Polystyrene Suspension Polymerization: The Effect of Polymerization Parameters on Particle Size and Distribution

Effects of polymerization parameters are studied to better understand interactions between parameters in stirred-tank polymerization reactors and to derive a regression model correlating polymer particle size and particle-size distribution with agitator speed, agitator diameter, tricalcium phosphate, dodecyl benzene sodium sulfonate concentrations, and mass cycle period. The derived equations give way to prediction of the polymerization conditions in order to obtain desired particle size and particle-size distributions which covers particle sizes between 0.3 and 5 mm. The roles of some other parameters and limiting agitation parameters are also investigated.     

Increasing single-lap joint strength by adherend curvature-induced residual stresses

Single-lap joint (SLJ) geometry is the most widely used type of adhesive joint geometry. In this joint, peel stresses occur at the overlap ends due to load eccentricity and the presence of shear-free adhesive termination surfaces. These peel stresses, along with the transverse tensile stresses which occur along the overlap longitudinal axes, and adhesive shear stresses, ultimately cause joint failure. Obviously, reductions in these stresses should result in higher joint strength and increased load capacity. To this end, we exploited elastic spring-back capability of (steel) metal adherends by initially forming curved segments of varying arc lengths and radii at overlap ends. These adherends with curved-end sections were then bonded in single-lap configuration, simply by applying sufficient bonding pressure to elastically flatten the curved segments to result in typically flat overlap sections subsequent to adhesive cure and the removal of bonding pressure. Since the elastic adherend overlap ends tend to revert back to their initial curved form, they exert compressive residual stresses on the adhesive layer in the overlap end regions. We determined that the compressive residual stresses induced in this fashion considerably increased the load capacity of SLJs subjected to tension.     

Steady‐State and Dynamic Reactor Models for Hydrotreatment of Oil Fractions: A Review

The modeling of catalytic hydrotreatment reactors for petroleum fractions have been classified in several ways, for example steady‐state and dynamic, pseudohomogeneous, and heterogeneous, and so on. Depending on the system to be modeled, operating conditions and type of feedstock, these approaches could exhibit some advantages and disadvantages, wide scopes and limitations. In this review, the discussion about those modeling aspects, already published, is used to develop a generalized reactor model, which can be simplified in order to derive each single model previously reported. Some guides to estimate model parameters are also given.     

Multi-methacrylated star-shaped,photocurable poly(methyl methacrylate) macromonomers via quasiliving ATRP with suppressed curing shrinkage

Novel, star-shaped multifunctional poly(methyl methacrylate) (PMMA) macromonomers with well-defined average number of pendant methacrylate groups were synthesized by copolymerizing MMA with 2-hydroxyethyl methacrylate (HEMA) via quasiliving ATRP with a tetrafunctional initiator in methanol at 10 °C, followed by methacrylation of the hydroxyl groups of the HEMA units. The resulting tailor-made poly(methyl methacrylate-co-2-methacryloylethyl methacrylate), P(MMA-co-MEMA), multifunctional macromonomers were used as cross-linking agents in photocuring of MMA, a solvent for its own polymer, and thus chemically homogeneous PMMA networks were formed in which the tetrafunctional initiator moiety provides inherent, additional branching points in the resulting cross-linked materials. This approach, even in the presence of relatively low amounts of macromonomers of ∼35–45%, provides sol-free products and up to ∼40% less polymerization shrinkage than that by curing of MMA with a conventional low molecular weight bifunctional methacrylate. These new, unique star-shaped PMMA macromonomers are potential cross-linkers in a variety of solvent-free applications where low curing shrinkage and high conversions are critical requirements, such as in several engineering materials, coatings, dental fillings and restorations, bone cements etc.     

A methodology for simultaneous process and product design in the formulated consumer products industry: The case study of the detergent business

In this work we present a mathematical optimization based methodology for simultaneous formulae and process design in the consumer product business applied to the case of the laundry detergent. The design of a new detergent is formulated as a modified pooling problem including process, performance, processability and environmental constraints. This new features add a number of nonlinearities related to the modeling of the different aspects of the process and customer acceptance. The problem becomes a multiobjective optimization problem that is solved using the ?-constraint method with global optimization techniques to minimize of the environmental impact while minimizing the production cost for a couple of case studies. As future work, further process, product and legal constraints can be added to make the problem more realistic.     

