Aukko-osuuden mittausmenetelmien kartoitus PWR PACTEL -koelaitteiston pystyhöyrystimen sekundääripuolella

Diplomityössä kartoitetaan mahdollisuuksia aukko-osuuden mittaamiseksi ydinvoimalaitosta mallintavan PWR PACTEL -koelaitteiston pystyhöyrystimen sekundääripuolella. Työ on toteutettu osana kansallista SAFIR2014-ydinturvallisuustutkimusohjelmaa. Diplomityön tavoitteena on löytää kustannuksiltaan mahdollisimman järkevä ja toimiva menetelmä aukko-osuuden määrittämiseksi. Aukko-osuuden mittaaminen on tärkeää sekundääripuolen kaksifaasivirtauksen käyttäytymisen paremman tuntemuksen lisäämiseksi. Aukko-osuusmittausdataa tarvitaan muun muassa laskentakoodien validointiin. Diplomityössä perehdytään kaksifaasivirtauksen ja aukko-osuuden fysiikkaan sekä esitellään erityyppisiä aukko-osuuden mittausmenetelmiä. Kunkin mittausmenetelmän soveltuvuutta PWR PACTEL -koelaitteistoon arvioidaan erikseen. Aukko-osuuden mittaaminen höyrystimen sekundääripuolella osoittautuu käytännössä erittäin hankalaksi. Pääasiassa tämä johtuu höyrystimen rakenteesta sekä mittausmenetelmien korkeista kustannuksista. Tämän vuoksi työssä tarkastellaan myös edellytyksiä aukko-osuuden mittaamiselle erillisessä höyrystintä mallintavassa koelaitteistossa. Mikäli aukko-osuutta haluttaisiin mitata erilliskoelaitteistossa, tulisi höyrystinmallin rakennetta, materiaaleja tai kiertoainetta muuttaa PWR PACTELin höyrystimeen verrattuna.

Decomposition kinetics of gaseous ozone in peanuts

This study was conducted to evaluate the decomposition kinetics of gaseous ozone in peanut grains. This evaluation was made with 1-kg peanut samples, moisture contents being 7.1 and 10.5% wet basis (w.b.), placed in 3-liter glass containers. The peanut grains were ozonated at the concentration of 450 µg L-1, at 25 and 35 ºC, with gas flow rates of 1.0 and 3.0 L min-1. Time of saturation was determined by quantifying the residual concentration of ozone after the gas passed through the grains to constant mass. The decomposition kinetics of ozone was evaluated after the grain mass was ozone-saturated. For the peanut grains whose moisture content was 7.1% (w.b.), at 25 and 35ºC and with flow rates of 1.0 and 3.0 L min-1, the values obtained for time of saturation of gaseous ozone ranged between 173 and 192 min; the concentration of saturation was approximately 260 µg L-1. For the grains whose moisture content was 10.5% (w.b.), a higher residual concentration of gaseous ozone was obtained at 25 ºC, that of 190 µg L-1. As regards the half-life of ozone, the highest value obtained was equivalent to 7.7 min for grains ozonated at 25 ºC, while for those with moisture content of 10.5% at 35 ºC, half-life was 3.2 min. In the process of ozone decomposition in peanut grains, temperature was concluded to be the key factor. An increase of 10 ºC in the temperature of the grains results in a decrease of at least 43% in the half-life of ozone.

Turbulenssimallien soveltuminen syklonien numeeriseen virtauslaskentaan

Tässä työssä tutkittiin miten totuudenmukaisia tuloksia syklonierottimen virtauskentästä saadaan numeerisella laskennalla, kun käytetään eri turbulenssimalleja. Tarkoitus oli myös selvittää yleisesti syklonin toimintaperiaatteita, haasteita sen käytössä sekä syklonin numeerisen virtauslaskennan perusteita. Numeerisen virtauslaskennan teoria selitetään pääpiirteittäin, samoin turbulenssin mallinnus. Työn laskentaosiossa simuloitiin Fluent-ohjelmalla syklonin virtauskenttää kuumalla ilmalla sekä kahdella eri turbulenssimallilla ja verrattiin tuloksia kirjallisuudesta löytyviin mittaustuloksiin. Simuloinnit suoritettiin sekä ajasta riippuvana että ajasta riippumattomana ja kahdella eri laskentahilalla. Simulointien tulokset osoittivat, että RNG k-ε turbulenssimalli ei kykene tuottamaan totuu-denmukaista virtauskenttää. Toisen käytetyn turbulenssimallin, Reynolds-jännitysmallin tulokset vastasivat enemmän mittaustuloksia. Reynolds-jännitysmallia voidaan pitää käyttökelpoisena syklonin simuloinnissa tämän työn ja kirjallisuuden perusteella. Mallissa oli yksinkertaistuksia, esimerkiksi kiinteää ainetta ei otettu huomioon lainkaan.

