Modelling intermittent microwave convective drying (IMCD) of food materials

This thesis develops comprehensive mathematical models for an advanced drying technology Intermittent Microwave Convective Drying (IMCD). The models provide an improved physical understanding of the heat and mass transport during the drying process, which will help to improve the quality of dried food and energy efficiency of the process, as well as will increase the ability of automation and optimization. The final model in this thesis represents the most comprehensive fundamental multiphase model for IMCD that considers 3D electromagnetics coupled with multiphase porous media transport processes. The 3D electromagnetics considers Maxwell's equation and multiphase transport model considers three different phases: solid matrix, liquid water and gas consisting water vapour and air. The multiphase transport includes pressure-driven flow, capillary diffusion, binary diffusion, and evaporation. The models developed in this thesis were validated with extensive experimental investigations.

On the mathematical modeling of wound healing angiogenesis in skin as a reaction-transport process

Over the last 30 years, numerous research groups have attempted to provide mathematical descriptions of the skin wound healing process. The development of theoretical models of the interlinked processes that underlie the healing mechanism has yielded considerable insight into aspects of this critical phenomenon that remain difficult to investigate empirically. In particular, the mathematical modeling of angiogenesis, i.e., capillary sprout growth, has offered new paradigms for the understanding of this highly complex and crucial step in the healing pathway. With the recent advances in imaging and cell tracking, the time is now ripe for an appraisal of the utility and importance of mathematical modeling in wound healing angiogenesis research. The purpose of this review is to pedagogically elucidate the conceptual principles that have underpinned the development of mathematical descriptions of wound healing angiogenesis, specifically those that have utilized a continuum reaction-transport framework, and highlight the contribution that such models have made toward the advancement of research in this field. We aim to draw attention to the common assumptions made when developing models of this nature, thereby bringing into focus the advantages and limitations of this approach. A deeper integration of mathematical modeling techniques into the practice of wound healing angiogenesis research promises new perspectives for advancing our knowledge in this area. To this end we detail several open problems related to the understanding of wound healing angiogenesis, and outline how these issues could be addressed through closer cross-disciplinary collaboration.

