Techn. Hochsch., Diss., 2005--Aachen.

No description available.

Colloidal suspensions of disk-like particles have been of interest in both colloidal and liquid crystal studies because they exhibit unique liquid crystalline phases different from those of rod-like molecules. Disk-like particles, such as asphaltenes in heavy oil industry, clay particles in agriculture, and red blood cells in biology, are of great interest in a variety of industries and scientific areas. However, to fabricate monodisperse microdisks, uniform in structure or composition with precise control of particle size and shape has not yet succeeded. In this thesis, we show an experimental strategy of using microfluidic technique to fabricate homogeneous α-eicosene microemulsions with chloroform in an aqueous solution of sodium dedecyl sulfate (SDS). The monodisperse chloroform emulsions, generated by the glass-based microfluidic devices, ensure the precise control on microdisk particle size and shape. A systematic investigation was performed to study the relation between the resulted microdisk size and the initial concentration of α-eicosene in chloroform before evaporation. The smectic liquid crystalline phase inside the wax particles controls the coin-like disk shape below the melting temperature of wax’s rotator phase. The kinetics of the disk formation is observed using a polarized light microscope. Dynamic light scattering is used to characterize the Brownian motion of the microdisks, and the rotational diffusion is estimated from the image sequences taken by the charge-coupled device (CCD) camera. Effort has been put into collecting a large quantity of microdisks to investigate the discotic liquid crystalline phases, which can be readily probed by light scattering and microscope. In comparison, X-ray and neutron have to be used for the atomic liquid crystalline phase investigation.

Colloidal suspensions of disk-like particles have been of interest in both colloidal and liquid crystal studies because they exhibit unique liquid crystalline phases different from those of rod-like molecules. Disk-like particles, such as asphaltenes in heavy oil industry, clay particles in agriculture, and red blood cells in biology, are of great interest in a variety of industries and scientific areas. However, to fabricate monodisperse microdisks, uniform in structure or composition with precise control of particle size and shape has not yet succeeded. In this thesis, we show an experimental strategy of using microfluidic technique to fabricate homogeneous α-eicosene microemulsions with chloroform in an aqueous solution of sodium dedecyl sulfate (SDS). The monodisperse chloroform emulsions, generated by the glass-based microfluidic devices, ensure the precise control on microdisk particle size and shape. A systematic investigation was performed to study the relation between the resulted microdisk size and the initial concentration of α-eicosene in chloroform before evaporation. The smectic liquid crystalline phase inside the wax particles controls the coin-like disk shape below the melting temperature of wax’s rotator phase. The kinetics of the disk formation is observed using a polarized light microscope. Dynamic light scattering is used to characterize the Brownian motion of the microdisks, and the rotational diffusion is estimated from the image sequences taken by the charge-coupled device (CCD) camera. Effort has been put into collecting a large quantity of microdisks to investigate the discotic liquid crystalline phases, which can be readily probed by light scattering and microscope. In comparison, X-ray and neutron have to be used for the atomic liquid crystalline phase investigation.

No description available.

No description available.

No description available.

No description available.

