Minimum-time strategy to produce nonuniform emulsion copolymers. II. Open-loop control

An iterative approach was developed to determine the optimal monomer addition policies in real emulsion copolymerization systems in which only limited kinetic information is available. The approach was applied to obtain widely different copolymer composition profiles for the emulsion copolymerization of butyl acrylate and styrene. The approach involves a series of semicontinuous emulsion copolymerizations carried out in an openloop control mode. Each reaction was used to obtain an estimation of the kinetics of the process that was used to calculate the monomer addition profiles for the next experiment. The method is model-independent and converges rapidly. © 1995 John Wiley & Sons, Inc.     

Effect of elemental sulfur in the crosslinking reaction of poly(vinyl chloride) with tetramethyl thiuram disulfide

The effect of elemental sulfur (S₈) and tetramethyl thiuram disulfide (TMTD) on the chemical crosslinking of PVC is studied. The tensile strength, elongation at break, and gel content of crosslinked and uncrosslinked PVC molded samples, cured at different times in hot air, are evaluated. It was found that crosslinking PVC with TMTD improves its mechanical properties, and adding S₈ produces a slight improvement. Also, the S₈ presence accelerated the PVC/TMTD crosslinking reaction when the crosslinking reaction was carried out under shear forces, but not when the curing was done in hot air, where the S₈ retards the process.     

A Multi-Disciplinary Contribution to the Provenance Determination of Ancient Greek and Roman Marble Artifacts

The problem of determining the provenance of the white marble used for antique artifacts has been tackled in different ways. During the past decade it became clear that a multimethod approach is required to solve the problem. In addition, reliable reference material, i.e., samples collected at the ancient quarry sites in an archaeologically and geologically justified manner, turned out to be a prerequisite for reliable provenance determination. A multimethod approach based on petrography, stable isotope analysis of O and C, and trace element analysis yields complementary information. These methods were applied to the same set of 225 quarry samples. When processed with powerful statistical methods, the data thus obtained allowed all major types of marble used in antiquity to be distinguished. Thus, most problems concerning the provenance of artifacts can be solved. This approach was successfully applied to the provenance determination of about 75 artifacts from different museums in Europe and the USA.     

The effect of silicon, aluminium and phosphor on the dynamic behavior and phenomenological modelling of multiphase TRIP steels

Multiphase TRansformation Induced Plasticity (TRIP) steels combine excellent ductility and high strength, making them ideally suited for shock absorbing parts in the automotive industry. When designing structures for impact, an understanding of the mechanical properties of materials under high strain rate conditions is essential. An extensive experimental program using a split Hopkinson tensile bar set-up was established in an effort to investigate the dynamic properties of various TRIP steel grades. Four different TRIP steels are described with varying contents of the alloying elements silicon, aluminium and phosphor. Moreover, several phenomenological models describing the strain rate and temperature-dependent mechanical behaviour are validated. TRIP steel grades in which aluminium is the main alloying element show high elongation values, whereas a high silicon content results in an increase in strength. The widely used Johnson-Cook model can describe the behaviour of TRIP steels and provides the opportunity to study its material and structural response.     

Role of the reversible electrochemical deprotonation of phosphate species in anaerobic biocorrosion of steels

Sulphate reducing bacteria are known to play a major role in anaerobic microbiological influenced corrosion of steels, but mechanisms behind their influence are still source of debates as certain phenomena remain unexplained. Some experiments have shown that hydrogen consumption by SRB or hydrogenase increased the corrosion rate of mild steel. This was observed only in the presence of phosphate species. Here the cathodic behaviour of phosphate species on steel was studied to elucidate the role of phosphate in anaerobic corrosion of steel. Results showed: a linear correlation between reduction waves in linear voltammetry and phosphate concentration at a constant pH value; that phosphate ions induced considerable anaerobic corrosion of mild steel, which was sensitive to hydrogen concentration in the solution; and that the corrosion potential of stainless steel in presence of phosphate was shifted to more negative values as molecular hydrogen was added to the atmosphere in the reaction vessel. Phosphate species, and possibly other weak acids present in biofilms, are suggested to play an important role in the anaerobic corrosion of steels via a reversible mechanism of electrochemical deprotonation that may be accelerated by hydrogen removal.     

Corrosion and mechanical properties of plasma electrolytic oxidation‐coated AZ80 magnesium alloy

Plasma electrolytic oxidation (PEO) coatings were produced on AZ80 magnesium alloy in a solution containing silicates and phosphates and working at high current densities with short treatment times. The effect of a sealing treatment in boiling water on corrosion and mechanical properties of the coatings were investigated. Moreover, the corrosion mechanism of the samples with and without the sealing treatment was evaluated. The microstructure of the coatings was characterized with scanning electron microscope observation and X‐ray diffraction analysis. The mechanical properties were evaluated with nanoindentation tests and the corrosion resistance was studied by potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning vibrating electrode technique. The results showed that the sealing did not influence the microstructure and the mechanical properties of the samples and instead produced a remarkable increase in the corrosion resistance. The crevice corrosion, present in the sample without the sealing, was avoided with the treatment in boiling water.     

