Improving the Manufacturability of Active Microfluidic Devices using Stereolithography (SL)

Thesis (Master's)--University of Washington, 2016-06

Biotechnological production of lactic acid integrated with potato wastewater treatment by Rhizopus arrhizus

This paper describes a feasibility study of a for lactic acid production integrated with are treatment of wastewater from an industrial starch plant. Rhizopus oryzae two strains, Rhizopus arrhizus and Rhizopus oligosporus were tested with respect to their capability to carry out simultaneous saccharification and fermentation to lactic acid using potato wastewater. Rhizopus arrhizus DAR 36017 was identified as a suitable strain that demonstrated a high capacity for starch saccharification and lactic acid synthesis. The optimal conditions, in terms of pH, temperature and starch concentration, for lactic acid production were determined. The selected fungal strain grew well in a pH range from 3.0 to 7.0. The addition of CaCO(3)10 g dm(-3) maintained the pH at 5.0-6.0 and significantly enhanced lactic acid production. Kinetic study revealed that almost complete starch saccharification and a lactic acid yield of 450g kg(-1) could be achieved in 20 h and 28 h cultivation, respectively. The maximum lactic acid production 21 g dm(-3) and mycelial biomass (1.7 g dm(-3)) were obtained at 30degreesC. Besides the multiple bioproducts, total removal of suspended solids and 90% reduction of COD were achieved in a single no-aseptic operation. (C) 2003 Society of Chemical Industry.

A population balance model for high shear granulation

In a previous paper, Hoornaert et al. (Powder Technol. 96 (1998); 116-128) presented data from granulation experiments performed in a 50 L Lodige high shear mixer. In this study that same data was simulated with a population balance model. Based on an analysis of the experimental data, the granulation process was divided into three separate stages: nucleation, induction, and coalescence growth. These three stages were then simulated separately, with promising results. it is possible to derive a kernel that fit both the induction and the coalescence growth stage. Modeling the nucleation stage proved to be more challenging due to the complex mechanism of nucleus formation. From this work some recommendations are made for the improvement of this type of model.

Strength and attrition resistance of agglomerates and particulate coatings

The mechanical properties of a range of agglomerates and particulate coatings have been measured using a nanoindenter. The effect of formulation properties such as powder and binder properties on coating hardness is described. An attempt is also made to measure the fracture hardness with the nanoindenter. The use of indentation technology to measure fundamental agglomerate properties is critically analysed. Based on the indentation measurements and standard attrition test results, the coating hardness is found closely related to the attrition rate under standard conditions and can be used to screen different powder/binder formulations. (C) 2002 Elsevier Science B.V All rights reserved.

Structural and mechanical properties of nanostructured granular alumina catalysts

Granular gamma-Al2O3 support and 8 wt % CuO/gamma-Al2O3 catalyst were synthesized by a sol-gel granulation method. The pore structure, crush strength, hardness, and elasticity of these sol-gel-derived catalysts were studied and compared with similar commercial catalysts prepared by non-sol-gel methods. Alumina and CuO-coated alumina granular particles prepared by different methods have different macro- and microstructure. The sol-gel-derived granular gamma-alumina and CuO-coated gamma-alumina granular particles have a structure defined by compact packing of uniform, nanosized gamma-alumina crystallites. They are characterized by a more uniform pore size distribution and larger surface area as compared to similar commercial samples with a structure defined by packing of aggregates consisting of nonuniform gamma-alumina crystallites. Because of the differences in the macro- and microstructure, the sol-gel-derived granular samples offer higher crush strength and greater hardness than the commercial samples.

Nucleation regime map for liquid bound granules

Nucleation is the first step in granulation where the powder and liquid first contact. Two types of nucleation in wet granulation processes are proposed. Drop controlled nucleation, where one drop forms one nucleus, occurs when drops hitting the powder surface do not overlap (low spray flux Psi(a)) and the drop must wet quickly into the bed (short drop penetration time t(p)). If either criterion is not met, powder mixing characteristics will dominate (mechanical dispersion regime). Granulation experiments were performed with lactose powder, water, PEG200, and 7% HPC solution in a 6 L and a 25 L mixer granulator. Size distributions were measured as the drop penetration time and spray flux were varied. At short penetration times, decreasing Psi(a) caused the nuclei distribution to become narrower. When drop penetration time was high, the nuclei size distribution was broad independent of changes in dimensionless spray flux. Nucleation regime maps were plotted for each set of experiments in each mixer as a function of the dimensionless distribution width delta. The nucleation regime map demonstrates the interaction between drop penetration time and spray flux in nucleation. The narrowest distribution consistently occurred at low spray flux and low penetration time, proving the existence of the drop controlled regime. The nucleation regime map provides a rational basis for design and scale-up of nucleation and wetting in wet granulation.