Large-eddy simulation of wind flows over complex terrains for wind energy applications

Wind energy has obtained outstanding expectations due to risks of global warming and nuclear energy production plant accidents. Nowadays, wind farms are often constructed in areas of complex terrain. A potential wind farm location must have the site thoroughly surveyed and the wind climatology analyzed before installing any hardware. Therefore, modeling of Atmospheric Boundary Layer (ABL) flows over complex terrains containing, e.g. hills, forest, and lakes is of great interest in wind energy applications, as it can help in locating and optimizing the wind farms. Numerical modeling of wind flows using Computational Fluid Dynamics (CFD) has become a popular technique during the last few decades. Due to the inherent flow variability and large-scale unsteadiness typical in ABL flows in general and especially over complex terrains, the flow can be difficult to be predicted accurately enough by using the Reynolds-Averaged Navier-Stokes equations (RANS). Large- Eddy Simulation (LES) resolves the largest and thus most important turbulent eddies and models only the small-scale motions which are more universal than the large eddies and thus easier to model. Therefore, LES is expected to be more suitable for this kind of simulations although it is computationally more expensive than the RANS approach. With the fast development of computers and open-source CFD software during the recent years, the application of LES toward atmospheric flow is becoming increasingly common nowadays. The aim of the work is to simulate atmospheric flows over realistic and complex terrains by means of LES. Evaluation of potential in-land wind park locations will be the main application for these simulations. Development of the LES methodology to simulate the atmospheric flows over realistic terrains is reported in the thesis. The work also aims at validating the LES methodology at a real scale. In the thesis, LES are carried out for flow problems ranging from basic channel flows to real atmospheric flows over one of the most recent real-life complex terrain problems, the Bolund hill. All the simulations reported in the thesis are carried out using a new OpenFOAM® -based LES solver. The solver uses the 4th order time-accurate Runge-Kutta scheme and a fractional step method. Moreover, development of the LES methodology includes special attention to two boundary conditions: the upstream (inflow) and wall boundary conditions. The upstream boundary condition is generated by using the so-called recycling technique, in which the instantaneous flow properties are sampled on aplane downstream of the inlet and mapped back to the inlet at each time step. This technique develops the upstream boundary-layer flow together with the inflow turbulence without using any precursor simulation and thus within a single computational domain. The roughness of the terrain surface is modeled by implementing a new wall function into OpenFOAM® during the thesis work. Both, the recycling method and the newly implemented wall function, are validated for the channel flows at relatively high Reynolds number before applying them to the atmospheric flow applications. After validating the LES model over simple flows, the simulations are carried out for atmospheric boundary-layer flows over two types of hills: first, two-dimensional wind-tunnel hill profiles and second, the Bolund hill located in Roskilde Fjord, Denmark. For the twodimensional wind-tunnel hills, the study focuses on the overall flow behavior as a function of the hill slope. Moreover, the simulations are repeated using another wall function suitable for smooth surfaces, which already existed in OpenFOAM® , in order to study the sensitivity of the flow to the surface roughness in ABL flows. The simulated results obtained using the two wall functions are compared against the wind-tunnel measurements. It is shown that LES using the implemented wall function produces overall satisfactory results on the turbulent flow over the two-dimensional hills. The prediction of the flow separation and reattachment-length for the steeper hill is closer to the measurements than the other numerical studies reported in the past for the same hill geometry. The field measurement campaign performed over the Bolund hill provides the most recent field-experiment dataset for the mean flow and the turbulence properties. A number of research groups have simulated the wind flows over the Bolund hill. Due to the challenging features of the hill such as the almost vertical hill slope, it is considered as an ideal experimental test case for validating micro-scale CFD models for wind energy applications. In this work, the simulated results obtained for two wind directions are compared against the field measurements. It is shown that the present LES can reproduce the complex turbulent wind flow structures over a complicated terrain such as the Bolund hill. Especially, the present LES results show the best prediction of the turbulent kinetic energy with an average error of 24.1%, which is a 43% smaller than any other model results reported in the past for the Bolund case. Finally, the validated LES methodology is demonstrated to simulate the wind flow over the existing Muukko wind farm located in South-Eastern Finland. The simulation is carried out only for one wind direction and the results on the instantaneous and time-averaged wind speeds are briefly reported. The demonstration case is followed by discussions on the practical aspects of LES for the wind resource assessment over a realistic inland wind farm.