Microbial life and deposits in paper machine circuits

Väitöskirjani käsittele mikrobien ja erilaisten kemikaalien rooleja saostumien ja biofilmien muodostumisessa paperi- ja kartonkikoneilla. "Saostuma" tässä työssä tarkoittaa kiinteän aineen kertymää konepinnoille tai rajapinnoille konekierroissa, jotka on tarkoitettu massasulppujen, lietteiden, vesien tai ilman kuljetukseen. Saostumasta tulee "biofilmi" silloin kun sen oleellinen rakennekomponentti on mikrobisolut tai niiden tuotteet. Väitöstyöni työhypoteesina oli, että i. tietämys saostumien koostumuksesta, sekä ii. niiden rakenteesta, biologisista, fysikaalis-kemiallisista ja teknisistä ominaisuuksista ohjaavat tutkijaa löytämään ympäristöä säästäviä keinoja estää epätoivottujen saostumien muodostus tai purkaa jo muodostuneita saostumia. Selvittääkseni saostumien koostumista ja rakennetta käytin monia erilaisia analytiikan työkaluja, kuten elektronimikroskopiaa, konfokaali-laser mikroskopiaa (CLSM), energiadispersiivistä röntgenanalyysiä (EDX), pyrolyysi kaasukromatografiaa yhdistettynä massaspektrometriaan (Py-GCMS), joninvaihtokromatografiaa, kaasukromatografiaa ja mikrobiologisia analyysejä. Osallistuin aktiivisesti innovatiivisen, valon takaisinsirontaan perustuvan sensorin kehittämistyöhön, käytettäväksi biofilmin kasvun mittaukseen suoraan koneen vesikierroista ja säiliöistä. Työni osoitti, että monet paperinvalmistuksessa käytetyistä kemikaaleista reagoivat keskenään tuottaen orgaanisia tahmakerroksia konekiertojen teräspinnoille. Löysin myös kerrostumia, jotka valomikroskooppisessa tarkastelussa oli tulkittu mikrobeiksi, mutta jotka elektronimikroskopia paljasti alunasta syntyneiksi, alumiinihydroksidiksi joka saostui pH:ssa 6,8 kiertokuitua käyttävän koneen viiravesistä. Monet paperintekijät käyttävät vieläkin alunaa kiinnitysaineena vaikka prosessiolot ovat muuttuneet happamista neutraaleiksi. Sitä pidetään paperitekijän "aspiriinina", mutta väitöstutkimukseni osoitti sen riskit. Löysin myös orgaanisia saostumia, joiden alkuperä oli aineiden, kuten pihkan, saippuoituminen (kalsium saippuat) niin että muodostui tahmankasvua ylläpitävä alusta monilla paperi- ja kartonkikoneilla. Näin solumuodoiltaan Deinococcus geothermalista muistuttavia bakteereita kasvamassa lujasti teräskoepalojen pintaan kiinnittyneinä pesäkkeinä, kun koepaloja upotettiin paperikoneiden vesikiertoihin. Nämä deinokokkimaiset pesäkkeet voivat toimia jalustana, tarttumisalustana muiden mikrobien massoille, joka selittäisi miksi saostumat yleisesti sisältävät deinokokkeja pienenä, muttei koskaan pääasiallisena rakenneosana. Kun paperikoneiden käyttämien vesien (raakavedet, lämminvesi, biologisesti puhdistettu jätevesi) laatua tutkitaan, mittausmenetelmällä on suuri merkitys. Koepalan upotusmenetelmällä todettu biofilmikasvu ja viljelmenetelmällä mitattu bakteerisaastuneisuus korreloivat toisiinsa huonosti etenkin silloin kun likaantumisessa oli mukana rihmamaiseti kasvavia bakteereja. Huoli ympäristöstä on pakottanut paperi- ja kartonkikoneiden vesikiertojen sulkemiseen. Vesien kierrätys ja prosessivesien uudelleenkäyttö nostavat prosessilämpötilaa ja lisäävät koneella kiertävien kolloidisten ja liuenneiden aineiden määriä. Tutkin kiertovesien pitoisuuksia kolmessa eriasteisesti suljetussa tehtaassa, joiden päästöt olivat 0 m3, 0,5 m3 ja 4 m3 jätevettä tuotetonnia kohden, perustuen puhdistetun jäteveden uudelleen käyttöön. Nollapäästöisellä tehtaalla kiertovesiin kertyi paljon orgaanisesti sidottua hiiltä (> 10 g L-1), etenkin haihtuvina happoina (maito-, etikka-, propioni- ja voi-). Myös sulfaatteja, klorideja, natriumia ja kalsiumia kertyi paljon, > 1 g L-1 kutakin. Pääosa (>40%) kaikista bakteereista oli 16S rRNA geenisekvenssianalyysien tulosten perusteella sukua, joskin etäistä (< 96%) ainoastaan Enterococcus cecorum bakteerille. 4 m3 päästävältä tehtaalta löytyi lisäksi Bacillus thermoamylovorans ja Bacillus coagulans. Tehtaiden saostumat sisälsivät arkkeja suurina pitoisuuksina, ≥ 108 g-1, mutta tunnistukseen riittävää sekvenssisamanlaisuutta löytyi vain yhteen arkkisukuun, Methanothrix. Tutkimustulokset osoittivat että tehtaan vesikiertojen sulkeminen vähensi rajusti mikrobiston monimuotoisuutta, muttei estänyt liuenneen aineen ja kiintoaineen mineralisoitumista.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.

Synthesis of ZnO Nanoneedles on Flexible Polymer Substrates at Room Temperature by Activated Reactive Evaporation

ZnO nanoneedles were successfully deposited on flexible polymer substrates at room temperature by activated reactive evaporation. Neither a catalyst nor a template was employed in this synthesis. These synthesized needles measured 500 - 600 nm in length and its diameter varied from 30 - 15 nm from the base to the tip. The single-crystalline nature of the nanoneedle was observed by high-resolution transmission electron microscopy studies. The Raman studies on these nanoneedles had shown that they are oxygen deficient in nature. A possible growth mechanism has been proposed here, in which the nanoneedles nucleate and grow in the gas phase by vapor-solid mechanism.

