A Model for Chlorine Dioxide Delignification of Chemical Pulp

Abstract

A phenomenon based model for chlorine dioxide delignification of chemical pulp is introduced. The pulp suspension environment is modeled using the concept of two liquid phases, one inside and the other external to the fiber wall. Physico-chemical processes taking place during delignification are implemented with thermodynamic, mass transfer and reaction kinetic models. A broad library of chemical reactions is introduced. Inclusion of each reaction is justified. The model response is tested against experimental laboratory delignification results (o-delignified birch pulp). The experimental data consists of kappa number, hexenuronic acid, inorganic oxy-chlorine compound, and organochlorine (AOX, OX) measurements at several time points during five delignification experiments. The model predictions are mainly in good agreement with the experimental results. The predictions regarding hypochlorous acid driven processes (HexA removal, organochlorine formation, chlorite and chlorate concentration) are somewhat incoherent, indicating that knowledge regarding the intermediately formed hypochlorous acid is presently insufficient.     

Short Vapour Residence Time Catalytic Pyrolysis of Spruce Sawdust in a Bubbling Fluidized-Bed Reactor with HZSM-5 Catalysts

Catalytic pyrolysis of spruce sawdust was carried out in a bubbling fluidized-bed reactor using HZSM-5 catalysts. The effects of space velocity, catalyst deactivation, catalyst acidity and catalyst regeneration were studied. The use of catalysts decreased the yield of organic liquids compared to non-catalytic yields while the yields of pyrolytic water and gases increased. Decreasing the space velocity enhanced these effects. The rate of catalyst deactivation depended on the acidity of the catalyst, with more acidic catalysts deactivating more rapidly. Using a catalyst with a Si/Al ratio of 140 resulted in the largest changes in bio-oil properties. Periodic regeneration of the catalyst in the fluidized-bed reactor was also demonstrated using varying regeneration times and temperatures. It was shown that compared to BFB reactors, CFB reactor types would offer better operating characteristics for commercial scale catalytic pyrolysis processes in regard to vapour residence times, and catalyst activity and regeneration.     

Novel Online Diagnostic Analysis for In-Flight Particle Properties in Cold Spraying

In cold spraying, powder particles are accelerated by preheated supersonic gas stream to high velocities and sprayed on a substrate. The particle velocities depend on the equipment design and process parameters, e.g., on the type of the process gas and its pressure and temperature. These, in turn, affect the coating structure and the properties. The particle velocities in cold spraying are high, and the particle temperatures are low, which can, therefore, be a challenge for the diagnostic methods. A novel optical online diagnostic system, HiWatch HR, will open new possibilities for measuring particle in-flight properties in cold spray processes. The system employs an imaging measurement technique called S-PTV (sizing-particle tracking velocimetry), first introduced in this research. This technique enables an accurate particle size measurement also for small diameter particles with a large powder volume. The aim of this study was to evaluate the velocities of metallic particles sprayed with HPCS and LPCS systems and with varying process parameters. The measured in-flight particle properties were further linked to the resulting coating properties. Furthermore, the camera was able to provide information about variations during the spraying, e.g., fluctuating powder feeding, which is important from the process control and quality control point of view.     

Fluorescence quenching-based assays for hydrolyzing enzymes. Application of time-resolved fluorometry in assays for caspase, helicase, and phosphatase

We have developed assay technologies to measure hydrolyzing enzymes based on homogeneous time-resolved fluorescence quenching (TruPoint). High sensitivity was obtained using fluorescent europium chelates as labels, internally quenched by suitable quenchers and released upon enzymatic reaction. This approach allows robust and sensitive monitoring of low enzyme activities. The assay technology and the choice of donor-acceptor pairs were evaluated in three different enzymatic assays, a protease related to apoptosis, helicase involved in DNA unwinding, and phosphatase having an important role in cellular signaling cascades. All the assays produced an increasing signal, were sensitive, and had a good dynamic range. There were significant differences in optimized quenchers for each of the assays depending on the size, flexibility, and rigidity of the substrates. Also, clear differences in the energy-transfer reactions, their requirements for spectral overlapping, ionic interactions, and energy-transfer distances were found. Each of the enzymatic assays was briefly tested in a high-throughput screening environment by analyzing signal dynamics and statistical relevance as Z' factors.     

Line‐Sweep Ambient Obscurance

Screen‐space ambient occlusion and obscurance have become established methods for rendering global illumination effects in real‐time applications. While they have seen a steady line of refinements, their computational complexity has remained largely unchanged and either undersampling artefacts or too high render times limit their scalability. In this paper we show how the fundamentally quadratic per‐pixel complexity of previous work can be reduced to a linear complexity. We solve obscurance in discrete azimuthal directions by performing line sweeps across the depth buffer in each direction. Our method builds upon the insight that scene points along each line can be incrementally inserted into a data structure such that querying for the largest occluder among the visited samples along the line can be achieved at an amortized constant cost. The obscurance radius therefore has no impact on the execution time and our method produces accurate results with smooth occlusion gradients in a few milliseconds per frame on commodity hardware.     

