Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

Experimental investigations and thermodynamic modelling of KCl–LiCl–UCl3 system

Experimental investigations and Gibbs energy modelling of KCl–LiCl–UCl₃ system employing CALPHAD method are reported. Gibbs energy modelling of the subsystems KCl–UCl₃ and LiCl–UCl₃ was carried out primarily using phase diagram data from the literature. For the Gibbs energy modelling of the KCl–LiCl subsystem, new phase boundary data corresponding to four terminal compositions $(x_{\mathrm{LiCl}}=0.03$, 0.05, 0.95 and 0.97) obtained through differential thermal analysis data along with thermochemical and phase diagram data from the literature were used. Thermal analysis was also carried out for KCl–LiCl eutectic mixture containing small amounts of UCl₃ $(x_{{\mathrm{UCl}}_3}=9.03\times {10}^{-3}$ and $1.79\times {10}^{-2}$). The liquidus temperatures for these compositions were found to be 637 K and 674 K. Electromotive force data for dilute solutions of UCl₃ in the KCl–LiCl eutectic melt, measured in the temperature range 708–833 K in the present work, were found to be in good agreement with the literature data. These data were also used as input for the Gibbs energy modelling of the KCl–LiCl–UCl₃ system. In order to improve the quality of the resulting Gibbs energy functions of the quasibinaries and the quasiternary, enthalpies of mixing of the corresponding melts estimated using an empirical correlation based on surrounded-ion model were also used as input. Finally, the generated Gibbs energy functions were used to compute phase equilibria.     

Synthesis of N-methylglucamine modified macroporous poly(GMA-co-TRIM) and its performance as a boron sorbent

A chelating polymeric sorbent was developed by functionalizing poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate), poly(GMA-co-TRIM), with N-methylglucamine (MG) via a simple post-grafting route. The resulting well-defined millimeter-sized spheres of poly(GMA-co-TRIM)–MG had permanent macropore structures and low swelling degree, with accessible ligands of 1.84 mmol/g. The boron adsorption behavior of the sorbent was studied in batch mode by varying different parameters like the pH value, the initial concentration of boron and the adsorption time under noncompetitive conditions. It was found that the sorbent always maintained the high capacity between pH 2.6 and 8.6, in which the optimum pH was 7.5. The adsorption behavior of the sorbent obeyed the Langmuir isotherm well. The adsorption capacity of the sorbent for boron was in the same level as that of a commercially available N-methylglucamine-type polystyrene resin. However, it adsorbed boron more quickly. The sorbent also showed good durability and reusability through the fixed-bed adsorption tests. The study on the separation of boron from brine of salt lake showed a high selectivity of the sorbent, though the capacity for boron decreased due to the interference of diverse ions in brine.     

Dependence of properties of liquid crystalline aromatic copolyesters on monomer sequence-copolyesters derived from terephthalic acid, 2,7-naphthalenediol and p-hydroxybenzoic acid

Summary An aromatic copolyester with the ordered sequence of terephthalic acid (TA)-p-hydroxybenzoic acid (HB)-2,7-naphthalenediol (ND)-p-hydroxybenzoic acid (HB) was prepared and its properties were compared with those of the corresponding random copolyester having the same overall monomer composition. Thermal and crystallizing properties of the two polymers are quite different. The former exhibits significantly higher glass transition and melting temperatures than the latter. The former's degree of crystallinity also is much higher than the latter's. Both polymers are thermotropic and form nematic melts.     

Steady-state target optimization designs for integrating real-time optimization and model predictive control

In industrial practice, the optimal steady-state operation of continuous-time processes is typically addressed by a control hierarchy involving various layers. Therein, the real-time optimization (RTO) layer computes the optimal operating point based on a nonlinear steady-state model of the plant. The optimal point is implemented by means of the model predictive control (MPC) layer, which typically uses a linear dynamical model of the plant. The MPC layer usually includes two stages: a steady-state target optimization (SSTO) followed by the MPC dynamic regulator. In this work, we consider the integration of RTO with MPC in the presence of plant-model mismatch and constraints, by focusing on the design of the SSTO problem. Three different quadratic program (QP) designs are considered: (i) the standard design that finds steady-state targets that are as close as possible to the RTO setpoints; (ii) a novel optimizing control design that tracks the active constraints and the optimal inputs for the remaining degrees of freedom; and (iii) an improved QP approximation design were the SSTO problem approximates the RTO problem. The main advantage of the strategies (ii) and (iii) is in the improved optimality of the stationary operating points reached by the SSTO-MPC control system. The performance of the different SSTO designs is illustrated in simulation for several case studies.     

Industrial TiO2 based nacreous pigments as functional building materials: Photocatalytic removal of NO

In this paper, the photocatalytic activity of industrial titanium dioxide (TiO₂) based nacreous pigments was researched as functional building materials for photocatalytic NO remove. Three industrial TiO₂ based nacreous pigments were selected to estimate the photocatalytic activity for NO remove. This study is a good proof that pearlescent pigments can eliminate NO, and its performance is positively correlated with its titanium dioxide content. And this research will widen the application of nacreous pigments in functional building materials, and provide a new way to eliminate in door nitric oxide pollution.     

