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Dissertation
A novel cation exchange membrane for the selective separation of lithium

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In recent years, increasingly efficient processes for lithium extraction from salt lake brines, mineral leachates and spent Li-ion battery leachates are needed due to high demand for Li-ion batteries for electric vehicles and handheld electronics. Electrodialysis (ED) provides a clean and efficient way of separating dissolved ions. The key elements of an ED installation are ion exchange membranes. However ion exchange membranes with high selectivity, scaling resistance and excellent physical properties are needed for new applications of ED in lithium production processes from primary and secondary resources. In this work, a novel cation exchange membrane was designed by interpenetrating networks of Kevlar aramid nanofibers (KANFs) and Poly(4-styrene sulfonic acid-co-maleic acid) (PSSMA). Kevlar membranes are known for their excellent mechanical and thermal properties, organic solvent resistance and tunable structure. 4-Amino-2,2,6,6-tetramethylpiperidine-1-oxyl (ATTO) was added onto the KANFs by amide condensation reaction to increase selectivity and anti-scaling properties. This resulted in membranes with a similar selectivity towards Li+ compared to current commercial monovalent selective membranes. The desalination efficiency was on par with commercial membranes (up to 99.9%), while the concentration efficiency was not as high due to low membrane thickness and high water permeation. There also was a significant increase in anti-scaling properties compared to commercial membranes. Moreover, the novel KANF membranes displayed excellent ion exchange capacity, water content, swelling rate, surface electrical resistance and mechanical and thermal properties. From electron microscopy images, the membranes exhibited a very low membrane thickness (5.2 μm to 8.0 μm) and a homogeneous structure. ATTO was shown to contribute to the hydrophobic properties, anti-scaling effects and physical strength of the membrane. Interpenetrating networks of PSSMA contributed to a high ion exchange capacity, low surface electrical resistance and increased mechanical properties (up to a certain concentration). The results of this research will be published in the Journal of Membrane Science by Yan Zhao et al.

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Dissertation
Sideways self-propulsion of microrods

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Over the past couple of years the topic of micro-and nanoswimmers has gained increasing interest, especially the use of Janus particles. The implementation of Janus particles as swimmers is widely reported, which is reflected in its ever-growing list of applications. However, research on their utilization at liquid-liquid interfaces is scarce. In order to apply Janus micro- and nanoswimmers at liquid-liquid interfaces, for example as microscopic sweepers, it is imperative that more research is performed in order to get a better understanding of how it influences the swimmers’ behaviour. The goal of this thesis was to provide fundamental research concerning the characterization and behaviour of sideways propelling microrods at the interface between water and decane and to compare it to the behaviour near the bottom wall. Polystrene microfibers with a diameter of 3 to 6µm were produced by electrospinning and coated with a bimetallic Pt/Au coating. Using ultrasonification these fibers were cut into pieces resulting in bimetallic Janus microrods. Next a spreading solution of rods was made and added into a specially designed cell with a circular well, filled with 5 wt.% hydrogen peroxide solution. The rods sank to the bottom and due to electrostatic repulsive forces remained on a height of approximately 550 nm above the bottom wall. Their movement was observed using an inverted optical microscope and image analysis showed that they propelled with a velocity of 2.16 ± 1.11 µm/s. Using a specially designed cell consisting of a well with an edge in the middle with water in the bottom half and purified decane on top, the behaviour of similar rods was examined at the water-decane interface by adding the same spreading solution on top of the decane layer. The rods would again sink down in the decane, but they were adsorbed to the interface, limiting their movement to the 2D interface. Analysis of the images, provided by the inverted optical microscope, revealed that the velocities were 2 to 4 times higher than near the wall. Furthermore the wetting behaviour of the microrods was examined by performing sessile drop contact angle measurements on polystyrene and both coating materials. Polystyrene proved to be hydrophobic but both coatings showed similar contact angles for water in decane and were considered neutral at first, but hydrophilic after contact with hydrogen peroxide. The position of the rods at the interface and the thickness of the Au coating was also examined by AFM measurements of the liquid-liquid surface. These measurements indicated that the rods protruded 1.34 ± 0.33 µm into the water phase and that the Au layer had a thickness of 21.4 nm.

