Influence of HMTA ligand in MMA AGET ATRP emulsion polymerization

Interactions of hexamethylenetetramine ligand in atom transfer radical polymerization initiated by activator generated by electron transfer were studied. Polymerization of methyl methacrylate was done using two-step experimental procedure in 2 L emulsion batch reactor at 50, 60, and 80°C. The selection of reactant ratios was quite challenging for a reactor of this size. Replicate runs were conducted for data reproducibility purpose. Gravimetry method and gel permeation chromatography were used to determine monomer conversion, Mn, and PDI of polymer samples. PMMA produced was also characterized by means of dynamic light scattering, Fourier-transform infrared spectroscopy and nuclear Magnetic Resonance spectroscopy. Results showed high monomer conversion up to 93% and Mn ranging 243–274 kg/mol with PDI from 1.45 to 1.60. Besides, combining HMTA with sodium dodecyl sulfate, an anionic surfactant, a well-controlled polymer with a lower Mn of 201 kg/mol and PDI of 1.56 was obtained in 3 hr reaction time.     

Modeling and simulation of the drying of thin sheets in a continuous infrared dryer

The model gives the temperature and moisture distributions of the air, and of the moist sheet, as a function of time and distance in the dryer. The influence of the sheet's velocity and that of the radiant energy on the dryer performance as well as the effect of the moisture content of the entering sheet have been studied. A set of 27 experiments was carried out using the infrared dryer in order to calibrate the model. In these, the following three variables each had three operational levels: web velocity, initial web moisture and heating power. The model predictions agreed very well with the experimental data. Model predictions using arithmetic averages for the parameters, and parameters correlated with operational variables, are also presented and discussed.     

Unscented Kalman filter based nonlinear model predictive control of a LDPE autoclave reactor

This paper presents a multivariable nonlinear model predictive control (NMPC) scheme for the regulation of a low-density polyethylene (LDPE) autoclave reactor. A detailed mechanistic process model developed previously was used to describe the dynamics of the LDPE reactor and the properties of the polymer product. Closed-loop simulations are used to demonstrate the disturbance rejection and tracking performance of the NMPC algorithm for control of reactor temperature and weight-averaged molecular weight (WAMW). In addition, the effect of parametric uncertainty in the kinetic rate constants of the LDPE reactor model on closed-loop performance is discussed. The unscented Kalman filtering (UKF) algorithm is employed to estimate plant states and disturbances. All control simulations were performed under conditions of noisy process measurements and structural plant–model mismatch. Where appropriate, the performance of the NMPC algorithm is contrasted with that of linear model predictive control (LMPC). It is shown that for this application the closed-loop performance of the UKF based NMPC scheme is very good and is superior to that of the linear predictive controller.     

Derivation of a control oriented low order model of the dynamics of an infrared oven for the continuous drying of a thin sheet of material

A model consisting of three partial non-linear differential equations for describing the humidity and temperature of a thin sheet of material and of the temperature of the air flow as a function of time and position in an infrared dryer was reduced to a model more adaptable to direct digital control. To begin with the original model was discretized along the length of the dryer and then linearized. Models of orders ranging from 12 to 72 were analyzed for controllability and observability. Using Moore's method, the models thus obtained were further reduced to a controllable state space model of order 5 that produced satisfactory results and for which stability was preserved. Simulated open loop responses of the reduced model to discrete perturbations in emitter electrical power, inlet humidity and velocity of the web, produced satisfactory dynamic and steady-state responses when compared to responses of the original model subjected to similar perturbations. The steady-state responses showed absolute errors for humidity and temperature of the web less than 1.3% [g water/100 g] and 2.2°C, respectively.     

