Physical aging of amorphous fructose

Physical aging of amorphous anhydrous fructose at temperature 5 degreesC and at 22 degreesC was studied using differential scanning calorimetry (DSC). The dynamic glass transitions temperature, T-g0 for unaged samples was 16 degreesC and 13.3 degreesC for heating rate of 10 degreesC/min and 1 degreesC/min, respectively. The fictive temperature, T-f0 for unaged samples calculated by Richardson and Savill method was 12 degreesC, which is close to the dynamic value obtained from the lower DSC heating rate. The fictive temperature T-f of the aged fructose glasses at temperatures both below and above the transition region was fitted well by a non-exponential decay function (Williams-Watts form). Aging above the transition region (22 degreesC) for 18 d increased both the dynamic glass transition temperature T and the fictive temperature T-f. However, aging below the transition region (5 degreesC) for I d increased the dynamic glass transition temperature T-g but decreased the fictive temperature T-f.

Body temperature regulation and outcome after cardiac arrest and therapeutic hypothermia.

OBJECTIVE: Therapeutic temperature modulation is recommended after cardiac arrest (CA). However, body temperature (BT) regulation has not been extensively studied in this setting. We investigated BT variation in CA patients treated with therapeutic hypothermia (TH) and analyzed its impact on outcome. METHODS: A prospective cohort of comatose CA patients treated with TH (32-34°C, 24h) at the medical/surgical intensive care unit of the Lausanne University Hospital was studied. Spontaneous BT was recorded on hospital admission. The following variables were measured during and after TH: time to target temperature (TTT=time from hospital admission to induced BT target <34°C), cooling rate (spontaneous BT-induced BT target/TTT) and time of passive rewarming to normothermia. Associations of spontaneous and induced BT with in-hospital mortality were examined. RESULTS: A total of 177 patients (median age 61 years; median time to ROSC 25 min) were studied. Non-survivors (N=90, 51%) had lower spontaneous admission BT than survivors (median 34.5 [interquartile range 33.7-35.9]°C vs. 35.1 [34.4-35.8]°C, p=0.04). Accordingly, time to target temperature was shorter among non-survivors (200 [25-363]min vs. 270 [158-375]min, p=0.03); however, when adjusting for admission BT, cooling rates were comparable between the two outcome groups (0.4 [0.2-0.5]°C/h vs. 0.3 [0.2-0.4]°C/h, p=0.65). Longer duration of passive rewarming (600 [464-744]min vs. 479 [360-600]min, p<0.001) was associated with mortality. CONCLUSIONS: Lower spontaneous admission BT and longer time of passive rewarming were associated with in-hospital mortality after CA and TH. Impaired thermoregulation may be an important physiologic determinant of post-resuscitation disease and CA prognosis. When assessing the benefit of early cooling on outcome, future trials should adjust for patient admission temperature and use the cooling rate rather than the time to target temperature.

The Gibbs free energy of formation of a glass alloy

A simple expression for the Gibbs free energy of formation of a pure component or a eutectic alloy glass, relative to the stable crystalline phase (or phases) at the same temperature is deduced by use of thermodynamic arguments. The expression obtained is supposed to apply to both monocomponent and multicomponent liquid alloys that might become glasses from the supercooled liquid state, irrespective of the critical cooling rate needed to avoid crystallization.