Flow patterns in granulating systems

Particle flow patterns were investigated for wet granulation and dry powder mixing in ploughshare mixers using Positron Emission Particle Tracking (PEPT). In a 4-1 mixer, calcium carbonate with mean size 45 mum was granulated using a 50 wt.% solution of glycerol and water as binding fluid, and particle movement was followed using a 600-mum calcium hydroxy-phosphate tracer particle. In a 20-1 mixer, dry powder flow was studied using a 600-mum resin bead tracer particle to simulate the bulk polypropylene powder with mean size 600 mum. Important differences were seen between particle flow patterns for wet and dry systems. Particle speed relative to blade speed was lower in the wet system than in the dry system, with the ratios of average particle speed to blade tip speed for all experiments in the range 0.01-015. In the axial plane, the same particle motion was observed around each blade; this provides a significant advance for modelling flow in ploughshare mixers. For the future, a detailed understanding of the local velocity, acceleration and density variations around a plough blade will reveal the effects of flow patterns in granulating systems on the resultant distribution of granular product attributes such as size, density and strength. (C) 2002 Elsevier Science B.V All rights reserved.

Layered silicate nanocomposites based on various high-functionality epoxy resins. Part II: The influence of an organoclay on the rheological behavior of epoxy prepolymers

The effect of an organically surface modified layered silicate on the viscosity of various epoxy resins of different structures and different functionalities was investigated. Steady and dynamic shear viscosities of the epoxy resins containing 0-10 wt% of the organoclay were determined using parallel plate rheology. Viscosity results were compared with those achieved through addition of a commonly used micron-sized CaCO3 filler. It was found that changes in viscosities due to the different fillers were of the same order, since the layered silicate was only dispersed on a micron-sized scale in the monomer (prior to reaction), as indicated by X-ray diffraction measurements. Flow activation energies at a low frequency were determined and did not show any significant changes due to the addition of organoclay or CaCO3. Comparison between dynamic and steady shear experiments showed good agreement for low layered silicate concentrations below 7.5 wt%, i.e. the Cox-Merz rule can be applied. Deviations from the Cox-Merz rule appeared at and above 10 wt%, although such deviations were only slightly above experimental error. Most resin organoclay blends were well predicted by the Power Law model, only concentrations of 10 wt% and above requiring the Herschel-Buckley (yield stress) model to achieve better fits. Wide-angle X-ray measurements have shown that the epoxy resin swells the layered silicate with an increase in the interlayer distance of approximately 15 Angstrom, and that the rheology behavior is due to the lateral, micron-size of these swollen tactoids.

Layered silicate nanocomposites based on various high-functionality epoxy resins: The influence of an organoclay on resin cure

The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities, was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p-amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems.

New insights into NO-carbon and N2O-carbon reactions from quantum mechanical calculations

Density functional theory calculations were used to investigate the mechanisms of NO-carbon and N2O-carbon reactions. It was the first time that the importance of surface nitrogen groups was addressed in the kinetic behaviors of the NO-carbon reaction. It was found that the off-plane nitrogen groups that are adjacent to the zigzag edge sites and in-plane nitrogen groups that are located on the armchair sites make the bond energy of oxygen desorption even ca. 20% lower than that of the off-plane epoxy group adjacent to zigzag edge sites and in-plane o-quinone oxygen atoms on armchair sites; this may explain the reason why the experimentally obtained activation energy of the NO-carbon reaction is ca. 20% lower than that of the O-2-carbon reaction over 923 K. A higher ratio of oxygen atoms can be formed in the N2O-carbon reaction, because of the lower dissociation energy of N2O, which results in a higher ratio of off-plane epoxy oxygen atoms. The desorption energy of semiquinone with double adjacent off-plane oxygen groups is ca. 20% less than that of semiquinone with only one adjacent off-plane oxygen group. This may be the reason why the activation energy of N2O is also ca. 20% less than that of the O-2-carbon reaction. The new mechanism can also provide a good qualitative comparison for the relative reaction rates of NO-, N2O-, and O-2-carbon reactions. The anisotropic characters of these gas-carbon reactions can also be well explained.