Korkeasti kuormitetun soodakattilan likaantumisen ja päästöjen vähentäminen

Tässä työssä perehdytään korkeasti kuormitettujen soodakattiloiden tyypillisiin ongelmiin. Ongelmia ovat likaantuminen ja tukkeutuminen sekä liialliset päästöt. Työn teoriaosassa esitetään taustat likaantumiselle ja päästöjen muodostumiselle. Molemmat johtuvat suurelta osin tulipesän huonosta toiminnasta. Soodakattilan ilmajärjestelmä ja mustalipeän ruiskutus vaikuttavat tulipesän toimintaan. Usein tulipesän toimintaa voidaan parantaa ilmajärjestelmän ja lipeänruiskutuksen säätöjä muuttamalla. Suurempi muutos tulipesän toimintaan saadaan uusimalla perinteinen sekundääri-ilmajärjestelmä vertikaali-ilmajärjestelmäksi. Nykyaikainen vertikaali-ilmajärjestelmä sekoittaa savukaasut tehokkaasti ja saa aikaan tasaisemman virtauksen tulipesään. Myös mustalipeän korkea kloori- ja kaliumpitoisuus voivat aiheuttaa lämpöpintojen likaantumista. Oikea nuohointen sijainti on tärkeä tekijä kattilan puhtaana pysymisen kannalta. Työn kokeellisessa osassa selvitetään, kuinka erään eukalyptussellutehtaan korkeasti kuormitetun soodakattilan käytettävyyttä voidaan parantaa ja kapasiteettia nostaa soodakattilan toimintaa virittämällä. Kattilan nykyinen ajomalli ja ongelmat selvitettiin. Tulipesän toimintaa testattiin muuttamalla ilmajakoa primääri-, sekundääri- ja tertiääri-ilman välillä ja muuttamalla sekundääri-ilman syöttöä tulipesään. Testien ja kerätyn tiedon perusteella voitiin päätellä, miten soodakattilaa kannattaa modernisoida kapasiteetin nostamiseksi ja käytettävyyden parantamiseksi. Usein tulipesän toimintaa ja käytettävyyttä voidaan parantaa paljon jo pienilläkin muutostöillä. Kapasiteetin nostaminen vaatii tavallisesti suuremman investoinnin ja pidennetyn vuosihuoltoseisokin.