Model-based multivariable control of the drying of a thin sheet of fibres in a continuous infrared dryer

We developed an Internal Model Control (IMC) algorithm for drying a thin textile fabric, continuously passing through an electric infrared dryer, based on a reduced linear model of the drying dynamics. This model relates the controlled variables, the humidity and temperature of the web at the dryer outlet, to the manipulated variables, the electrical power supplied to the sources and the web speed through the dryer, and also to changes in the initial humidity of the web at the dryer inlet. The control algorithm was first tested by simulation using the model in regulation mode, and in set-point tracking mode, to vary the manipulated variables so as to maintain the controlled variables at their respective set-points when the inlet web temperature and humidity were changed. The performance under simulated operational conditions was compared to that of a conventional feedback proportional-integral (PI) controller coupled with a feedforward control. The IMC controller was then tested directly in regulation mode using a pilot scale infrared dryer, acting simultaneously on the manipulated variables, the emitter power and the web speed, to control the fabric temperature and humidity at the dryer outlet. The experimental results were compared with those from the above feedback-feedforward controller, on the pilot scale dryer. The results have indicated that the closed-loop stability of the process is assured simply by choosing a stable IMC controller. Also, such a controller does not require the design of specific compensators for the strong interactions between variables of the drying process.     

Optimal Control of Continuous Infrared Dryers

In this work, the optimal control policies of radiant temperature versus dryer length are determined for the continuous, steady-state operation of infrared dryers. The optimal control objective is to minimize the product humidity subject to a mathematical model of infrared dryers as well as a set of process inequality constraints. A robust optimal control method based on genetic algorithms is applied. Multiple air injections are also considered. The optimal results show considerable reduction in product humidity. Comparisons with corresponding base cases (using maximum possible uniform radiant temperatures) indicate improvements greater than 50% with the application of optimal control policies.     

Experimental Study of a Tetrafunctional Peroxide Initiator: Bulk Free Radical Polymerization of Butyl Acrylate and Vinyl Acetate

Summary This investigation examines the use of a tetrafunctional peroxide initiator in the bulk free radical homopolymerization of butyl acrylate and vinyl acetate. Rate of polymerization, molecular weights and in certain cases, gel fraction data were collected for selective experiments and compared to the results obtained with a monofunctional counterpart. In order to avoid the formation of insoluble gel material, further experiments were completed with varying concentrations of a chain transfer agent. Experimental results showed that when used at identical concentrations, the tetrafunctional initiator produced a faster rate in the polymerization of both butyl acrylate and vinyl acetate compared to the monofunctional initiator. Without the use of a chain transfer agent, runs with butyl acrylate produced significant amounts of gel material isolated by Soxhlet extraction. For a particular reaction time, the tetrafunctional initiator produced higher levels of gel compared to its monofunctional counterpart. When a chain transfer agent was used, the molecular weights were determined by its concentration and in turn, initiator functionality did not have an impact. In the polymerization of vinyl acetate, similar observations were made and no discernable difference could be seen between the molecular weight results of samples produced with either initiator.     

Infrared Drying: From Process Modeling to Advanced Process Control

The article surveys the drying of solids materials and polymer solutions when infrared radiation (IR) is employed as the main heating source. The study reviews the current research trends of IR drying of specific applications. A case study similar to an industrial setting is presented to illustrate a model development and control scheme of an IR drying unit. The design and online implementation of an internal model controller (IMC) is discussed. The study demonstrates the controller capabilities to suppress random variations of the moisture content in the material entering the dryer. Simulation results also showed the success of model predictive control (MPC) multivariable controller ability, while handling process interactions and process constraints, to track setpoint changes in the humidity and temperature of the material exiting the dryer and to reject unmeasured stochastic disturbances in the inlet humidity stream.     

Mass diffusivity of different species of wood in convective drying

This study is devoted to the determination of the diffusion coefficient in convective drying of four local wood species: Aleppo pine, Stone pine, Zeen oak and date palm. A numerical method based on a diffusive model is used which consists of three complementary steps: experimentation, analysis of experimental data and minimization of the gap between experimental drying kinetics data and calculated ones. The coefficient of water for the four wood species is considered depending on both temperature and moisture content, and is obtained by the numerical solution of the conservation equation of the solid phase and the water transfer equation coupled to the shrinkage rate of the solid phase. The found values of diffusion coefficient are consistent with the range of variation in the literature. The mass diffusion coefficient varies with increase in temperature between 1.510^?11 and 4.10^?11 (m²/s) for the Aleppo pine, Stone pine and Zeen oak woods, however for the “palm wood”, it varies from 10 to 11 to 6.10^?11 (m²/s). Arrhenius type relationship allows determining the activation energy, which varies between 135.64 and 150.49 (kJ/mol) for all species of wood treated, and these values are comparable with those of other species cited in literature.