Reliability of complex chemical engineering processes

This paper presents a stochastic performance modelling approach that can be used to optimise design and operational reliability of complex chemical engineering processes. The framework can be applied to processes comprising multiple units, including the cases where closed form process performance functions are unavailable or difficult to derive from first principles, which is often the case in practice. An interface that facilitates automated two-way communication between Matlab^® and process simulation environment is used to generate large process responses. The resulting constrained optimisation problem is solved using both Monte Carlo Simulation (MCS) and First Order Reliability Method (FORM); providing a wide range of stochastic process performance measures. Adding such capabilities to traditional deterministic process simulators provides a more informed basis for selecting optimum design factors; giving a simple way of enhancing overall process reliability and cost-efficiency. Two case study systems are considered to highlight the applicability and benefits of the approach.     

Design of functionalized α-Fe2O3 (III) films with long-term anti-wetting properties

The design of functional anti-wetting ceramic coatings is always a bottleneck restricting the development of ceramic techniques. This study proposes a liquid phase synthesis method to fabricate α-Fe₂O₃ (III) ceramic powders with promising applications and introduces a facile electrophoretic deposition (EPD) technique to construct the corresponding functionalized hydrophobic films – superhydrophobic functionalized α-Fe₂O₃ ceramic films (SFOFS) with roughly even distribution and a high water contact angle (CA) of 169°±1° – followed by heat posttreatments. The microtopography and crystalline structures of the product were investigated by FESEM, EDX, and XRD techniques. The EPD controllability of SFOFS was studied by adjusting the EPD time and the applied field strengths. In addition, the SFOFS show excellent long-term anti-wetting properties for twenty-four months after undergoing a series of tests, including soaking, water droplet impacting, immersion by droplets with different surface tensions and exposure to different gases and relative humidity conditions, etc. This study substantially helps the design of other kinds of functional anti-wetting films through the proposed convenient method beyond the oxide limit.     

Impact behavior and fractographic study of carbon nanotubes grafted carbon fiber-reinforced epoxy matrix multi-scale hybrid composites

Carbon nanotubes are the most promising reinforcement for high performance composites. Multiwall carbon nanotubes were directly grown onto the carbon fiber surface by catalytic thermal chemical vapor deposition technique. Multi-scale hybrid composites were fabricated using the carbon nanotubes grown fibers with epoxy matrix. Morphology of the grown carbon nanotubes was investigated using field emission scanning electron microscopy and transmission electron microscopy. The fabricated composites were subjected to impact tests which showed 48.7% and 42.2% higher energy absorption in Charpy and Izod impact tests respectively. Fractographic analysis of the impact tested specimens revealed the presence of carbon nanotubes both at the fiber surface and within the matrix which explained the reason for improved energy absorption capability of these composites. Carbon nanotubes presence at various cracks formed during loading provided a direct evidence of micro crack bridging. Thus the enhanced fracture strength of these composites is attributed to stronger fiber–matrix interfacial bonding and simultaneous matrix strengthening due to the grown carbon nanotubes.     

Ionic liquid-based deep eutectic solvents as novel solvent-cum-catalyst media for thermal dehydrogenation of chemical hydrides

The current work explores the usage of novel synthesized Deep Eutectic Solvent (DES) as a catalyst cum solvent media for the thermal dehydrogenation of chemical hydrides, namely Ammonia Borane (AB) and Ethylene diamine bisborane (EDAB). In the first instance, the quantum chemistry based COSMO-SAC (COnductor like Screening MOdel Segment Activity Coefficient) model was used for the selection of the pertinent solvent. 1-Butyl-3-methylimidazolium methanesulfonate: Imidazole ([BMIM][MeSO₃]:[Im]) turned out to be an ideal eutectic mixture with the highest predicted solubility with amine boranes. The DES was synthesized by combining the Hydrogen Bond Acceptor (HBA), namely 1-Butyl-3-methylimidazolium methanesulfonate and Imidazole as Hydrogen Bond Donor (HBD) at a molar ratio of 1:2 and T = 70 °C. The formation of DES was confirmed by recording the NMR spectra. Further, the thermal dehydrogenation study was performed at a vacuum of 4 × 10^?2 mbar (gauge pressure) of AB/DES and EDAB/DES systems at 105 °C, where a hydrogen equivalent of 1.40 and 2.55 was produced, respectively. The residual samples were further analyzed through ¹H NMR analysis for the reaction mechanism and to confirm the role of Ionic Liquid-based DES as catalyst cum solvent media.     

Investigation on phase shifting for a 4 K Stirling pulse tube cryocooler with He-3 as working fluid

He-3 is generally recognized for its ability to provide more excellent thermophysical performance than He-4, especially in the 4 K temperature range. However, this was not always the case in our preliminary experiments on a three-stage Stirling-type pulse tube cryocooler (SPTC). Our ongoing studies, as reported in this paper, demonstrate that the different working fluids also affect the performance through their phase shifting capability. This feature has been passed over in large part by researchers considering refrigerant substitution. Unlike previous theoretical analyses that focus primarily on regenerator losses, this report investigates the effects of the working fluid on the phase angle at the cold end in order to quantitatively reveal the relationship between the lowest attainable temperature and the cooling capacity. The analysis agrees well with our experimental results on a three-stage SPTC. While running with the operating parameters optimized for He-3, the lowest temperature of the SPTC decreased from 5.4 K down to 4.03 K. This is the lowest refrigeration temperature ever achieved with a three-stage SPTC.     