Measurement of O2-N2 binary sorption on 5A zeolite by isotope tracer and perturbation chromatography

Isotope tracer chromatography allows to extract simply and quickly multi component adsorption data and is demonstrated for single component and binary adsorption equilibria for O₂ and N₂ on 5A zeolite as an example. In this modification of conventional tracer chromatography, a small pulse of an isotope tracer is injected in an adsorbable carrier gas (pure or multicomponent mixture) flowing through a column filled with adsorbent and is designed to operate at almost uniform pressure. Isotherm parameters are readily extracted by fitting measurements of residence times at various pressures and carrier composition. The isotherms were in excellent agreement with volumetric measurements. Isotope tracer chromatography is shown to be superior to perturbation chromatography since the influence of the injection volume on the carrier gas composition is substantially smaller for tracer experiments. Unfortunately, this new improved gas chromatographic technique requires rather expensive isotopes. The strength of this new approach lies in the advantage of working with small adsorbent samples (1 g) making a rapid screening of newly developed materials possible.Nomenclature K _exp,tr,i experimental tracer adsorption constant (mol/kg pure adsorbent/Pa) - K _i Henry adsorption equilibrium constant (mol/kg pure adsorbent/Pa) - K _i,part partition coefficient - K _pert composite Henry constant (mol/kg pure adsorbent/Pa) - L column length (m) - L _i Langmuir adsorption constant (1/Pa) - n _i amount adsorbed on the solid (mol/kg adsorbent) - N _i adsorbent loading (Pa) - p total pressure (Pa) - p _i partial pressure of component i (Pa) - p _in column inlet pressure (Pa) - p _out column outlet pressure (Pa) - q _i amount of component i in the micropores (Pa) - R gas constant (J/mol/K) - t time (s) - T temperature (K) - v _f superficial velocity in adsorbent column (m/s) - v _out velocity at the outlet of the column (m/s) - V _inlet volumetric flow rate at inlet conditions (ml/s) - x molar fraction of tracer - y molar fraction of component i in the carrier gas - z axial coordinate (m) Greek letters _ext bed voidage, external porosity - _macr macropore porosity [_macr= _p (1–_ext)] - _micr micropore porosity - _tot total porosity - _p pellet porosity - volume fraction of binder material - _d dead time (s) - _tracer tracer residence time (s) - _pert perturbation residence time (s) - _crys crystal density (kg/m³)     

Removal of formaldehyde from aqueous solutions via oxygen reduction using a reticulated vitreous carbon cathode cell

The removal of formaldehyde from waste streams to <0.3 ppm has been demonstrated using a cell with a reticulated vitreous carbon cathode; the formaldehyde is oxidized by hydrogen peroxide, formed at the cathode by reduction of oxygen. In most electrolytes studied (e.g. NaOH, NaCl and Na₂SO₄), the formaldehyde is oxidised only to formic acid. On the other hand, the addition of a low concentration of an iron salt (i.e. 0.5 mm), catalyses the complete oxidation to carbon dioxide. The removal of formaldehyde can be achieved in media of low ionic strength (< 10 mm) although the use of iron salts necessitates the adjustment of pH to 3 to maintain the catalyst in solution.     

Effect of chemical interaction between surface oxidized carbon black and carboxylated nitrile rubber on dynamic properties

Monsanto rheometric, dynamic mechanical, and solvent swelling studies indicate that functional groups of oxidized carbon black chemically react with carboxylated nitrile rubber (XNBR) when heated at high temperature for prolonged time. The reinforcing ability of the surface oxidized carbon black, measured by failure and hysteresis properties, is higher than the nonoxidized counterpart. © 1995 John Wiley & Sons, Inc.     

基于DSP的单脉冲焊及双脉冲焊全数字控制系统的研究

设计并实现了脉冲焊电流和弧长的全数字控制，取得了良好的控制性能：电流波形的灵活精确控制和弧长的高速稳定调节。采用变参数数字PI调节器，取得了良好的脉冲电流波控效果，同时在孤长调节中不再应用PI或PID控制器，实现了在全范围内对孤长的快速、稳定调节，满足自动焊、无人干涉焊接的需要。实验结果表明，设计的脉冲焊全数字控制系统取得了一致性好的理想电流波形，在焊矩高度等扰动发生时。孤长可以实现快速、稳定地调节。同时将上述设计应用于双脉冲焊焊铝的设计中，实验证明同样获得了好的控制效果和工艺效果。