Tandem-MAG-welding of high strength steels for shipbuilding applications

Tämän työn tavoitteena oli hitsata tandem MAG –laitteistolla 25 mm paksua Ruukin E500 TMCP terästä. Työssä oli tarkoituksena vähentää railotilavuutta mahdollisimman paljon sekä suorittaa testihitsaukset 0.8 kJ/mm sekä 2.5 kJ/mm lämmöntuonneilla. Teoriaosuudessa käsiteltiin Tandem MAG-hitsaukseen, sen tuottavuuteen ja laatukysymyksiin liittyviä asioita sekä siinä perehdyttiin suurlujuusteräksien käyttöön hitsauksessa sekä laivanrakennuksessa. Kokeellisessa osuudessa perehdyttiin hitsauksessa huomattuihin etuihin, ongelmiin sekä ongelmien ratkaisumahdollisuuksiin. Hitsausliitoksen mekaaniset ominaisuudet tutkittiin rikkomattomin sekä rikkovin menetelmin. Alustavat hitsausohjeet luotiin kummallekin lämmöntuonnille. Testaukset aloitettiin 30 º railokulmalla pienentäen kulmaa mahdollisuuksien mukaan. Testauksissa ei saatu hitsattua onnistuneesti alle 30 º railokulmalla. Hitsaustestien aikana huomattiin magneettisen puhalluksen vaikutus hitsaustapahtumaan. Kaasunvirtausnopeuden tuli olla tietyn suuruinen jotta palkokerrokset onnistuivat ilman huokoisuusongelmaa. Pienemmällä lämmöntuonnilla hitsattaessa kaasunvirtausnopeudet olivat tärkeämpiä hitsatessa ylempiä palkokerroksia. Kääntämällä hitsauspoltinta sivuttaissuunnassa 7-10 astetta auttoi ehkäisemään reunahaavan syntymistä. Rikkovista menetelmistä testitulokset olivat hyväksyttyjä kaikkien muiden paitsi päittäishitsin sivutaivutuskokeen osalta.

Rheological characterization of polysaccharide gels

In this Master’s Thesis work the rheological properties of different polysaccharide gels have been studied. The results of this study are used as a starting point for further investigations of potential applications. In order to understand rheological behavior of studied materials, the commercial hydrocolloids such as sodium carboxymethyl cellulose, xanthan gum and guar gum were used as reference and comparison material for rheological studies. As a part the rheological research the development and implementation of proper measurement methods for studied materials were carried out. In the literature review, short introductions of studied materials and application areas of rheological modifiers are summarized. In addition, basic rheological concepts and key fundamentals are explained. In the experimental part the focus was on the rheological characterization of aqueous suspensions of studied materials. Especially, gel strength and solution stability were investigated. The rheological measurements included both rotational and oscillatory measurements in different conditions, where several chemical and physical properties were measured with Anton Paar MCR302 dynamic rotational rheometer. Studied polysaccharide gels can be clearly defined to be shear thinning and thixotropic materials. They have strong gel forming properties even at low concentrations, which explains the superior thickening behavior for some of the samples. Along with rheological characterization of selected materials the factors behind different phenomena were investigated. To reveal value and potential use of polysaccharide gels the influence of various factors such as concentration, temperature and ionic strength were determined. The measurements showed a clear difference between studied materials under investigated external parameters.

Effect of whey protein concentrate on texture of fat-free desserts: sensory and instrumental measurements

It is important to understand how changes in the product formulation can modify its characteristics. Thus, the objective of this study was to investigate the effect of whey protein concentrate (WPC) on the texture of fat-free dairy desserts. The correlation between instrumental and sensory measurements was also investigated. Four formulations were prepared with different WPC concentrations (0, 1.5, 3.0, and 4.5 wt. (%)) and were evaluated using the texture profile analysis (TPA) and rheology. Thickness was evaluated by nine trained panelists. Formulations containing WPC showed higher firmness, elasticity, chewiness, and gumminess and clearly differed from the control as indicated by principal component analysis (PCA). Flow behavior was characterized as time-dependent and pseudoplastic. Formulation with 4.5% WPC at 10 °C showed the highest thixotropic behavior. Experimental data were fitted to Herschel-Bulkley model. The addition of WPC contributed to the texture of the fat-free dairy dessert. The yield stress, apparent viscosity, and perceived thickness in the dairy desserts increased with WPC concentration. The presence of WPC promotes the formation of a stronger gel structure as a result of protein-protein interactions. The correlation between instrumental parameters and thickness provided practical results for food industries.