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Dissertation
Unraveling the structure-property relationships of an intrinsically conducting polymer in suspension

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This thesis focussed on understanding the relationship between the structure and the properties of a partially soluble polymer, PEDOT, in a suspension of EG. In this suspension, conjugated structures of amorphous and crystalline phases of PEDOT are formed with EG. Solution-induced crystallization of the suspension was investigated in situ in order to study the effects of PEDOT concentration and temperature on the final properties. Firstly, the conductivity of solid PEDOT was studied by using a dielectric set-up. The conductivity was shown to be limited due to the low amount of dopant added during synthesis of PEDOT. However, it was demonstrated that a slower cooling rate of the crystallization process could significantly enhance the resulting conductivity. The established increase in the conductivity was linked to the larger fraction of the crystalline phase by DSC analysis. The conductivity could be increased by approximately three decades by decreasing the cooling rate from 5 to 0.1 °C/min. This was calculated to correspond to a crystallinity increase of around 30 %. Secondly, the influence of concentration and temperature was investigated by performing rheological and conductivity experiments. In order to do so, the suspension preparation was optimized by focussing on decreasing the aggregate size, which mainly influenced the sedimentation rate and suspension stability. Rheological experiments showed that a rheological percolation was achieved at a concentration of 10 mg/mL, resulting in an increase of the storage modulus by approximately three decades. Conductivity experiments did not show a significant increase at these conditions. However, at a concentration of 40 mg/mL, a twofold increase of conductivity could be obtained. A study of the influence of temperature on the rheological percolation kinetics was performed to ascertain the optimal temperature for solution-induced crystallization, which followed an Arrhenius dependency. Finally, the contribution of the amorphous and crystalline phases to the bulk properties were separated by heating above the melting temperature. At these conditions, rheological experiments showed that the rheological percolation was destroyed. This indicated that the rheological percolation was mostly formed by the connectivity of the crystalline phase of PEDOT. At similar conditions, a concurrent change in the conducting properties was however restricted.

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Dissertation
Stochastic model predictive control for heterogeneous population systems using Gaussian processes

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Population balance modelling and its applications is an area that is growing rapidly. In chemical engineering, population balance equations (PBEs) can be used to model various heterogeneous population systems such as crystallization, precipitation, deposition, granulation, flocculation, drying and mixing, cell growth and many more processes. The control of heterogeneous population systems is important, these systems need to have certain characteristics that are imposed by the industry or user. Model predictive control can be selected to handle this as it is a well-established method with a simple algorithm, on the condition the system dynamics can be captured accurately in a model. Population balance modelling will generate a multi-variate partial differential equation of the particle system in the number density function. There exist many methods to solve the PBE for the number density function but none take into account the randomness and the uncertainty of the model that is obtained. The use of Gaussian processes (GPs) to solve regression problems in a non-parametric and probabilistic way, is a machine-learning method that has gained interest over the years. These GPs can be propagated through time by the use of numerical GPs. Numerical GPs can thus be applied as a solution method for the PBE to approximate the number density function over time. The strength of this method is that the model will include the uncertainty of the solution which can be implemented in the probabilistic framework of stochastic model predictive control (SMPC). The purpose of this thesis is to illustrate the feasibility of the implementation of a numerical GP solution scheme into a stochastic model predictive control scheme. First of all, the algorithm was created that combined the solution scheme of a numerical Gaussian process for a heterogeneous population system with a stochastic model predictive control algorithm. The newly developed method was then put to the test by applying it to a simple case study. The case study considered a crystallization process where the growth rate was assumed to be constant and the dilution rate became the controlled input. The control objective of the case study was to let the particle size distribution (defined as a number density function) converge to a defined steady state in a purposed time. The system could reach this control objective by adjusting the dilution rate starting from a chosen initial dilution rate. The investigation of this case study provides a proof of concept that numerical Gaussian processes can be combined with stochastic model predictive control for the determination of important characteristics of a heterogeneous population system.

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Dissertation
Freeze-casting: An interesting route to porous ceramics

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SMaRT works in the context of product design with the use of “complex fluids” or “soft matter”. One of many researches conducted at this facility is the production of porous scaffolds. The main goalof this research is to replicate bone implants with the utilization of the freeze-casting process. This study focuses on the use of a capillary suspension with camphene as a primary liquid, alumina as the building blocks and a sucrose solution as an immiscible secondary liquid. Freezing of the suspension was followed by freeze-drying and sintering afterwards. First, scaffolds with 10 vol% alumina content and 0 vol%, 1 vol% or 2 vol% sucrose solution were produced. Further, the alumina content was decreased to 7 vol% and mixing time was increased to enhance homogenization. In addition, camphene growth, mass losses, linear shrinkage and temperature gradient were tracked. The scaffolds were analyzed with scanning electron microscopy to investigate pore sizes, porosity and pore properties. Mean porosities of the scaffolds with 10 vol% alumina and 0 vol%, 1 vol% or 2 vol% sucrose solution are 38%, 43% and 41% respectively. Furthermore, their respective mean pore sizes are 79 µm, 74 µm and 84 µm. After increasing the mixing time to 3 hours and reducing the alumina content to 7 vol%, porosity increases to approximately 50% and smaller and less agglomerates are present. The mean pore sizes increase with the addition of sucrose solution, lowering of the solid loading and the increase of the freezing time. Additionally, the growth direction of the dendrites is a challenge to control due to the radial temperature gradient. Lastly, the linear shrinkage during sintering was found to be 18.1%.