Control and Simulation of Batch Crystallization

Concerning process control of batch cooling crystallization the present work focused on the cooling profile and seeding technique. Secondly, the influence of additives on batch-wise precipitation process was investigated. Moreover, a Computational Fluid Dynamics (CFD) model for simulation of controlled batch cooling crystallization was developed. A novel cooling model to control supersaturation level during batch-wise cooling crystallization was introduced. The crystallization kinetics together with operating conditions, i.e. seed loading, cooling rate and batch time, were taken into account in the model. Especially, the supersaturation- and suspension density- dependent secondary nucleation was included in the model. The interaction between the operating conditions and their influence on the control target, i.e. the constant level of supersaturation, were studied with the aid of a numerical solution for the cooling model. Further, the batch cooling crystallization was simulated with the ideal mixing model and CFD model. The moment transformation of the population balance, together with the mass and heat balances, were solved numerically in the simulation. In order to clarify a relationship betweenthe operating conditions and product sizes, a system chart was developed for anideal mixing condition. The utilization of the system chart to determine the appropriate operating condition to meet a required product size was introduced. With CFD simulation, batch crystallization, operated following a specified coolingmode, was studied in the crystallizers having different geometries and scales. The introduced cooling model and simulation results were verified experimentallyfor potassium dihydrogen phosphate (KDP) and the novelties of the proposed control policies were demonstrated using potassium sulfate by comparing with the published results in the literature. The study on the batch-wise precipitation showed that immiscible additives could promote the agglomeration of a derivative of benzoic acid, which facilitated the filterability of the crystal product.

Cristalização e taxa crítica de resfriamento para vitrificação do poli(sebacato de decametileno)

We synthesized Poly(decamethylene sebacate) - P10MS - and studied its overall crystallization rates in a range of temperatures using Differential Scanning Calorimetry in isothermal conditions, which enabled us to identify the crystallization mechanism by means of the Johnson-Mehl-Avrami-Kolmogorov equation. The critical cooling rate (Rc) to vitrify the P10MS was determined using a non-isothermal method proposed by Barandiarán & Colmenero (BC). The value of Rc is around 50-250 K/s, which confirms the experimentally observed difficulty to vitrify this polymer.

The influence of crystallization conditions on the filtration characteristics of sulphathiazole suspensions

Cooling crystallization is one of the most important purification and separation techniques in the chemical and pharmaceutical industry. The product of the cooling crystallization process is always a suspension that contains both the mother liquor and the product crystals, and therefore the first process step following crystallization is usually solid-liquid separation. The properties of the produced crystals, such as their size and shape, can be affected by modifying the conditions during the crystallization process. The filtration characteristics of solid/liquid suspensions, on the other hand, are strongly influenced by the particle properties, as well as the properties of the liquid phase. It is thus obvious that the effect of the changes made to the crystallization parameters can also be seen in the course of the filtration process. Although the relationship between crystallization and filtration is widely recognized, the number of publications where these unit operations have been considered in the same context seems to be surprisingly small. This thesis explores the influence of different crystallization parameters in an unseeded batch cooling crystallization process on the external appearance of the product crystals and on the pressure filtration characteristics of the obtained product suspensions. Crystallization experiments are performed by crystallizing sulphathiazole (C9H9N3O2S2), which is a wellknown antibiotic agent, from different mixtures of water and n-propanol in an unseeded batch crystallizer. The different crystallization parameters that are studied are the composition of the solvent, the cooling rate during the crystallization experiments carried out by using a constant cooling rate throughout the whole batch, the cooling profile, as well as the mixing intensity during the batch. The obtained crystals are characterized by using an automated image analyzer and the crystals are separated from the solvent through constant pressure batch filtration experiments. Separation characteristics of the suspensions are described by means of average specific cake resistance and average filter cake porosity, and the compressibilities of the cakes are also determined. The results show that fairly large differences can be observed between the size and shape of the crystals, and it is also shown experimentally that the changes in the crystal size and shape have a direct impact on the pressure filtration characteristics of the crystal suspensions. The experimental results are utilized to create a procedure that can be used for estimating the filtration characteristics of solid-liquid suspensions according to the particle size and shape data obtained by image analysis. Multilinear partial least squares regression (N-PLS) models are created between the filtration parameters and the particle size and shape data, and the results presented in this thesis show that relatively obvious correlations can be detected with the obtained models.