Use of anion clay hydrotalcite to remove coloured organics from aqueous solutions

Anion clay hydrotalcite sorbents were prepared to investigate their adsorption capabilities in the removal of coloured organic substances from various aqueous systems. Anion clay hydrotalcite was found to be particularly effective at removing negatively charged species. Its excellent uptake levels of anionic species can be accounted for by its high surface area and anion exchange ability. That is, coloured substances can be adsorbed on the surface or enter the interlayer region of the clay by anion exchange. In the adsorption of Acid Blue 29 on the anion clay hydrotalcite, an equilibrium time of 1 h with dye removal exceeding 99% was obtained. The hydrotalcite was found to have an adsorption capacity marginally below that of commercial activated carbon. It should be noted that the spent sorbents can be regenerated easily by heating at 723 K to remove all adsorbed organics. The reused sorbents displayed greater adsorption capabilities than the newly prepared hydrotalcite. Hence, the anion clay hydrotalcite is easily recoverable and reusable such that it is a promising sorbent for environmental and purification purposes. (C) 2002 Elsevier Science B.V. All rights reserved.

Degradation of azo-dye Orange II by a photoassisted Fenton reaction using a novel composite of iron oxide and silicate nanoparticles as a catalyst

A novel nanocomposite of iron oxide and silicate, prepared through a reaction between a solution of iron salt and a dispersion of Laponite clay, was used as a catalyst for the photoassisted Fenton degradation of azo-dye Orange II. This catalyst is much cheaper than the Nafion-based catalysts, and our results illustrate that it can significantly accelerate the degradation of Orange II under the irradiation of UV light (lambda = 254 nm). An advantage of the catalyst is its long-term stability that was confirmed through using the catalyst for multiple runs in the degradation of Orange II. The effects of the H2O2 molar concentration, solution pH, wavelength and power of the LTV light, catalyst loading, and initial Orange II concentration on the degradation of Orange 11 were studied in detail. In addition, it was also found that discoloration of Orange 11 undergoes a faster kinetics than mineralization of Orange II and 75% total organic carbons of 0.1 mM Orange II can be eliminated after 90 min in the presence of 1.0 g of Fe-nanocomposite/L, 4.8 mM H2O2, and 1 x 8W UVC.

Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2

Since the start of last century, methanol synthesis has attracted great interests because of its importance in chemical industries and its potential as an environmentally friendly energy carrier. The catalyst for the methanol synthesis has been a key area of research in order to optimize the reaction process. In the literature, the nature of the active site and the effects of the promoter and support have been extensively investigated. In this updated review, the recent progresses in the catalyst innovation, optimization of the reaction conditions, reaction mechanism, and catalyst performance in methanol synthesis are comprehensively discussed. Key issues of catalyst improvement are highlighted, and areas of priority in R&D are identified in the conclusions.

Performance of hydrophobic and hydrophilic silica membrane reactors for the water gas shift reaction

In this study, a novel molecular sieve silica (MSS) membrane packed bed reactor (PBR) using a Cu/ZnO/Al2O3 catalyst was applied to the low-temperature water gas shift reaction (WGS). Best permeation results were H-2 permeances of 1.5 x 10(-6) mol(.)s(-1) m(-2) Pa-1, H-2/CO2 selectivities of 8 and H-2/N-2 selectivities of 18. It was shown that an operation with a sweep gas flow of 80 cm 3 min(-1), a feed flow rate of 50 cm(3) min(-1) and a H2O/CO molar ratio of one at 280 degreesC reached a 99% CO conversion. This is well above the thermodynamic equilibrium and achievable PBR conversion. Hydrophilic membranes underwent pore widening during the reaction while hydrophobic membranes indicated no such behaviour and also showed increased H-2 permeation with temperature, a characteristic of activated transport. (C) 2003 Elsevier Science B.V. All rights reserved.

A novel laponite clay-based Fe nanocomposite and its photo-catalytic activity in photo-assisted degradation of Orange II

A novel laponite RD clay-based Fe nanocomposite (Fe-Lap-RD) has been successfully synthesized through a reaction between a solution of iron salt and an aqueous dispersion of laponite RD clay. The X-ray diffraction (XRD) results reveal that the Fe-Lap-RD mainly consists of Fe2O3 (maghemite) and Fe2Si4O10(OH)2 (iron silicate hydroxide), which have tetragonal and monoclinic structures, respectively, and has a high specific surface area as well as a high pore volume. The photo-catalytic activity of the Fe-Lap-RD was examined in the photo-assisted degradation of an organic azo dye Orange II. It was found that the mineralization of Orange 11 undergoes a slower kinetics than discoloration, and 70% total organic carbon (TOC) of 0.2 mM Orange 11 can be removed in 90 min, implying that the Fe-Lap-RD exhibited a high photo-catalytic activity in the presence of H2O2 and UV light (254 nm) in the photo-assisted degradation of Orange II. In addition, our experiments also illustrate that the Fe-Lap-RD has a long-term stability but is of low cost. This study illustrates the possibility of photo-assisted degradation of organic compounds without the requirements to remove the Fe ions after reaction. Two possible catalytic reaction mechanisms are also proposed. (C) 2003 Elsevier Science Ltd. All rights reserved.