Mathematical programming and game theory optimization-based tool for supply chain planning in cooperative/competitive environments

This work proposes to improve the tactical decision-making of a supply chain (SC) under an uncertain competition scenario through the use of different optimization criteria, which allows to manage not only the specific objectives of the SC of interest, but also the way how its clients address their selection between different potential suppliers, identifying best market share for the SC of interest and the strategy to attain it. The resulting multi-objective optimization problem has been solved using the ?-constraint method in order to approximate the Pareto space of non-dominated solutions while a framework based on game theory is used as a reactive decision making support tool to deal with the uncertainty of the competitive scenario. The use of the proposed system is illustrated through its application to a multi-product, multi-echelon supply chain case study, which is intended to cooperate or to compete with another SC of similar characteristics.     

Fabrication and characterization of Mn-doped CuO thin films by the SILAR method

Thin films of un-doped and Mn-doped CuO nanostructures have been deposited on glass substrates via the SILAR method. The morphological, compositional, structural and optical properties of the films have been investigated by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction analysis and UV–vis spectrophotometry. The analyzed results indicate that the obtained films consist of plate-like nanostructures. From the EDS analysis it is seen that Mn-doping concentration affects the shapes of the nanostructures. XRD results show that all of the films have monoclinic structure. From the room temperature UV–vis analysis it is found that the optical band gap of the films increases with increasing Mn-doping concentrations.     

Plasma polymerization‐modified bacterial polyhydroxybutyrate nanofibrillar scaffolds

The design and the development of novel scaffold materials for tissue engineering have attracted much interest in recent years. Especially, the prepared nanofibrillar scaffold materials from biocompatible and biodegradable polymers by electrospinning are promising materials to be used in biomedical applications. In this study, we propose to produce low‐cost and cell‐friendly bacterial electrospun PHB polymeric scaffolds by using Alcaligenes eutrophus DSM 545 strain to PHB production. The produced PHB was characterized by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Nanofibrous scaffolds were fabricated via electrospinning method that has a fiber diameter approximately 700–800 nm. To investigate cell attachment, cell growth, and antioxidant enzyme activity on positively and negatively charged PHB scaffold, PHB surface was modified by plasma polymerization technique using polyethylene glycol (PEG) and ethylenediamine (EDA). According to the results of superoxide dismutase (SOD) activity study, PEG‐modified nanofibrillar scaffolds indicated more cellular resistance against oxidative stress compared to the EDA modification. As can be seen in cell proliferation results, EDA modification enhanced the cell proliferation more than PEG modification, while PEG modification is better as compared with nonmodified scaffolds. In general, through plasma polymerization technique, surface modified nanofibrillar structures are effective substrates for cell attachment and outgrowth. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optimal design and operation of a steel plant integrated with a polygeneration system

A process integration approach has been applied to integrate a traditional steelmaking plant with a polygeneration system to increase energy efficiency and suppress carbon dioxide emissions from the system. Using short‐cut models and empirical equations for different units and available technologies for gas separation, methane gasification, and methanol synthesis, a mixed integer nonlinear model is applied to find the optimal design of the polygeneration plant and operational conditions of the system. Due to the complexity of the blast furnace (BF) operation, a surrogate model technique is chosen based on an existing BF model. The results show that from an economic perspective, the pressure swing adsorption process with gas‐phase methanol unit is preferred. The results demonstrate that integration of conventional steelmaking with a polygeneration system could decrease the specific emissions by more than 20 percent. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3659–3670, 2013     

Global optimization of large‐scale mixed‐integer linear fractional programming problems: A reformulation‐linearization method and process scheduling applications

Mixed‐integer linear fractional program (MILFP) is a class of mixed‐integer nonlinear programs (MINLP) where the objective function is the ratio of two linear functions and all constraints are linear. Global optimization of large‐scale MILFPs can be computationally intractable due to the presence of discrete variables and the pseudoconvex/pseudoconcave objective function. We propose a novel and efficient reformulation–linearization method, which integrates Charnes–Cooper transformation and Glover's linearization scheme, to transform general MILFPs into their equivalent mixed‐integer linear programs (MILP), allowing MILFPs to be globally optimized effectively with MILP methods. Extensive computational studies are performed to demonstrate the efficiency of this method. To illustrate its applications, we consider two batch scheduling problems, which are modeled as MILFPs based on the continuous‐time formulations. Computational results show that the proposed approach requires significantly shorter CPU times than various general‐purpose MINLP methods and shows similar performance than the tailored parametric algorithm for solving large‐scale MILFP problems. Specifically, it performs with respect to the CPU time roughly a half of the parametric algorithm for the scheduling applications. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4255–4272, 2013