Hitsausvirtalähteen ohjaus lämmöntuonnin ja jatkuvan jäähtymisen S-käyrän perusteella

Lämmöntuonnilla on oleellinen vaikutus hitsausliitoksen ominaisuuksiin, koska se vaikuttaa liitoksen jäähtymisnopeuteen, jolla on puolestaan suuri vaikutus jäähtymisessä syntyviin mikrorakenteisiin. Jatkuvan jäähtymisen S-käyrältä voidaan ennustaa hitsausliitokseen syntyvät mikrorakenteet. S-käyrät voidaan laatia hitsausolosuhteiden mukaisesti, jolloin faasimuutoskäyttäytyminen sularajalla saadaan selvitettyä. Tämän diplomityön tavoitteena oli kehittää hitsausvirtalähteen ohjaustapaa lämmöntuontiin ja jatkuvan jäähtymisen S-käyriin perustuen. Jatkuvan jäähtymisen S-käyrillä ja lämmöntuontiin perustuvalla hitsausparametrien säädöllä on yhteys. Työssä tutkittiin, miten haluttuun jäähtymisnopeuteen johtava lämmöntuonti voidaan määrittää S-käyrälle luotettavasti. Työssä perehdyttiin jatkuvan jäähtymisen S-käyriin ja eri jäähtymisnopeuksilla hitsausliitokseen syntyviin mikrorakenteisiin sekä hitsaus-inverttereiden ohjaus- ja säätötekniikkaan. Teoriaosuuden jälkeen tarkasteltiin eri vaihtoehtoja, miten hitsattavan materiaalin koostumusvaihtelut sekä lämmöntuontiin vaikuttavat tekijät voidaan ottaa huomioon virtalähteen ohjauksessa lämmöntuonnin perusteella. S-käyrältä määritettyjen lämmöntuonnin arvojen perusteella tehtiin kahdet koehitsaukset, joissa käytettiin kolmea eri aineenpaksuutta. Tulosten perusteella arvioitiin lämmöntuonnin arvojen toimivuutta käytännössä ja tutkittiin liitokseen syntyviä mikrorakenteita. Tutkimuksen pohjalta esitettiin jatkokehitystoimenpiteitä, joiden mukaan voidaan edetä lämmöntuontiin perustuvan säätöjärjestelmän kehitysprojektissa.

Surface transformation hardening of carbon steel with high power fiber laser

This study investigated the surface hardening of steels via experimental tests using a multi-kilowatt fiber laser as the laser source. The influence of laser power and laser power density on the hardening effect was investigated. The microhardness analysis of various laser hardened steels was done. A thermodynamic model was developed to evaluate the thermal process of the surface treatment of a wide thin steel plate with a Gaussian laser beam. The effect of laser linear oscillation hardening (LLOS) of steel was examined. An as-rolled ferritic-pearlitic steel and a tempered martensitic steel with 0.37 wt% C content were hardened under various laser power levels and laser power densities. The optimum power density that produced the maximum hardness was found to be dependent on the laser power. The effect of laser power density on the produced hardness was revealed. The surface hardness, hardened depth and required laser power density were compared between the samples. Fiber laser was briefly compared with high power diode laser in hardening medium-carbon steel. Microhardness (HV0.01) test was done on seven different laser hardened steels, including rolled steel, quenched and tempered steel, soft annealed alloyed steel and conventionally through-hardened steel consisting of different carbon and alloy contents. The surface hardness and hardened depth were compared among the samples. The effect of grain size on surface hardness of ferritic-pearlitic steel and pearlitic-cementite steel was evaluated. In-grain indentation was done to measure the hardness of pearlitic and cementite structures. The macrohardness of the base material was found to be related to the microhardness of the softer phase structure. The measured microhardness values were compared with the conventional macrohardness (HV5) results. A thermodynamic model was developed to calculate the temperature cycle, Ac1 and Ac3 boundaries, homogenization time and cooling rate. The equations were numerically solved with an error of less than 10-8. The temperature distributions for various thicknesses were compared under different laser traverse speed. The lag of the was verified by experiments done on six different steels. The calculated thermal cycle and hardened depth were compared with measured data. Correction coefficients were applied to the model for AISI 4340 steel. AISI 4340 steel was hardened by laser linear oscillation hardening (LLOS). Equations were derived to calculate the overlapped width of adjacent tracks and the number of overlapped scans in the center of the scanned track. The effect of oscillation frequency on the hardened depth was investigated by microscopic evaluation and hardness measurement. The homogeneity of hardness and hardened depth with different processing parameters were investigated. The hardness profiles were compared with the results obtained with conventional single-track hardening. LLOS was proved to be well suitable for surface hardening in a relatively large rectangular area with considerable depth of hardening. Compared with conventional single-track scanning, LLOS produced notably smaller hardened depths while at 40 and 100 Hz LLOS resulted in higher hardness within a depth of about 0.6 mm.