An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery

In this overview we discuss how aqueous-phase catalytic processes can be used to convert biomass into hydrogen and alkanes ranging from C₁ to C₁₅. Hydrogen can be produced by aqueous-phase reforming (APR) of biomass-derived oxygenated hydrocarbons at low temperatures (423–538 K) in a single reactor over supported metal catalysts. Alkanes, ranging from C₁ to C₆ can be produced by aqueous-phase dehydration/hydrogenation (APD/H). This APD/H process involves a bi-functional pathway in which sorbitol (hydrogenated glucose) is repeatedly dehydrated by a solid acid (SiO₂–Al₂O₃) or a mineral acid (HCl) catalyst and then hydrogenated on a metal catalyst (Pt or Pd). Liquid alkanes ranging from C₇ to C₁₅ can be produced from carbohydrates by combining the dehydration/hydrogenation process with an upstream aldol condensation step to form C–C bonds. In this case, the dehydration/hydrogenation step takes place over a bi-functional catalyst (4 wt.% Pt/SiO₂–Al₂O₃) containing acid and metal sites in a specially designed four-phase reactor employing an aqueous inlet stream containing the large water-soluble organic reactant, a hexadecane alkane sweep stream, and a H₂ inlet gas stream. The aqueous organic reactant become more hydrophobic during dehydration/hydrogenation, and the hexadecane sweep stream removes these species from the catalyst as valuable products before they go on further to form coke.     

Modification of silk with aminated polyepichlorohydrin to improve dyeability with reactive dyes

Reactive dyes have almost complete exhaustion and ideal fixation on aminated polyepichlorohydrin pretreated silk without addition of salt or alkali. The effects of varying pretreatments and dyeing conditions were studied. The dyeing behaviour of CI Reactive Red 15 on modified silk under pH 6 was investigated. Dyeings of modified silk showed good wash fastness, dry and wet rub fastnesses as well as light fastness. The quality of the dyed silks obtained after pretreatment was shown to be satisfactory and the dyeing effluent was less polluted.     

Critical evaluation of coupling particle size distribution with the shrinking core model

The shrinking core model (SCM) is widely used to model fluid-solid reactions such as the leaching of metals from minerals. In most cases, however, the particle size distribution (PSD) of the solid material was disregarded. In this paper the erroneous shift in the control regime when neglecting PSD was quantified and the dependence of the shift on the coefficients of variation (CV) and the type of PSD was analysed. By coupling the SCM with a Gamma PSD, it was found that neglecting the PSD would shift the control regime from chemical reaction to inert/ash layer diffusion, when the CV was between 0.7 and 1.2. For a system controlled by liquid film diffusion, neglect of the PSD, would shift the control regime to chemical reaction when CV is between 0.3 and 0.7 or to inert/ash layer diffusion when CV is greater (0.9-1.5). It was therefore postulated that some researchers had unknowingly made invalid conclusions about the control regime due to the neglect of PSD. However, an inert/ash layer diffusion-controlled process was insensitive to the neglect of PSD. When CV<0.3, neglect of the PSD would not cause any erroneous shifts, irrespective of the control regime. Experimental data confirmed the observation. For a given CV, the deviation in the fraction reacted from the mono-PSD increases with CV and decreases with time. The maximum deviation, which occurs at the beginning, is about 10% with a gamma PSD of CV=0.3. The percent deviation is dependent of the type of PSDs. Gamma PSD gives the lowest deviation while Gaudin-Schuhmann results in the largest deviation (maxi. ∼19%, with CV=0.3) in the first half of dissolution process. Log-normal distribution gives a larger deviation than gamma but quickly approaches the latter with time. The deviation for Rosin-Rammler is between log-normal and Gaudin-Schuhmann. For systems with CV less than 0.3, the SCM can be fairly used without considering PSD. When CV is greater than 0.3, particularly in the early stage of a dissolution process with a PSD other than gamma, PSD should be included to avoid substantial errors.     

Electrochemical micromachining of nitinol by confined-etchant-layer technique

The confined etchant layer technique has been applied to fabricate complex three-dimensional microstructures on nitinol for the first time. HF and HNO₃ were locally and simultaneously electrogenerated at the mold surface to etch a nitinol workpiece. NaOH was used as an efficient scavenger to confine the etchant close to the mold. Cyclic voltammetry was employed to study the electrochemical behavior of a Pt electrode in the etching solution in order to choose an appropriate potential for etchant generation on the mold. The thickness of the confined etchant layer was estimated to be several micrometers by inspecting the deviation of the sizes of the etched spots from the sizes of those on the microelectrode. Thus, the composition of the electrolyte could be optimized for better etching precision. By optimizing the composition of the electrolyte, complex microstructures on a Pt-Ir mold bearing the logo “XMU” of Xiamen University were successfully fabricated on nitinol. The etched patterns were approximately negative copies of the mold, and the precision of duplication could easily reach the micrometer scale.