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Dissertation
Metal Ion Recovery from an Industrial Waste Stream

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Catalytic oxidation of HMF is among the most promising and extensively studied processes for FDCA production. A possible catalyst for this oxidation is a homogeneous Co/Mn/Br catalyst. However, the separation and recycling of the catalyst has proven to be challenging. Recycling of the metal ions does not only rely on economic and strategic incentives. The environmental impact of cobalt and manganese production is the main driving force for the recuperation of the metal ions from the waste stream in order to reuse them. Removing cobalt and manganese from the process waste stream is also adding value in the effort towards a more sustainable process. In this work, the application of cobalt and manganese removal from the waste stream, obtained by the production of FDCA using a homogeneous Co/Mn/Br catalyst, by metal ion separation processes through selective separation processes such as solvent extraction (SE) and electrodialysis (ED) is studied experimentally. For solvent extraction, polymer inclusion membranes (PIMs) are observed whereby a selective extractant is integrated in the membrane. Membrane based separation methods are known for their economical and sustainable way to extract and separate compounds. The effects of various operating conditions such as pH, residence time, current density, etc. have been investigated in order to characterize the performance of the techniques and determine optimal conditions. Leveraging the obtained experimental data, a conceptual design of the process is made. The experiments have shown that electrodialysis is a viable technique to remove cobalt and manganese metal ions from the waste stream. The optimal voltage has been determined. Furthermore, the effects of the presence of bromine and the concentration of acetic acid in the receiving solution has been investigated. It was found that a PIM with a composition of 55 wt% PVC and 45 wt % D2EHPA is able to separate manganese from cobalt. Furthermore, the optimal pH for the process has been determined. As the experiments are time intensive, addition of an electric current has been investigated to decrease the duration of the PIM tests. Finally, the effect of the applied electric current density on the separation performance of the PIM has been studied. A final two-stage experiment was conducted. In a first stage, an electrodialysis experiment has been performed using the determined, optimal conditions for the removal of cobalt and manganese from the waste stream. The aim of this experiment was to achieve the specified goal to lower the cobalt concentration in the dilute compartment or waste stream to 20 ppm. In a second stage, a PIM at optimal conditions has been used in order to separate the removed metal ions. Finally, a path forward has been suggested with some recommendations on what and how further research can fine tune the process and make it more cost efficient.

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Dissertation
Plasma-assisted methane coupling to added-value products

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One of the major challenges in this century is to keep global warming well below a 2°C increase compared to pre-industrial levels. Currently, the ethylene industry is the second most polluting industry and is mostly based on fossil fuels which are processed by steam cracking. CO2 emissions might be reduced by (i) averting methane flaring, (ii) using plasma-assisted methane-to-ethylene processes while avoiding fuel combustion, and (iii) coupling these processes with green electricity. In this work, a plate-to-plate plasma reactor performed a non-oxidative methane coupling reaction into C2 products, of which acetylene and ethylene are of main interest. It was found that lower discharge gap, lower operation pressure, higher pulse frequency and higher power output resulted in higher energy input that is channeled into the plasma zone. Although higher energy input should result in higher methane conversion, low methane conversion was obtained at the lowest tested discharge gap of 1.5 mm where presumably not all the energy was used to convert methane. Furthermore, at largest discharge gap of 5 mm, low energy input resulted in lower methane conversion leading to an optimal operating window of discharge gaps between 2.5 and 4 mm. When comparing the plate-to-plate to coaxial and pin-to-plate configurations, the plate-to-plate plasma reactor seems to be the most optimal choice offering decent methane conversion (34%), high acetylene selectivity (68%), efficient energy use (1306 kJ/mol acetylene) and excellent stability over time. No clogging of the reactor was observed in all experiments that were performed in the plate-to-plate reactor, while in pin-to-plate and coaxial configuration this was a major issue limiting their use in long-term experiments. Two long-term continuous experiments were performed in the plate-to-plate plasma reactor at most optimal conditions. Both experiments were performed for over 12 hours without any signs of reactor clogging. Methane conversion, however, decreased from approximately 33% to 18%. By using an air-based cleaning method, in which air was sent through the plasma reactor for 10 min during plasma discharge, it was found that the reactor performance was able to be restored to its initial level. This method does not require any manual action, and could allow long-term autonomous operation at high C2 yields. At last, a two-step process was examined in which the formed acetylene in the plasma chamber was converted into ethylene in a catalyst chamber using a Pd-based catalyst. It was found that by simply preheating the catalyst chamber, initially all acetylene could be converted into ethylene.

