Characterization of rapeseed (Brassica napus) oils by bulk C, O, H, and fatty acid C stable isotope analyses

Rapeseed (Brassica napus) oils differing in cultivar, sites of growth, and harvest year were characterized by fatty acid concentrations and carbon, hydrogen, and oxygen stable isotope analyses of bulk oils (delta(13)C(bulk), delta(2)H(bulk), delta(18)O(bulk) values) and individual fatty acids (delta(13)C(FA)). The delta(13)C(bulk), delta(2)H(bulk), and delta(18)O(bulk) values were determined by continuous flow combustion and high-temperature conversion elemental analyzer isotope ratio mass spectrometry (EA/IRMS, TC-EA/IRMS). The delta(13)C(FA) values were determined using gas chromatography-combustion isotope ratio mass spectrometry (GC/C/IRMS). For comparison, other C(3) vegetable oils rich in linolenic acid (flax and false flax oils) and rich in linoleic acid (poppy, sunflower, and safflower oils) were submitted to the same chemical and isotopic analyses. The bulk and molecular delta(13)C values were typical for C(3) plants. The delta(13)C value of palmitic acid (delta(13)C(16:0)) and n-3 alpha-linolenic acid (delta(13)C(18:3n-3)) differed (p < 0.001) between rape, flax, and poppy oils. Also within species, significant differences of delta(13)C(FA) were observed (p < 0.01). The hydrogen and oxygen isotope compositions of rape oil differed between cultivars (p < 0.05). Major differences in the individual delta(13)C(FA) values were found. A plant-specific carbon isotope fractionation occurs during the biosynthesis of the fatty acids and particularly during desaturation of C(18) acids in rape and flax. Bulk oil and specific fatty acid stable isotope analysis might be useful in tracing dietary lipids differing in their origin.

Development of Non-Petroleum Based Binders for Use in Flexible Pavements, TR-594, 2010

Most bituminous adhesives or binders that are used for pavement materials are derived primarily from fossil fuels. With petroleum oil reserves becoming depleted and the drive to establish a bio-based economy, there is a push to produce binders from alternative sources, particularly from biorenewable resources. However, until now, no research has studied the applicability of utilizing bio-oils as a bitumen replacement (100% replacement) in the pavement industry. The main objective of this research was to test various properties of bio-oils in order to determine the applicability of using bio-oils as binders in the pavement industry. The overall conclusions about the applicability of using bio-oils as bio-binders in the pavement industry can be summarized as follows: 1. Bio-oils cannot be used as bio-binders/pavement materials without any heat pre-treatment/upgrading procedure. 2. Current testing standards and specifications, especially Superpave procedures, should be modified to comply with the properties of bio-binders. 3. The temperature range of the viscous behavior for bio-oils may be lower than that of bitumen binders by about 30°–40° C. 4. The rheological properties of the unmodified bio-binders vary in comparison to bitumen binders, but the rheological properties of these modified bio-binders change significantly upon adding polymer modifiers. 5. The high-temperature performance grade for the developed bio-binders may not vary significantly from that of the bitumen binders, but the low-temperature performance grade may vary significantly

The Utilization of Agriculturally Derived Lignin as an Antioxidant in Asphalt Binder, TR-557, 2008

Oxidation is the primary cause of long-term aging in asphalt pavements. As a pavement oxidizes, it stiffens and can eventually crack. The use of an antioxidant as a performance enhancer in an asphalt binder could delay aging, thus increasing the life of an asphalt pavement. Lignin is a highly available and well-studied antioxidant. A wet-mill ethanol plant produces several co-products, some of which contain lignin. The use of lignin from ethanol production could provide a benefit to asphalt pavements and also give more value to the co-products. The following research examined the effects of lignin on asphalt pavements. Three lignin-containing co-products were separately combined with four asphalt binders in varying amounts to determine the optimum amount of co-product that would provide the greatest benefit to the asphalt binders. The asphalt binder and co-product blends were evaluated according to Superpave specifications and performance graded on a continuous scale. The data indicated a stiffening effect on the binder caused by the addition of the co-products. The more a co-product was added, the more a binder stiffened. Binder stiffening benefited the high temperature properties and the low temperature binder properties were negatively affected. However, the low temperature stiffening effects were small and in many cases not significant. The co-products had an overall effect of widening the temperature range of the binders. This result suggests some antioxidant activity between the binder and the lignin. Testing with a fourth co-product with no lignin supported the idea that lignin acts as an antioxidant. The samples with no lignin aged significantly more than the samples with lignin. Infrared spectrometry also supported the idea that lignin acts as an antioxidant by observing decreases in some oxidative aging products.

Predicting spinor condensate dynamics from simple principles

We study the spin dynamics of quasi-one-dimensional F=1 condensates both at zero and finite temperatures for arbitrary initial spin configurations. The rich dynamical evolution exhibited by these nonlinear systems is explained by surprisingly simple principles: minimization of energy at zero temperature and maximization of entropy at high temperature. Our analytical results for the homogeneous case are corroborated by numerical simulations for confined condensates in a wide variety of initial conditions. These predictions compare qualitatively well with recent experimental observations and can, therefore, serve as a guidance for ongoing experiments.