Doctor of Philosophy(PhD) / Polymer manufacturing is a major worldwide industry, attracting the attention of numerous industrial units and research institutes. Increasing demands on polymer quality, process safety and cost reduction are the main reasons for growing interest in the design and control of emulsion polymerisation. Emulsion polymerisation process implemented with free radical polymerisation has significant advantages over other processes, such as the production of polymer of higher molecular weights at high conversion rates, easier temperature control due to the low viscosity of the reaction media, high degree of selectivity and more friendly to environment due to the use of an aqueous medium. It allows for the production of particles with specially-tailored properties, including size, composition, morphology, and molecular weights. Introducing two or more different monomers to the polymerisation process (named multi-polymerisation) can lead to the synthesis of an almost unlimited number of new polymers types. Emulsion polymers are products by process, meaning that the manner in which the polymerisation is carried out is perhaps more important than the raw materials in determining the form of the final product. This highlights the significance of the systematic approach in online process control which requires thorough understanding of the process phenomena as a prerequisite for development of a mathematical description of the process as the model. It is thus evident and based on research observations that process control for emulsion terpolymerisation is a particularly difficult task because of the lack of validated models and the lack of online measurements of most of polymer properties of interest. Therefore, a well validated model is crucial for optimising and controlling the emulsion terpolymerisation operations allowing for design of the polymer product properties. In this study, a framework for process design and control of emulsion terpolymerisation reactors was developed. This framework consisted of three consecutive stages, dynamic modelling of the process, optimising the process for finding the optimal operating strategies and final online controlling the obtained optimal trajectories through multivariable constrained model predictive control. Within this framework, a comprehensive dynamic model was developed. Then a test case of emulsion terpolymerisation of styrene, methyl methacrylate and methyl acrylate was investigated on state of the art facilities for predicting, optimising and control end-use product properties including global and individual conversions, terpolymer composition, the average particle diameter and concentration, glass transition temperature, molecular weight distribution, the number- and weight-average molecular weights and particle size distribution. The resulting model was then exploited to understand emulsion terpolymerisation behavior and to undertake model-based optimization to readily develop optimal feeding recipes. The model equations include diffusion-controlled kinetics at high monomer conversions, where transition from a ‘zero-one’ to a ‘pseudo-bulk’ regime occurs. Transport equations are used to describe the system transients for batch and semi-batch processes. The particle evolution is described by population balance equations which comprise of a set of integro-partial differential and nonlinear algebraic equations. Backward finite difference approximation method is used to discretise the population equation and convert them from partial differential equations to ordinary differential equations. The model equations were solved using the advanced simulation environment of the gPROMS package. The dynamic model was then used to determine optimal control policies for emulsion terpolymerisation in a semi-batch reactor using the multiobjective dynamic optimisation method. The approach used allows the implementation of constrained optimisation procedures for systems described by complex mathematical models describing the operation of emulsion terpolymerisation reactors. The control vector parameterisation approach was adopted in this work. Styrene monomer feed rate, MMA monomer feed rate, MA monomer feed rate, surfactant feed rate, initiator feed rate and the temperature of reactor were used as the manipulating variables to produce terpolymers of desired composition, molecular weight distribution (MWD) and particle size distribution (PSD). The particle size polydispersity index (PSPI), molecular weight polydispersity index (MWPI) and the overall terpolymer composition ratios were incorporated as the objective functions to optimise the PSD, MWD and terpolymer composition, respectively. The optimised operational policies were successively validated with experiments via one stirred tank polymerisation reactor. Due to the lack of online measurements of key process product attributes for emulsion terpolymerisation, an inferential calorimetric soft sensor was developed based on temperature measurements. The calorimetric soft sensor obtains online measurements of reactor temperature, jacket inlet and outlet temperatures helped estimate the rate of polymerisation. The model includes the mass and energy balance equations over the reactor and its peripherals. Energy balance equations include the heat of reaction, internal and external heat transfer effects, as well as external heat losses. An online multivariable constrained model predictive control was formulated and implemented for online control of the emulsion terpolymerisation process. To achieve this implementation, a novel generic multilayer control architecture for real-time implementation of optimal control policies for particulate processes was developed. This strategy implements the dynamic model for the emulsion terpolymerisation as a real-time soft sensor which is incorporated within the implemented MPC. The methodology was successively validated using six case studies within the on-line control of terpolymerisation reactors. The cases were online controlled the composition of terpolymers, PSD and Mn with specific constraints for the operation conversion and particle average radius. An advanced Supervisory Control Architecture named ROBAS was used in this work. It provides a completely automated architecture allowing for the real time advanced supervisory monitoring and control of complex systems. The real time control application strategy was developed within MATLAB, Simulink, gPROMS and Excel Microsoft softwares and implemented on line through ROBAS Architecture. The manipulated variables are measured using on-line measurements connected to the DCS system through Honeywell. These measurements were sent to MATLAB and then to the dynamic model in gPROMS through an excel spread-sheet interface. Then the dynamic model used them to estimate the controlled variables of the MPC. The estimated values of the controlled variables obtained from the dynamic model, were then sent to the Simulink and fed through the DCS system to the MPC developed in MATLAB. The MPC would then calculate optimal trajectories, which are then sent as set point signals through the DCS system to the regulatory controller. The MPC formulation was found to be robust and handles disturbances to the process. The result showed that the online multivariable constrained MPC controller was able to control the desired composition and Mn as specified set points with great accuracy. The MPC algorithm succeeded under constrained conditions, in driving the PSD to the desired target. Although some offset was observed with a certain degree of model mismatch, the experimental results agreed well with predictions.

Generating droplets using flow-focusing microfluidics in multiphase flows has reached its limit that it cannot generate submicrometer droplets in size. Flow focusing geometry together with an electric field has been used to make smaller droplets in microchannels. The droplet size was controllable by the flow rate ratio as well as the electric field. The droplets size decreased as the voltage increased. A Taylor cone was formed to generate very fine droplets which were less than 1mμ in diameter. The tip made smaller droplets due to the tangential force by the electric field. A small inner flow rate and high electric field were required to form a stable Taylor cone in a DC electric field. The droplet size, however, was not stable at a small water flow rate because the flow rate was not as accuate as required. When I used a modified syringe pump with more accurate flow rate control, I was able to obtain a stable set of data. A small change in droplet size occurred at low voltage. The drop size changed dramatically, when the voltage was high enough. I also observed how an AC electric field affects the droplet size. The droplet size was not solely determined by the voltage. This is because of the imbalance of the supplied flow rate and the emitted flow rate. I also found that the droplet size is related to the tip position of the dispersed phase. The droplet size decreased as the tip stretched more. Typically, the microfluidic device generated monodispese droplets in narrow size distribution. It also generated a bigger droplet followed by a smaller one consecutively at low flow rate ratio of inner and outer fluid flow ()265.0/09.0≤≤oiQQ. To understand this instability of drop formation, a numerical calculation was conducted. The simulation results showed inside of the tip still pointed downstream after it generated a big droplet. Then, the tip generated another smaller droplet while the tip was stretched. Finally, the tip moved back and began a new cycle.