Role of entropy in the stability of cobalt titanates

The standard molar Gibbs free energy of formation of Co2TiO4, CoTiO3,and CoTi2O5 as a function of temperature over an extended range (900 to 1675) K was measured using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte, with CoO as reference electrode and appropriate working electrodes. For the formation of the three compounds from their component oxides CoO with rock-salt and TiO2 with rutile structure, the Gibbs free energy changes are given by:Delta(f)G degrees((ox))(Co2TiO4) +/- 104/(J . mol(-1)) = -18865 - 4.108 (T/K)Delta(f)G degrees((ox))(CoTiO3) +/- 56/(J . mol(-1)) = -19627 + 2.542 (T/K) Delta(f)G degrees((ox))(CoTi2O5) +/- 52/(J . mol(-1)) = -6223 - 6.933 (T/K) Accurate values for enthalpy and entropy of formation were derived. The compounds Co2TiO4 with spinel structure and CoTi2O5 with pseudo-brookite structure were found to be entropy stabilized. The relatively high entropy of these compounds arises from the mixing of cations on specific crystallographic sites. The stoichiometry of CoTiO3 was confirmed by inert gas fusion analysis for oxygen. Because of partial oxidation of cobalt in air, the composition corresponding to the compound Co2TiO4 falls inside a two-phase field containing the spinet solid solution Co2TiO4-Co3O4 and CoTiO3. The spinel solid solution becomes progressively enriched in Co3O4 with decreasing temperature. (c) 2010 Elsevier Ltd. All rights reserved.

An SOx (x = 2, 3) sensor using ?-alumina/Na2SO4 couple

A solid-state sensor for SOx (x = 2, 3) species has been designed using ?-alumina as the solid electrolyte and Na2SO4 as the auxiliary electrode. The measured e.m.f. of the cell Pt, O?2 + SO?2 + SO?3|Na2SO4short parallel?-aluminashort parallelNa2SO4|SO?3 + SO?2 + O?2, PT in the temperature range 700 K to 1150 K agrees well with values calculated using the Nernst equation. The sodium sulphate acts both as a protective covering, preventing direct access of the gaseous SOx species to the ?-alumina electrolyte, and as an auxiliary electrode, converting chemical potentials of SOx species and O2 into an equivalent sodium potential. The open-circuit e.m.f. varies non-linearly with temperature for fixed composition of inlet gas mixtures containing SO2, O2 and Ar. The response time (t0.99) of the cell varies between 1.9 ks at 750 K and 0.06 ks at 1100 K. The e.m.f. response is faster when the partial pressure of SOx at the electrode is increased than when it is decreased.

Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

Effect of laser processing parameters on the structure of ductile iron

Laser processing of structure sensitive hypereutectic ductile iron, a cast alloy employed for dynamically loaded automative components, was experimentally investigated over a wide range of process parameters: from power (0.5-2.5 kW) and scan rate (7.5-25 mm s(-1)) leading to solid state transformation, all the way through to melting followed by rapid quenching. Superfine dendritic (at 10(5) degrees C s(-1)) or feathery (at 10(4) degrees C s(-1)) ledeburite of 0.2-0.25 mu m lamellar space, gamma-austenite and carbide in the laser melted and martensite in the transformed zone or heat-affected zone were observed, depending on the process parameters. Depth of geometric profiles of laser transformed or melt zone structures, parameters such as dendrile arm spacing, volume fraction of carbide and surface hardness bear a direct relationship with the energy intensity P/UDb2, (10-100 J mm(-3)). There is a minimum energy intensity threshold for solid state transformation hardening (0.2 J mm(-3)) and similarly for the initiation of superficial melting (9 J mm(-3)) and full melting (15 J mm(-3)) in the case of ductile iron. Simulation, modeling and thermal analysis of laser processing as a three-dimensional quasi-steady moving heat source problem by a finite difference method, considering temperature dependent energy absorptivity of the material to laser radiation, thermal and physical properties (kappa, rho, c(p)) and freezing under non-equilibrium conditions employing Scheil's equation to compute the proportion of the solid enabled determination of the thermal history of the laser treated zone. This includes assessment of the peak temperature attained at the surface, temperature gradients, the freezing time and rates as well as the geometric profile of the melted, transformed or heat-affected zone. Computed geometric profiles or depth are in close agreement with the experimental data, validating the numerical scheme.

Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Phase relations in the system SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K were established by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 105 Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y2O3-CuO-O2, except for the limited substitution of Y3+ for Sr2+ ions in the ternary oxide Sr14Cu24O41, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr14−xYxCu24O41 and the compound SrCuO2+δ lie above the plane containing SrO, Y2O3, and CuO,displaced towards the oxygen apex. However, in the system CaO-Y203-CuO-O2 at 1173 K, all the condensed phases lie on the plane containing CaO, Y203, and CuO, and a new quaternary oxide YCa2Cu306.s is present. The quaternary phase has a composition that lies at the center of the nonstoichiometric field of the analogous phase YBa2Cu307_~ in the BaO-Y203-CuO-O2 system. The compound YCa2Cu306.s has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y203-CuO-O2, SrO-Y203-CuO-O2, and BaO-Y203-CuO-O2 are found to be quite different.

USEFUL EXTENSIONS OF THE HENRY REACTION: EXPEDITIOUS ROUTES TO NITROALKANES AND NITROALKENES IN AQUEOUS MEDIA

The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu)(3)SnH in water under microwave irradiation (80 degrees C/10 min), or dehydrated to the corresponding nitroalkenes with K2CO3 in water (generally 0-5 degrees C/20 min). Both ``one-pot'' reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.

Effect of Zirconium on the Densification of Reactively Hot-Pressed Zirconium Carbide

Densification mechanisms involved during reactive hot pressing (RHP) of zirconium carbide (ZrC) have been studied. RHP has been carried out using zirconium (Zr) and graphite (C) powders in the molar ratios 1:0.5, 1:0.67, 1:0.8, and 1:1 at 40MPa, 800 degrees C-1200 degrees C for different durations. The volume fractions of phases formed, including porosity, are determined from the measured density and from Rietveld analysis. Increased densification with an increasing nonstoichiometry in carbon has been observed. Microstructural and X-ray diffraction observations coupled with the predictions of a model based on the constitutive laws governing plastic flow of zirconium suggest that the better densification of nonstoichiometric compositions arise from the higher amount of starting Zr and also the longer duration of its availability for plastic flow during RHP. Volume shrinkage due to reaction between Zr and C and the gradual elimination of the soft metal phase limit the final density achievable. Based on these observations, a two-step RHP carried out at 800 degrees C and 1200 degrees C leads to a better densification than a single RHP at 1200 degrees C.

Computational modeling of reactive hot pressing of zirconium carbide

A model of reactive hot pressing of zirconium carbide (ZrCx, 0.5 < x < 1) has been constructed that incorporates four processes that occur in parallel: creep of zirconium (Zr), reaction of Zr and carbon (C), increase in volume fraction of hard phase with progressive reaction that reduces the creep of Zr and, finally, de-densification associated with volume reduction during reaction. The reasonable agreement of the model with experimental results verifies that plastic deformation of Zr is the main factor that is responsible for the low-temperature reactive densification of ZrC and that ZrC may be treated as a rigid inclusion that contributes little to densification. It predicts that densification is impaired by increasing carbon stoichiometry due to the increasing amount of starting hard phase and the greater contraction upon reaction. Additionally, the model predicts that mixtures of Zr and ZrC should show equal or better densification than Zr and C mixtures.

TiO2-RGO hybrid nanomaterials for enhanced water splitting reaction

The production of H-2 via photocatalytic water splitting reaction has attracted a great attention as a clean and renewable energy for next generation. Despite tremendous efforts, the present challenge for materials scientist is to develop highly active photo catalysts for splitting of water at low cost. This article reports the synthesis of TiO2-reduced graphene oxide hybrid nanomaterials through ionothermal method using functionalized ionic liquid for the enhanced hydrogen generation via water splitting reaction. The structural and morphological properties of the samples were investigated by XFtD, Raman spectroscopy, TG-DTA, UV-vis spectroscopy and TEM. A substantial increase of H-2 evolution was observed for TiO2-reduced graphene oxide hybrid nanomaterials. This is due to the high migration efficiency of photo-induced electrons and the inhibition of charge carrier recombination due to the electronic interaction between TiO2 and reduced graphene oxide. i.e, reduced graphene oxide acts as an electron-acceptor which effectively hinders the electron hole pair recombination of TiO2. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.