Dynamic modeling and simulation of the airflow cleaning device

The objective of the work is to study the flow behavior and to support the design of air cleaner by dynamic simulation.In a paper printing industry, it is necessary to monitor the quality of paper when the paper is being produced. During the production, the quality of the paper can be monitored by camera. Therefore, it is necessary to keep the camera lens clean as wood particles may fall from the paper and lie on the camera lens. In this work, the behavior of the air flow and effect of the airflow on the particles at different inlet angles are simulated. Geometries of a different inlet angles of single-channel and double-channel case were constructed using ANSYS CFD Software. All the simulations were performed in ANSYS Fluent. The simulation results of single-channel and double-channel case revealed significant differences in the behavior of the flow and the particle velocity. The main conclusion from this work are in following. 1) For the single channel case the best angle was 0 degree because in that case, the air flow can keep 60% of the particles away from the lens which would otherwise stay on lens. 2) For the double channel case, the best solution was found when the angle of the first inlet was 0 degree and the angle of second inlet was 45 degree . In that case, the airflow can keep 91% of particles away from the lens which would otherwise stay on lens.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Analyse par spectrométrie de masse d’hormones stéroïdiennes dans les eaux usées et abattement par oxydation chimique

Thèse réalisée en cotutelle avec Michèle Prévost (Ph.D), Professeure titulaire au département des génies civil, géologique et des mines de l'École Polytechnique de Montréal.

Plasma polymerization of C[subscript 4]F[subscript 8] thin film on high aspect ratio silicon molds

High aspect ratio polymeric micro-patterns are ubiquitous in many fields ranging from sensors, actuators, optics, fluidics and medical. Second generation PDMS molds are replicated against first generation silicon molds created by deep reactive ion etching. In order to ensure successful demolding, the silicon molds are coated with a thin layer of C[subscript 4]F[subscript 8] plasma polymer to reduce the adhesion force. Peel force and demolding status are used to determine if delamination is successful. Response surface method is employed to provide insights on how changes in coil power, passivating time and gas flow conditions affect plasma polymerization of C[subscript 4]F[subscript 8].

A review and simplification of the in vitro incubation medium

The requirement to rapidly and efficiently evaluate ruminant feedstuffs places increased emphasis on in vitro systems. However, despite the developmental work undertaken and widespread application of such techniques, little attention has been paid to the incubation medium. Considerable research using in vitro systems is conducted in resource-poor developing countries that often have difficulties associated with technical expertise, sourcing chemicals and/or funding to cover analytical and equipment costs. Such limitations have, to date, restricted vital feed evaluation programmes in these regions. This paper examines the function and relevance of the buffer, nutrient, and reducing solution components within current in vitro media, with the aim of identifying where simplification can be achieved. The review, supported by experimental work, identified no requirement to change the carbonate or phosphate salts, which comprise the main buffer components. The inclusion of microminerals provided few additional nutrients over that already supplied by the rumen fluid and substrate, and so may be omitted. Nitrogen associated with the inoculum was insufficient to support degradation and a level of 25 mg N/g substrate is recommended. A sulphur inclusion level of 4-5 mg S/g substrate is proposed, with S levels lowered through omission of sodium sulphide and replacement of magnesium sulphate with magnesium chloride. It was confirmed that a highly reduced medium was not required, provided that anaerobic conditions were rapidly established. This allows sodium sulphide, part of the reducing solution, to be omitted. Further, as gassing with CO2 directly influences the quantity of gas released, it is recommended that minimum CO, levels be used and that gas flow and duration, together with the volume of medium treated, are detailed in experimental procedures. It is considered that these simplifications will improve safety and reduce costs and problems associated with sourcing components, while maintaining analytical precision. (c) 2005 Elsevier B.V. All rights reserved.

A rheological and SAXS study of the lamellar order in a side-on liquid crystalline block copolymer

We study the structure and shear flow behavior of a side-on liquid crystalline triblock copolymer, named PBA-b-PA444-b-PBA (PBA is poly(butyl acrylate) and PA444 is a poly(acrylate) with a nematic liquid crystal side-on mesogen), in the self-assembled lamellar phase and in the disordered phase. Simultaneous oscillatory shear and small-angle X-ray scattering experiments show that shearing PBA-b-PA444-b-PBA at high frequency and strain amplitudes leads to the alignment of the lamellae with normals perpendicular to the shear direction and to the velocity gradient direction, i.e., in the perpendicular orientation. The order-to-disorder transition temperature (T-ODT) is independent of the applied strain, in contrast to results reported in the literature for coil-coil diblock copolymers, which show an increase in T-ODT with shear rate. It is possible that in our system, T-ODT does not depend on the applied strain because the fluctuations are weaker than those present in coil-coil diblock copolymer systems.