Lämpökynttilän palo-ominaisuuksiin vaikuttavien tekijöiden analytiikka: raaka-aineet, sydänlanka, rakenne ja olosuhteet

Työn tavoitteena oli tutkia lämpökynttilän palo-ominaisuuksiin vaikuttavia tekijöitä. Työn taustalla on yhteistyö suomalaisen kynttilävalmistajan kanssa. Kynttilävalmistajan lämpökynttilöissään käyttämän raaka-aineen hinnan noustessa, on valmistaja kiinnostunut käyttämään edullisempia raaka-aineita. Palamisen kriteerit saavuttavan kynttilän valmistaminen markkinoilla olevista uusista raaka-aineista on havaittu olevan haastavaa, ja vaatii edelleen kehitystyötä. Teoriaosassa käytiin läpi kynttilänvalmistusta yleisesti, RAL-laatustandardin asettamat kriteerit lämpökynttilälle, palamiseen vaikuttavia tekijöitä sekä työn kokeellisessa osassa käytettyjen analyysimenetelmien periaatteet. Työn kokeellisessa osassa tutkittiin erilaisten kynttiläraaka-aineiden koostumusta ja ominaisuuksia sekä sydänlankojen rakennetta. Lisäksi tutkittiin, miten sydänlangan sisältämien säikeiden määrä, eri raaka-aineiden seossuhteiden muutos sekä jäähdytyslämpötilan muutos vaikuttavat lämpökynttilän palo-ominaisuuksiin. Työssä myös selvitettiin muutaman markkinoilla olevan kynttilän raaka-ainekoostumus. Tutkimuksissa havaittiin, että vaadittavan liekin korkeuden saavuttamiseksi viskositeetti on yksi raaka-aineen tärkeimmistä ominaisuuksista. Raaka-aineen viskositeetin kasvaessa tarvitaan paksumpi sydänlanka. Raaka-aineen viskositeetin kasvaessa liekin korkeus ei aina pienene, koska liekin korkeuteen vaikuttaa myös langalle tehty kemiallinen käsittely. Mitä korkeampi kynttilän liekki on, sitä suurempi on raaka-aineen kulutus eli palovuo ja tällöin liekin korkeus vaikuttaa myös kynttilän paloaikaan. Kokeissa havaittiin, että liekin korkeuden ollessa vakio, palovuo oli korkein steariinilla. Steariinin jälkeen tulivat palmuvaha ja parafiini. Tällöin parafiinia tarvittiin vähemmän vastaavan paloajan saavuttamiseksi. Nopean jäähdytyksen havaittiin vaikuttavan palmuvahan palovuohon alentavasti, vaikka jäähdytystavalla ei ollut vaikutusta liekin korkeuteen.

