-out bond strength test were submitted to two-way ANOVA and Tukey's test (p = 0.05), while the values obtained from the polymerization stress test were subjected to one-way ANOVA and Tukey's test (alpha = 0.05). Results: Mechanical cycling did not affect the bond strength values (p = 0.236), while cementation strategies affected the push-out bond strength (p < 0.001). Luting with RelyX U100 and Scotch Bond Multi Purpose + RelyX ARC yielded higher push-out bond strength values. The polymerization stress results were affected by the factor "cement" (p = 0.0104): the self-adhesive cement RelyX U100 exhibited the lowest values, RelyX ARC resulted in the highest values, while Multi link Automix presented values statistically similar to the other two cements. Conclusion: The self-adhesive cement appears to be a good alternative for luting fiber posts due to the high push-out bond strengths and lower polymerization stress values.

High Cholesterol Feeding May Induce Tubular Dysfunction Resulting in Hypomagnesemia

Background/Aims: Hypomagnesemia may induce hypercholesterolemia, but the contrary has not been described yet. Thus, magnesium homeostasis was evaluated in rats fed a cholesterol-enriched diet for 8 days. This study has a relevant clinical application if hypomagnesemia, due to hypercholesterolemia, is confirmed in patients with long-term hypercholesterolemia. Methods: Both hypercholesterolemic (HC) and normocholesterolemic rats (NC) were divided into sets of experiments to measure hemodynamic parameters, physiological data, maximum capacity to dilute urine (C-H2O), variations (Delta) in [Ca2+](i) and the expression of transporter proteins. Results: HC developed hypomagnesemia and showed high magnesuria in the absence of hemodynamic abnormalities. However, the urinary sodium excretion and C-H2O in HC was similar to NC. On the other hand, the responses to angiotensin II by measuring Delta [Ca2+](i) were higher in the thick ascending limb of Henle's loop (TAL) of HC than NC. Moreover, high expression of the cotransporter NKCC2 was found in renal outer medulla fractions of HC. Taken together, the hypothesis of impairment in TAL was excluded. Actually, the expression of the epithelial Mg2+ channel in renal cortical membrane fractions was reduced in HC. Conclusion: Impairment in distal convoluted tubule induced by hypercholesterolemia explains high magnesuria and hypomagnesemia observed in HC. Copyright (C) 2011 S. Karger AG, Basel