Developing novel liquid crystal technologies for display and photonic applications

Modern liquid crystal displays (LCDs) require novel technologies, such as new alignment methods to eliminate alignment layers, fast response and long operation time. To this end, we report an overview of recent efforts in LCD technologies devoted to realize more display modes having no alignment layer, faster switching time and low battery consumption. In particular, we overview recent advances on the liquid crystals (LCs) alignment for display applications, which includes superfine nanostructures, polymeric microchannels and polymer stabilized LCs. Furthermore, we analyze the main optical and electro-optical properties of new generation LCDs displays addressing a particular attention to LCs blue phase hosting gold nanoparticles. Moreover, we focus on the progress of electrofluidic displays, which demonstrates characteristics that are similar to LCDs, with attention on various pixel designs, operation principles and possible future trends of the technology.     

Viscoelastic Behavior of Synthesized Liquid Soaps and Surface Activity Properties of Surfactants

In the present work, a rheological study of liquid soaps prepared from different mixture of surfactants as a function of surfactant type and concentration was performed. The curves of shear stress vs. shear rate and viscosity vs. shear rate were recorded at constant temperature, 294 ± 0.1 K. The surface activity properties were also studied. The results of the study showed that values of surface tension, γ, were in the range 31–40 mN m⁻¹ and the critical micelle concentration (CMC), was of the order 10⁻⁴ mol L⁻¹. The calculated maximum surface excess, Γ_max, varied from 2.40 to 3.66 μmol m⁻², while minimum area per molecule, A_min, varied from 41.1 (for amphoterics) to 81.4 Ų (for nonionic surfactants). The standard free energy of micellization, −29.8 and −29.3 kJ mol⁻¹ for anionic and amphoteric surfactants, respectively, were while values for nonionic surfactants varied between −31.8 and − 30.3 kJ mol⁻¹. The free energy of adsorption, was the lowest for amphoteric surfactants (−37.9 kJ mol⁻¹), followed by anionics (−40.4 kJ mol⁻¹) and nonionics (−43.34 to −46.84 kJ mol⁻¹), indicating that micellization process is spontaneous in the examined medium. The synthetized liquid soaps show pseudoplastic behavior and they achieved pipe flow. The results of this research indicate that flow behavior was affected significantly by the ionic charge of the surfactant and the ionic strength of the formulation, suggesting that the flow behavior could be changed by manipulating the choice of the surfactant and salinity. The pH value of all liquid soaps examined were weakly acidic, in the range of 5.0–6.4.     

Rate equation theory for the hydrogenation kinetics of Mg-based materials

A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H₂ adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H₂ adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion.     

Chemically modified organic/inorganic nanoporous composite particles for the adsorption of reactive black 5 from aqueous solution

In the present work, we report a chemically modified polyacrylamide/silica nanoporous composite adsorbent for the removal of reactive black 5 (RB5) azo dye from aqueous solutions. The composite adsorbent was synthesized in a packed bed and modified by ethylenediamine (EDA). The adsorbent was characterized by Fourier transformation infrared (FT-IR), thermogravimetric analysis (TGA), thermoporometry, Brunauer, Emmett and Teller (BET) method and scanning electron microscopy (SEM). Mechanical stability of the adsorbent was examined in a packed bed by following the back-pressure of the column. Pore diameter of the composite adsorbent in dry and wet states was estimated to be about 18.71 nm and 12.61 nm, respectively. Adsorption experiments were performed in batch mode and effect of various operational parameters on the adsorption capability of the adsorbent was studied systematically. The maximum adsorption capacity of the modified composites was found to be 454.5 mg RB5/g of adsorbent. The equilibrium data were analyzed by Langmuir, Freundlich, Sips, BET and Redlich–Peterson isotherm models and found to fit well to the BET isotherm. The data kinetically followed the pseudo-second-order model. High adsorption capacity, fast removal mechanism, and good mechanical stability are three advantages of the presented composite for the removal of RB5.     

Review on zirconate-cerate-based electrolytes for proton-conducting solid oxide fuel cell

The performance of low-to-intermediate temperature (400–800?°C) solid oxide fuel cells (SOFCs) depends on the properties of electrolyte used. SOFC performance can be enhanced by replacing electrolyte materials from conventional oxide ion (O^2-) conductors with proton (H⁺) conductors because H⁺ conductors have higher ionic conductivity and theoretical electrical efficiency than O^2- conductors within the target temperature range. Electrolytes based on cerate and/or zirconate have been proposed as potential H⁺ conductors. Cerate-based electrolytes have the highest H⁺ conductivity, but they are chemically and thermally unstable during redox cycles, whereas zirconate-based electrolytes exhibit the opposite properties. Thus, tailoring the properties of cerate and/or zirconate electrolytes by doping with rare-earth metals has become a main concern for many researchers to further improve the ionic conductivity and stability of electrolytes. This article provides an overview on the properties of four types of cerate and/or zirconate electrolytes including cerate-based, zirconate-based, single-doped cerate–zirconate and hybrid-doped cerate–zirconate. The properties of the proton electrolytes such as ionic conductivity, chemical stability and sinterability are also systematically discussed. This review further provides a summary of the performance of SOFCs operated with cerate and/or zirconate proton conductors and the actual potential of these materials as alternative electrolytes for proton-conducting SOFC application.