Microstructural study of synthesized polyethylenes by homogeneous and heterogeneous nickel α-diimine catalysts

In this work, ethylene polymerization was investigated by using homogeneous and heterogenouse nickel α-diimine catalysts [1,4-bis(2,6-diisopropylphenyl) acenaphthene diimine nickel(II) dibromide]. Methyl aluminoxane (MAO) and triethyl aluminum (TEA) were used as cocatalysts in homogenous and heterogeneous polymerizations, respectively. The heterogeneous catalyst showed lower activity than its homogeneous equivalent. The influence of polymerization temperature and heterogenization conditions was studied on the microstructure properties of the prepared polymers. Increasing polymerization temperature (T _P) up to 50 °C decreased the activity of both homogenous (LN) and heterogeneous (LNS) nickel α-diimine catalysts. The highest activities were 1286 and 982 kg PE (mol Ni bar h)^?1 obtained at T _P = 30 °C for LN and LNS catalysts, respectively. The polymer samples obtained by supported catalyst (LNS) showed lower unsaturation contents. Moreover, DSC analysis did not show any melting peaks for polymers obtained by LN catalyst due to their amorphous structure, which was confirmed by XRD analysis. The microstructure of the prepared polymers was completed by successive self-nucleation annealing (SSA) and was investigated by ¹³C NMR studies. The SSA thermogram of samples made by LNS catalyst exhibited several crystal types with different lamella thicknesses. The branches in polyethylene samples produced by homogenous catalyst were higher and showed more diversity. The total methyl branch percentages for both LN and LNS catalysts were 13.1 and 3.4%, respectively.     

Electrocatalytic oxidation of p-nitrophenol from aqueous solutions at Pb/PbO2 anodes

In this work, the elimination of p-nitrophenol (p-NPh) from aqueous solutions by electrochemical oxidation at Pb/PbO₂ anodes was investigated. The process was studied under galvanostatic polarization mode in acidic and alkaline media, as a function of the temperature (20, 40 and 60 °C) and of the anodic current density (J = 10, 20 and 30 mA cm⁻²). In acidic media (0.5 M H₂SO₄), the oxidation process allowed a 94% p-NPh conversion in 7 h, at 20 °C and with J = 20 mA cm⁻², with a wide distribution of degradation products (in particular: 39% p-benzoquinone and 26% hydroquinone, as given by a mass balance at the above electrolysis time). Under these conditions, the current efficiency for the substrate oxidation was 15.4% ([Ah L⁻¹]_exp = 7 versus [Ah L⁻¹]_theo = 1.08 Ah L⁻¹). In alkaline media (0.1 M NaOH, pH 8.5), the most effective p-NPh elimination (97%) was obtained at 60 °C, 20 mA cm⁻² and 420 min of electrolysis time, again with the production of p-benzoquinone and hydroquinone (52.7 and 15.1%, respectively). Under the latter conditions, an almost complete chemical oxygen demand (COD) abatement was attained, with a high level of p-NPh mineralization (>80%), a yield of p-NPh conversion greater than 95% and a scarce formation of aliphatic acids (most probably maleic acid). From the degradation curves ([p-NPh] versus t), in both acidic and alkaline media, the UV analyses and/or COD measurements, a complete oxidation of aliphatic acids to form CO₂ could be predicted for electrolysis time >420 min, according to a suggested oxidation pathway.     

Metal ion retention properties of poly(acrylic acid) and poly[N‐3‐(dimethylamino)propyl acrylamide‐co‐acrylic acid]

The crosslinked resins poly(acrylic acid) (PAA) and poly[N‐3‐(dimethylamino)propyl acrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] are obtained by radical polymerization and characterized by FTIR spectroscopy. PAA at basic pH exists basically as an acrylate anion that may contain end carboxylate groups or form bridges acting as mono‐ or bidentate ligands. P(NDAPA‐co‐AA) presents three potential ligand groups in its structure: carboxylic acid, amide, and amine. The trace metal ion retention properties of these two resins is compared by using the batch equilibrium procedure. The metal ions are contained in saline aqueous solutions and are found in natural seawater. The retention of Cu(II), Pb(II), Cd(II), and Ni(II) metal ions is studied under competitive and noncompetitive conditions. The effects on the pH, contact time, amount of adsorbent, temperature, and salinity are investigated. The PAA resin presents a high affinity (>80%) for Cu(II) and Cd(II) ions. The P(NDAPA‐co‐AA) resin shows a high affinity for Pb(II) and Cd(II) ions. With 4M HNO₃ it is possible to completely recover the PAA resin charged with Cu(II) ions and the P(NDAPA‐co‐AA) resin charged with Pb(II) ions. The two resins show a high affinity for Cd(II) ions from the seawater containing Cu(II) and Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1385–1394, 2005     

Methane transformation into aromatic hydrocarbons by activation with LPG over Zn‐ZSM‐11 zeolite

Methane (C₁) can be activated by interaction with liquefied petroleum gas (LPG) even at very high C₁ molar fractions in the feed (C₁/(C₁ + LPG)=0.85) at temperatures of 450–550°C, GHSV(LPG)=2240 and 810 ml/g h, over Zn‐ZSM‐11 (molar fraction Zn²⁺/(Zn²⁺H⁺=0.86) and total pressure of 1 atm. The isobutane (i‐C₄) of LPG could be the main responsible of this interaction. Aromatic hydrocarbons were the main products in the whole range of C₁ molar fractions (0.4–0.85) studied, reaching excellent levels of 10–45%. This revised version was published online in July 2006 with corrections to the Cover Date.     

