Heat exchanger network synthesis with detailed exchanger designs: Part 1. A discretized differential algebraic equation model for shell and tube heat exchanger design

A new method for the detailed design of shell and tube heat exchangers is presented through the formulation of coupled differential heat equations, along with algebraic equations for design variables. Heat exchanger design components (tube passes, baffles, and shells) are used to discretize the differential equations and are solved simultaneously with the algebraic design equations. The coupled differential algebraic equation (DAE) system is suitable for numerical optimization as it replaces the nonsmooth log mean temperature difference (LMTD) term. Discrete decisions regarding the number of shells, fluid allocation, tube sizes, and number of baffles are determined by solving an LMTD-based method iteratively. The resulting heat exchanger topology is then used to discretize the detailed DAE model, which is solved as a nonlinear programming model to obtain the detailed exchanger design by minimizing an economic objective function through varying the tube length. The DAE model also provides the stream temperature profiles inside the exchanger simultaneously with the detailed design. It is observed that the DAE model results are almost equal to the LMTD-based design model for one-shell heat exchangers with constant stream properties but shows significant differences when streams properties are allowed to vary with temperature or the number of shells are increased. The accuracy of the solutions and the required computational costs show that the model is well suited for solving heat exchanger network synthesis problems combined with detailed exchanger designs, which is demonstrated in Part 2 of the paper.     

Hydrothermal microwave-assisted synthesis of LaFeO3 catalyst for N2O decomposition

Lanthanum orthoferrite powders were synthesized via one-step hydrothermal reactions under mild conditions using microwave and conventional heating. The use of microwave irradiation during the synthesis allows one to obtain nanocrystalline LaFeO₃ with a higher yield and reduced crystallite and particle size within a 16 times shorter duration (3 hours) at a lower temperature of 220°C as compared to the conventional heating. The catalytic decomposition of nitrous oxide was performed over both samples, it was shown that the sample obtained under microwave conditions demonstrates enhanced activity as a catalyst: N₂O decomposes completely at 700°C over the catalyst formed at microwave conditions, while the comparative catalyst prepared by conventional heating reaches a lower conversion of only 60% at the same temperature and catalytic reaction conditions.     

Tailorable thermal expansion in leucite-pollucite materials derived from geopolymers for environmental barrier coatings

The K[AlSi₂O₆]-Cs[AlSi₂O₆] pseudo-binary system was synthesized by geopolymer crystallization. The thermal expansion properties of these materials were studied by in situ high-temperature X-ray diffraction to characterize thermal expansion behavior for potential application as environmental barrier coatings. Tailorable thermal expansion through changing cation stoichiometry allowed reduced thermal expansion mismatch with SiC_f/SiC composites compared to rare-earth-based coatings.     

Synthesis method comparison of compositionally complex rare earth-based Ruddlesden–Popper n = 1 T′-type cuprates

The multicomponent approach has been successfully expanded to the Ruddlesden–Popper structure with the synthesis of two different high-entropy cuprate compositions: (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ and (La_0.2Pr_0.2Nd_0.2Sm_0.2Eu_0.2)₂CuO₄. The effect of synthesis method is explored using both solid-state reaction and polymeric steric entrapment (PSE) methods. It is found that PSE leads to more randomly distributed cation species, providing an advantageous method of synthesis for the growing field of high entropy oxides. In situ high-temperature x-ray diffraction tracks the amorphous to crystalline phase transformation in (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ powder, synthesized using the PSE method. Using the High-Temperature XRD data, a method for gaining information on the kinetic behavior is also applied. Magnetometry of both compositions indicates ferrimagnetic behavior at low temperatures.     

Fine TiC dispersed Al2O3 composites fabricated via in situ reaction synthesis and conventional process

To further improve the mechanical performance and reduce the percolation threshold by controlling microstructures, Al₂O₃-TiC composites containing 0-20 vol% TiC were fabricated via in situ reaction synthesis. Graphite (ATC) and carbon nanotubes (ATCT) were used as carbon sources. The composites were also fabricated via a conventional process using a TiC starting powder (AT). X-ray diffraction analysis and scanning electron microscopy observation results indicated successful fabrication of the composites with various microstructures. TiC particles in ATCT were completely dispersed at grain boundaries, whereas in ATC and AT, these particles were either intragranular or intergranular dispersed. The composites could be listed as follows, ATCT > ATC > AT, that is, in descending order of the reinforcing flexural strength and fracture toughness. The nanoindentation measurement indicated the optimum hardening effect of ATCT. The ATCT composite also exhibited the highest fracture toughness, which was 49% higher than that of the monolithic Al₂O₃. Crack deflection was considered as the main toughening mechanism while crack bridging behavior also occurred in ATCT. For a given TiC content, ATCT exhibited the lowest electrical resistivity, owing mainly to the complete grain-boundary dispersion of the relatively large TiC particles. The similarity of the Al₂O₃ grain size and TiC particle size of ATCT contributed to the lowest percolation threshold achieved (11.2%), which (to date) is the lowest value that has been reported for the Al₂O₃-TiC system.     