Lumen varastointi ja hyödyntäminen tilojen jäähdytykseen, Case: Kone Oyj

Tämän diplomityön tarkoituksena on selvittää mahdollisuutta hyödyntää lunta tilojen jäähdytykseen Koneen Hyvinkään tehdasalueella. Työssä kerrotaan myös yleisesti eri jäähdytysmuodoista ja tuotantotavoista. Eri kirjallisuuslähteiden pohjalta tutkittiin erilaisia lumijäähdytysjärjestelmiä, joiden energiataseiden pohjalta tehtiin sopiva malli kohdealueelle. Mallin avulla selvitettiin lumesta hyödynnettävä jäähdytysenergian määrä. Esitetylle varastolle hahmoteltiin investointi- ja käyttökustannukset kirjallisuuslähteiden ja asiantuntijoiden avulla. Kustannuksien ja jäähdytysenergiamäärien avulla laskettiin lumijäähdytyksen tuotantokustannukset, joita verrattiin perinteiseen kompressorijäähdyttimeen. Lopuksi pohdittiin vielä takaisinmaksuaikoja lumivaraston liittyessä nykyisiin jäähdytysjärjestelmiin ja kokonaan uuteen jäähdytysverkostoon. Tuloksien mukaan lumijäähdytys ei ole taloudellisesti kannattavaa Koneen Hyvinkään tehdasalueella. Ongelmaksi muodostui investointikustannusten suuruus verrattuna saatuihin säästöihin. Ympäristöllisesti ja yrityksellisesti hanketta voidaan pitää kannattavana. Lumijäähdytyksestä voidaan saada kannattavampi suuremmilla lumimäärillä, mikä vaatisi myös suuremmat jäähdytysenergiankulutukset kuin Koneella on. Myös hyödyntämällä luonnon omia rakenteita voidaan parantaa kannattavuutta.

Influence of Pulsed-Electric Field Irradiation in Crystallization

The growing pharmaceutical interest, among others, in the polymorphic composition of the emerging solid end-products from production processes has been traced to the need for attainment of high product purity. This is more so as the presence of different polymorphs may constitute physical impurity of the product. Hence, the need for optimization of the yield of desired product component(s) through controlled crystallization kinetics for instance. This study was carried out to investigate the impact of pulsed electric field (PEF) irradiation on the crystal morphology of glycine obtained by cooling crystallization (without seeding) from commercial glycine sample in distilled deionized water solution. In doing so, three different pulse frequencies (294, 950 and 145 Hz) and a case without PEF were studied at three cooling rates (5, 10 and 20 ºC/h). The crystal products obtained were analyzed for polymorphic composition by powder x-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy while the particles characterization was done on Morphologi G3. The results obtained from this study showed that pulsed electric field irradiation had significant impact on metastability of the aqueous solution as well as on the polymorphic composition of the end product. With increasing PEF frequency applied, nucleation started earlier and the γ-glycine polymorph content of the product crystals increased. These were found to have been aided by cooling rate, as the most significant effect was observed at 5 ºC/h. It was also discovered that PEF application had no measurable impact on the pH of the aqueous solution as well as the size distribution of the particles. Cooling on the contrary was believed to be responsible for the broadening of the particle size distribution with a downward shift of the lower limit of the raw material from about 100 μm to between 10 and 50 μm.