Implementation of a Scale-Lab Lower-Limb Exoskeleton with Motion in Three Anatomical Planes

Abstract

This work deals with modeling, simulating and construction of a lower-limb exoskeleton with motion in the three anatomical planes, as well as to evaluate its performance to resolve trajectory tracking by means of feedback control schemes. The purpose is to create a scale-lab platform of a full-actuated exoskeleton to test tracking control of the main lower-limb joints to reproduce anatomical movements of a human being with no neuromuscular diseases. This functional scale-lab platform is the first step towards the design of neuromuscular rehabilitation tests based in full-automated assistive devices such as a lower-limb exoskeleton.     

Local-homogeneity-based global continuous control for mechanical systems with constrained inputs: finite-time and exponential stabilisation

A global continuous control scheme for the finite-time or (local) exponential stabilisation of mechanical systems with constrained inputs is proposed. The approach is formally developed within the theoretical framework of local homogeneity. This has permitted to solve the formulated problem not only guaranteeing input saturation avoidance but also giving a wide range of design flexibility. The proposed scheme is characterised by a saturating-proportional-derivative type term with generalised saturating and locally homogeneous structure that permits multiple design choices on both aspects. The work includes a simulation implementation section where the veracity of the so-cited argument claiming that finite-time stabilisers are faster than asymptotical ones is studied. In particular, a way to carry out the design so as to, indeed, guarantee faster stabilisation through finite-time controllers (beyond their finite-time convergence) is shown.     

Optimization of olefin copolymerization: effects of reaction parameters on catalytic activity and properties

The copolymerization of ethylene with 1-hexene using Et[Ind]₂ZrCl₂/MAO as catalyst was studied by multivariate methods. Three complete factorial designs were performed to study the influence of 1-hexene concentration, reaction temperature and [Al]/[Zr] ratio on catalytic activity, copolymer viscosity, crystallinity and melting point. Since the [Al]/[Zr] ratio has a small effect on the catalytic activity, a fourth design with 1-hexene and temperature was developed, giving higher catalytic activities. Temperature and 1-hexene concentration were the main effects found in the system. A second order effect arising from 1-hexene versus [Al]/[Zr] ratio was also detected. Polymer viscosity, crystallinity and melting points decreased with 1-hexene concentration. Viscosity decreased with temperature whereas crystallinity increased when the temperature was raised from 30 to 60 °C. Received: 13 June 1997/Revised version: 2 November 1997/Accepted: 21 November 1997     

Preparation of poly(ethylene-co-dicyclopentadiene) copolymers and a study on their post-polymerization epoxidation

The copolymerization of ethylene with dicyclopentadiene (DCP) using the metallocene catalyst rac-dimethylsilylbis(indenyl)zirconium dichloride (Me₂Si(Ind)₂ZrCl₂) proceeds with high activity producing materials with DCP incorporations of 0.5–2.7 mol%. The residual olefin moiety of the DCP comonomer is still available for reaction following polymerization and was epoxidized using H₂O₂ and formic acid. This reaction was optimized and proceeds with good conversion and the resulting materials show increased physical properties compared to the untreated copolymers.     

Structural optimization for performance-based design in earthquake engineering: Applications of neural networks

This work addresses an approach to performance-based design in the context of earthquake engineering. The objective is the optimization of the total structural cost, under constraints related to minimum target reliabilities specified for the different limit states or performance requirements. The problem involves (1) the use of a nonlinear, time-stepping dynamic analysis to investigate the responses of relevance to the performances’ evaluation and (2) the integration of the responses into measures of damage accumulated during the earthquake. The random responses are deterministically obtained for different combinations of the design parameters and the intervening random variables, of which some are associated with the structure and some with the earthquake characteristics. The approach uses a neural network representation of the responses and, for each one, the variability associated with different earthquake records is accommodated by developing two networks: one for the mean response over the records, and another for the corresponding standard deviation. The neural network representation facilitates the estimation of reliability by Monte Carlo simulation, and the reliability achieved in each performance level, for a specific combination of the design parameters, is itself represented with a neural network. This is then used within an optimization algorithm for minimum total cost under reliability constraints. An application example uses a reinforced concrete, multi-storey plane structure with seismic demands corresponding to the city of Mendoza, Argentina.