One pot synthesis of nano Ag in calcium alginate beads and its catalytic application in p‐Nitrophenol reduction with kinetic parameter estimation and model fitting

In this work, one step process of synthesis of silver nanoparticles (Agnp) embedded in insitu formed calcium alginate (CA) beads is stated. CA, formed from the reaction between sodium alginate and calcium hydroxide, acts as reducing and stabilizing agent as well as support for nanoparticles. The reaction mechanism for the formation and stabilization of Agnp is proposed where the vicinal dihydroxy groups of alginate are assumed to act as the reducing agent for Ag⁺ to Ag°. Transmission electron microscopy (TEM), x‐ray diffraction (XRD), UV‐vis spectroscopy, field emission scanning electron microscopy (FESEM), and atomic absorption spectroscopy (AAS) were used to characterize the Agnp. The formation of spherical nanoparticles with average size range of 4‐5 nm was confirmed by TEM. Catalytic activity of this nano silver‐calcium alginate (Agnp‐CA) composite was evaluated in the reduction of p‐nitrophenol. Concentrations of sodium alginate, calcium hydroxide, and AgNO₃ are found to be the parameters that critically affect the synthesis of Agnp. The efficacy of the catalyst is expressed on the basis of suitable reaction parameters. Both pseudo‐homogeneous and heterogeneous kinetic models are proposed for the reaction to find the best model and the Eley‐Riedel model is found to fit well with the experimental data. The novelty of this work is that the tandem process of CA bead formation, Agnp formation, and Agnp entrapment in CA have been transformed into a single‐step process. Moreover, elaborations of each step of the ionic mechanisms of Agnp formation and p‐NP reduction with Agnp and the establishment of a heterogeneous kinetic model for the reaction are reported for the first time here.     

Tailoring new bisphenol a ethoxylated shape memory polyurethanes

Shape memory polyurethanes (SMPUs) have generated great attention because of their unique properties. These properties are result of a particular molecular structure consisting of flexible molecular chains with low glass transition temperatures alternating with hard urethane segments. In this field, bisphenol A (BA) has been used for a long time as chain extender due to the good properties of the obtained SPMU materials. Nevertheless, the high toxicity of this compound has caused a high decrease on its use. For this reason, it has been selected a lower toxicity compound, bisphenol A ethoxylate (BAE). In this work, it is described a new SMPUs based on BAE and the influence of the hard segment on the thermo-mechanical properties and shape memory capacity. For that, both the proportion of the components and the diisocyanate employed (2,4-toluene diisocyanate (TDI), 4,4′-methylene bis(phenylisocyanate) (MDI) or a TDI/MDI mixture) have been modified. Then, depending on the molecular architecture achieved, the polyurethanes present different properties, which were studied by different techniques, such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic-mechanical thermal analysis (DMTA). It has been observed that glass transition temperature (T_g) increases as the hard phase content in the PU samples increases. In addition, T_g-MDI > T_g-MDI-TDI > T_g-TDI, so it is possible to control the T_g of the material, that is, shape memory transition temperature varying the diisocyanate. Finally, the shape memory capacity of the PUs was evaluated by thermo-mechanical analysis (TMA). All the synthesized PUs have shown good shape memory effect with fixation ratios up to 80% and recovery ratios close to 100%.     

Gelatin supports with immobilized laccase as sustainable biocatalysts for water treatment

Millimeter-size beads of gelatin are manufactured by dripping process to give enzyme supports qualified for micropollutants biodegradation in alternative wastewater treatment. The bead diameter is dependent on the tip diameter, the gelatin solution viscosity and the swelling of polymer chains in the collecting bath. Chemical crosslinking was performed with glutaraldehyde using optimal concentration to give mechanical and thermal properties suitable for application in stirred reactor in aqueous medium. Laccases from Trametes versicolor are grafted on the gelatin beads with glutaraldehyde. Sixty percentage of the initial enzymatic activity, evaluated by the oxidation of 2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) is maintained after 10 successive cycles of reaction. Thermal stability at 60°C of immobilized biocatalysts is improved when compared to free enzymes (45% vs 10% of relative activity after 6 h of incubation). The simplicity of the procedure to form gelatin beads and their properties make them promising bio-based and biodegradable support for enzyme immobilization.     

Spray-coated PDMS/PVDF composite membrane for enhanced butanol recovery by pervaporation

In this study, spray-coating was used to prepare dihydroxypolydimethylsiloxane (PDMS) composite membranes with high flux and separation factor for biobutanol recovery from aqueous solution. A thin, smooth, and defect-free PDMS layer was prepared by spray-coating on polyvinylidene difluoride ultrafiltration membrane with little PDMS penetration. The effects of process parameters for membrane fabrication and pervaporation on membrane performance were investigated. A membrane with 2 μm active layer was obtained with a high flux of 1306.9 g/m² h. The optimal membrane with the highest pervaporation separation index (PSI) (19.15 kg/m² h) showed a total flux of 530.6 g/m² h and a separation factor of 36.1 at 37°C, and a PSI of 65.61 kg/m² h and a flux of 1927.0 g/m² h at 70°C. Membrane performance was affected by feed composition and temperature. Acetone-butanol-ethanol solution and fermentation broth gave lower butanol fluxes and separation factors compared to butanol model solution.     

Covalent surface functionalization of nonwoven fabrics with controlled hydrophobicity,water absorption,and pH regulation properties

A modular method for functionalization of nonwoven fabrics was developed using a two-step process. In the first step, the fabrics were grafted with a linker molecule, 10-undecenoyl chloride, via esterification, followed by attachment of a functional material under UV irradiation. Perfluorodecanethiol and 3-mercaptopropionic acid (MPA) were connected to the linker-modified fabrics using thiol-ene click chemistry. Perfluorodecanethiol modified fabrics exhibited hydrophobicity with water contact angle of about 140° while MPA-modified fabrics were able to lower the pH of a solution by about 1.6. We additionally demonstrated the possibility to connect functional polymers to the linker-modified fabrics by radical graft polymerization of acrylic acid; this produced a thin layer of the polymer on the surface of the fabric. Fabrics modified with poly(acrylic acid) exhibited increased hydrophilicity with water contact angle of 0° for both cotton and viscose-polyester fabrics, while the water absorption capability for polypropylene fabrics increased from about 50 to 1200%.