Simple and low-cost fabrication of PDMS microfluidic round channels by surface-wetting parameters optimization

Convenient for both biologists and MEMS designers, Polydimethylsiloxane (PDMS) polymer is intensively investigated for its biocompatibility, transparency, high resistance under plasma treatment, flexibility and resistance to high temperature. However, for microfluidic applications, the fabrication of PDMS circular channels is difficult to achieve except by wire moulding. In this article, we present a simple, fast and low-cost fabrication method which can be applied out of clean-room environment. It is based on the deposition of alginic acid sodium salt aqueous solution, enabling the formation of a liquid cylinder on the most hydrophilic part of a hydrophilic/hydrophobic patterned surface. We experimentally studied the interaction between liquid rivulets and surfaces presenting a contrast of wettability and/or a stepwise texture. Subsequent moulding of the half-cylinder of liquid produces round PDMS microfluidic channels. The optimal parameters for hydrophilic/hydrophobic patterns have then been applied to produce the roundest possible channels. The realisation of both straight channels 300–500 μm wide, 1 cm long and 75° tangent chord angle at best, and Y-shaped channels with the same dimensions and 55° TCA is demonstrated.     

Prospecting hydrogen production of Escherichia coli by metabolic network modeling

Genome-scale model was applied to analyze the anaerobic metabolism of Escherichia coli. Three different methods were used to find deletions affecting fermentative hydrogen production: flux balance analysis (FBA), algorithm for blocking competing pathways (ABCP), and manual selection. Based on these methods, 81 E. coli mutants possessing one gene deletion were selected and cultivated in batch experiments. Experimental results of H₂ and biomass production were compared against the results of FBA. Several gene deletions enhancing H₂ production were found. Correctness of gene essentiality predictions of FBA for the selected genes was 78% and 77% in glucose and galactose media, respectively. 33% of the mutations that were predicted by FBA to increase H₂ production had a positive effect in experiments. Batch cultivation is a simple and straightforward experimental way to screen improvements in H₂ production. However, the ability of FBA to predict the H₂ production rate cannot be evaluated by batch experiments. Metabolic network models provide a method for gaining broader understanding of the complicated metabolic system of a cell and can aid in prospecting suitable gene deletions for enhancing H₂ production.     

Effect of hot drawing on properties of wet‐spun poly(L,D‐lactide) copolymer multifilament fibers

Polylactide stereocopolymer multifilament fibers were prepared by wet spinning and subsequent hot drawing. The stereocopolymers were poly‐(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4, and poly‐(L,DL ‐lactide) [P(L,DL )LA], L/DL ratio 70/30. They were dissolved in dichloromethane and coagulated in a spin bath containing ethanol. The hot‐drawing temperature was 65°C. The draw ratios (DR) were upto 4.5 to the P(L,D )LA 96/4 filaments and upto 3 to the P(L,DL )LA 70/30 filaments. Wet spinning decreased crystallinities of both copolymers. Hot drawing increased the crystallinity of the P(L,D )LA 96/4 filament but not to the level of the original copolymer, whereas the as‐spun and the hot‐drawn P(L,DL )LA 70/30 filaments were amorphous. The filament diameter, tenacity, Young's modulus, and elongation at break were dependent on the DR. The maximum tenacity (285 MPa) and Young's modulus (2.0 GPa) were achieved with the P(L,D )LA 96/4 filament at the DR of 4.5. Respectively, the maximum tenacity of the hot‐drawn P(L,DL )LA 70/30 filament was 175 MPa and Young's modulus 1.3 GPa at the DR of 3. Hot drawing slowed down in vitro degradation rate of both stereocopolymer filaments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Use of adipose stem cells and polylactide discs for tissue engineering of the temporomandibular joint disc

There is currently no suitable replacement for damaged temporomandibular joint (TMJ) discs after discectomy. In the present study, we fabricated bilayer biodegradable polylactide (PLA) discs comprising a non-woven mat of poly(L/D)lactide (P(L/D)LA) 96/4 and a P(L/DL)LA 70/30 membrane plate. The PLA disc was examined in combination with adipose stem cells (ASCs) for tissue engineering of the fibrocartilaginous TMJ disc in vitro. ASCs were cultured in parallel in control and chondrogenic medium for a maximum of six weeks. Relative expression of the genes, aggrecan, type I collagen and type II collagen present in the TMJ disc extracellular matrix increased in the ASC-seeded PLA discs in the chondrogenic medium. The hypertrophic marker, type X collagen, was moderately induced. Alcian blue staining showed accumulation of sulphated glycosaminoglycans. ASC differentiation in the PLA discs was close to that observed in pellet cultures. Comparison of the mRNA levels revealed that the degree of ASC differentiation was lower than that in TMJ disc-derived cells and tissue. The pellet format supported the phenotype of the TMJ disc-derived cells under chondrogenic conditions and also enhanced their hyalinization potential, which is considered part of the TMJ disc degeneration process. Accordingly, the combination of ASCs and PLA discs has potential for the development of a tissue-engineered TMJ disc replacement.     

Processing characteristics of tin and tungsten oxides relevant to production of gas sensors

Tungsten trioxide and two types of tin dioxide were compacted at different pressures and then sintered at different temperatures in order to study how the microstructure formed is dependent on these parameters. The structures were studied using dilatometric and porosimetric techniques and also using electron microscopy. X-ray diffraction was used to ascertain the completeness of the decomposition reaction of SnSO₄ being converted to SnO₂. Tin dioxide, which was prepared from tin sulphate by calcining, was characterised by a large specific surface area. For all three materials studied the mean pore size was found to increase and the specific surface area was found to decrease with increasing sintering temperature. In the case of WO₃ the total pore volume decreased markedly as the sintering temperature was increased from 900 to 1000° C. However, in the case of SnO₂, the total pore volume remained almost constant in the sintering temperature range of 600 to 1500° C. In the case of SnO₂ derived from SnSO₄ the sintered density was about 45% of the theoretical value while for the conventionally made SnO₂ the sintered density was about 55% of the theoretical value. The sintered density of WO₃ was found to show a marked increase, from 55% to 70% of the theoretical value, as the sintering temperature was raised from 1000 to 1100° C.