Underwater Remote Welding Technology for Offshore Structures

The construction of offshore structures, equipment and devices requires a high level of mechanical reliability in terms of strength, toughness and ductility. One major site for mechanical failure, the weld joint region, needs particularly careful examination, and weld joint quality has become a major focus of research in recent times. Underwater welding carried out offshore faces specific challenges affecting the mechanical reliability of constructions completed underwater. The focus of this thesis is on improvement of weld quality of underwater welding using control theory. This research work identifies ways of optimizing the welding process parameters of flux cored arc welding (FCAW) during underwater welding so as to achieve desired weld bead geometry when welding in a water environment. The weld bead geometry has no known linear relationship with the welding process parameters, which makes it difficult to determine a satisfactory weld quality. However, good weld bead geometry is achievable by controlling the welding process parameters. The doctoral dissertation comprises two sections. The first part introduces the topic of the research, discusses the mechanisms of underwater welding and examines the effect of the water environment on the weld quality of wet welding. The second part comprises four research papers examining different aspects of underwater wet welding and its control and optimization. Issues considered include the effects of welding process parameters on weld bead geometry, optimization of FCAW process parameters, and design of a control system for the purpose of achieving a desired bead geometry that can ensure a high level of mechanical reliability in welded joints of offshore structures. Artificial neural network systems and a fuzzy logic controller, which are incorporated in the control system design, and a hybrid of fuzzy and PID controllers are the major control dynamics used. This study contributes to knowledge of possible solutions for achieving similar high weld quality in underwater wet welding as found with welding in air. The study shows that carefully selected steels with very low carbon equivalent and proper control of the welding process parameters are essential in achieving good weld quality. The study provides a platform for further research in underwater welding. It promotes increased awareness of the need to improve the quality of underwater welding for offshore industries and thus minimize the risk of structural defects resulting from poor weld quality.

Grain refinement studies on Mg and Mg-Al based alloys

Demand on magnesium and its alloys is increased significantly in the automotive industry because of their great potential in reducing the weight of components, thus resulting in improvement in fuel efficiency of the vehicle. To date, most of Mg products have been fabricated by casting, especially, by die-casting because of its high productivity, suitable strength, acceptable quality & dimensional accuracy and the components produced through sand, gravity and low pressure die casting are small extent. In fact, higher solidification rate is possible only in high pressure die casting, which results in finer grain size. However, achieving high cooling rate in gravity casting using sand and permanent moulds is a difficult task, which ends with a coarser grain nature and exhibit poor mechanical properties, which is an important aspect of the performance in industrial applications. Grain refinement is technologically attractive because it generally does not adversely affect ductility and toughness, contrary to most other strengthening methods. Therefore formation of fine grain structure in these castings is crucial, in order to improve the mechanical properties of these cast components. Therefore, the present investigation is “GRAIN REFINEMENT STUDIES ON Mg AND Mg-Al BASED ALLOYS”. The primary objective of this present investigation is to study the effect of various grain refining inoculants (Al-4B, Al- 5TiB2 master alloys, Al4C3, Charcoal particles) on Pure Mg and Mg-Al alloys such as AZ31, AZ91 and study their grain refining mechanisms. The second objective of this work is to study the effect of superheating process on the grain size of AZ31, AZ91 Mg alloys with and without inoculants addition. In addition, to study the effect of grain refinement on the mechanical properties of Mg and Mg-Al alloys. The thesis is well organized with seven chapters and the details of the studies are given below in detail.

Vertical velocity variance and skewness in clear and cloud-topped boundary layers as revealed by Doppler lidar

In this paper, observations by a ground-based vertically pointing Doppler lidar and sonic anemometer are used to investigate the diurnal evolution of boundary-layer turbulence in cloudless, cumulus and stratocumulus conditions. When turbulence is driven primarily by surface heating, such as in cloudless and cumulus-topped boundary layers, both the vertical velocity variance and skewness follow similar profiles, on average, to previous observational studies of turbulence in convective conditions, with a peak skewness of around 0.8 in the upper third of the mixed layer. When the turbulence is driven primarily by cloud-top radiative cooling, such as in the presence of nocturnal stratocumulus, it is found that the skewness is inverted in both sign and height: its minimum value of around −0.9 occurs in the lower third of the mixed layer. The profile of variance is consistent with a cloud-top cooling rate of around 30Wm−2. This is also consistent with the evolution of the thermodynamic profile and the rate of growth of the mixed layer into the stable nocturnal boundary layer from above. In conditions where surface heating occurs simultaneously with cloud-top cooling, the skewness is found to be useful for diagnosing the source of the turbulence, suggesting that long-term Doppler lidar observations would be valuable for evaluating boundary-layer parametrization schemes. Copyright c 2009 Royal Meteorological Society

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.