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Dissertation
Monitoring of activated sludge flocs and granules through quantitative fluorescent image analysis

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For the purification of wastewater, a water purification installation is needed. In this installation, activated sludge or granules are used for the removal of pollutants from the wastewater. To monitor the working of the activated sludge or granules, a quantitative fluorescent image analysis can be used. The first goal of this work is finding a suitable fluorescent staining dye capable of staining all the biomass in activated sludge. This to make a quantitative comparison possible when the total biomass is stained in combination with other dyes with specific targets. The second goal is to design a filament detection method that can be used with a three-dimensional (3D) quantitative fluorescent staining. This to quantify the amount of filaments in activated sludge samples. For the quantitative fluorescent image analysis, different activated sludge samples of both flocs and granules are used. For the granules samples, also a slicing step was executed. The staining of the total biovolume is preformed with the dyes DAPI, Hoechst 33342, SYTO 9 and Rodamine 6G. Also ThT has been used as a validation step, wich only stains amyloids. For the staining, the procedures of Hoechst 33342, SYTO 9 and Rodamine 6G were optimised. After the staining, a 3D image was made in the image acquisitions step using a confocal laser scanning microscope (CLSM). In this step the image quality was optimised by changing the laser intensity and detector voltage. The image data was extracted using COMSTAT a program written in MATLAB and adapted from an existing program. In this program, different methods are compared to detect the total biovolume where the Otsu, cross-entropy and a new thresholding method was designed in this work. When comparing the used methods, the Otsu and new threshlding methode gave an under and over estimation respectively, the cross-entropy thresholding method seemed to give the best result. The comparison of the different stainings shows that the result of the SYTO 9, DAPI and Hoechst 33342 staining gave about the same biovolumes, the Rodamine 6G detected more biovolume. Not one of the dyes detected a higher biovolume than ThT, resulting in an incomplete staining of the biovolume for every dye. Though, when a washing step is introduced in the staining process of the Rodamine 6G dye, probably more biovolume could be detected. The designed filament detection method showed a good detection of filaments throughout different activated sludge flocs samples. The added value of the filament detection in 3D and of a specific dye is that it enables the comparison between different dyes. The created filament detection method is based on a two-dimensional (2D) method which is adapted for 3D images.

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Dissertation
Uncertainty analyses of artificial neural networks for applications in the chemical industry

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The recent developments in the area of artificial neural networks have allowed the modelling of very complex processes which could not be modelled before. These developments have also been applied in the field of chemical engineering. However not many research has been done into the uncertainty of these models, especially concerning chemical engineering applications. This thesis attempts to use and verify two proposed methods for modelling uncertainty in artificial neural networks, with the use of a self-generated dataset and a real life dataset of carbon capture spray columns. The two methods that are verified, are methods based on bootstrapping. One method can be seen as the standard version of bootstrapping, where multiple models are generated and the average prediction is taken as final prediction (also in literature referred to as committee approach) and the variance of the predictions is used as a measure for the uncertainty. The second approach, the model generation approach, which is a subtype of the bootstrapping, uses the model parameters of each model as a set gaussian distributed values and generates the best fitting gaussian distribution for these parameters. The gaussian distributions are then subsequently used to randomly generate model parameters. The results for the model generation approach were rather disappointing. Not only was the predicted uncertainty completely nonsensical. But also the error on output predictions made by the randomly generated models were extremely high, which led us to conclude that the method did not work for our neural network. The standard bootstrapping network showed more promising results, especially for the self-generated data. Studying the real life data, more inconstancies were observed. At the end is concluded that more research is necessary in the behaviour of this uncertainty analyses method, especially looking toward unsymmetric uncertainties.

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Dissertation
Capillary suspensions: a new route for porous structures

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A camphene-based suspension with alumina as the solid phase was prepared by mixing for 3 h at 600 rpm, at 60◦C with an overhead stirrer. By performing an amplitude stress sweep, it was found that the storage modulus (G

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