Combining phospholipases and a liquid lipase for one-step biodiesel production using crude oils

Background Enzymatic biodiesel is becoming an increasingly popular topic in bioenergy literature because of its potential to overcome the problems posed by chemical processes. However, the high cost of the enzymatic process still remains the main drawback for its industrial application, mostly because of the high price of refined oils. Unfortunately, low cost substrates, such as crude soybean oil, often release a product that hardly accomplishes the final required biodiesel specifications and need an additional pretreatment for gums removal. In order to reduce costs and to make the enzymatic process more efficient, we developed an innovative system for enzymatic biodiesel production involving a combination of a lipase and two phospholipases. This allows performing the enzymatic degumming and transesterification in a single step, using crude soybean oil as feedstock, and converting part of the phospholipids into biodiesel. Since the two processes have never been studied together, an accurate analysis of the different reaction components and conditions was carried out. Results Crude soybean oil, used as low cost feedstock, is characterized by a high content of phospholipids (900 ppm of phosphorus). However, after the combined activity of different phospholipases and liquid lipase Callera Trans L, a complete transformation into fatty acid methyl esters (FAMEs >95%) and a good reduction of phosphorus (P <5 ppm) was achieved. The combination of enzymes allowed avoidance of the acid treatment required for gums removal, the consequent caustic neutralization, and the high temperature commonly used in degumming systems, making the overall process more eco-friendly and with higher yield. Once the conditions were established, the process was also tested with different vegetable oils with variable phosphorus contents. Conclusions Use of liquid lipase Callera Trans L in biodiesel production can provide numerous and sustainable benefits. Besides reducing the costs derived from enzyme immobilization, the lipase can be used in combination with other enzymes such as phospholipases for gums removal, thus allowing the use of much cheaper, non-refined oils. The possibility to perform degumming and transesterification in a single tank involves a great efficiency increase in the new era of enzymatic biodiesel production at industrial scale.

Niobium and rare earth minerals from the Virulundo carbonatite, Namibe, Angola

The Virulundo carbonatite in Angola, one of the biggest in the world, contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias, trachytoids). The composition of the primary pyrochlore crystals is very close to fluornatrocalciopyrochlore in all these units. High-temperature hydrothermal processes caused the pseudomorphic replacement of the above crystals by a second generation of pyrochlore, characterized by lower F and Na contents. Low-temperature hydrothermal replacement of the above pyrochlores, associated with production of quartz-carbonates-fluorite veins, controled the development of a third generation of pyrochlore, characterized by high Sr contents. Finally, supergene processes produced the development of a secondary paragenesis in the carbonatite, consisting in late carbonates, goethite, hollandite and REE minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Separation of Ce from the other REE was allowed by oxidizing conditions. Therefore, Ce4+ was also incorporated into a late generation of pyrochlore, which is also strongly enriched in Ba and strongly depleted in Ca and Na

General electromagnetic simulation tool to predict the microwave nonlinear response of planar, arbitrarily-shaped HTS structures

This work describes a simulation tool being developed at UPC to predict the microwave nonlinear behavior of planar superconducting structures with very few restrictions on the geometry of the planar layout. The software is intended to be applicable to most structures used in planar HTS circuits, including line, patch, and quasi-lumped microstrip resonators. The tool combines Method of Moments (MoM) algorithms for general electromagnetic simulation with Harmonic Balance algorithms to take into account the nonlinearities in the HTS material. The Method of Moments code is based on discretization of the Electric Field Integral Equation in Rao, Wilton and Glisson Basis Functions. The multilayer dyadic Green's function is used with Sommerfeld integral formulation. The Harmonic Balance algorithm has been adapted to this application where the nonlinearity is distributed and where compatibility with the MoM algorithm is required. Tests of the algorithm in TM010 disk resonators agree with closed-form equations for both the fundamental and third-order intermodulation currents. Simulations of hairpin resonators show good qualitative agreement with previously published results, but it is found that a finer meshing would be necessary to get correct quantitative results. Possible improvements are suggested.

Bud dormancy in apple trees after thermal fluctuations

The objective of this work was to evaluate the effect of heat waves on the evolution of bud dormancy, in apple trees with contrasting chilling requirements. Twigs of 'Castel Gala' and 'Royal Gala' were collected in orchards in Papanduva, state of Santa Catarina, Brazil, and were exposed to constant (3°C) or alternating (3 and 15°C for 12/12 hours) temperature, combined with zero, one or two days a week at 25°C. Two additional treatments were evaluated: constant temperature (3°C), with a heat wave of seven days at 25°C, in the beginning or in the middle of the experimental period. Periodically, part of the twigs was transferred to 25°C for daily budburst evaluation of apical and lateral buds. Endodormancy (dormancy induced by cold) was overcome with less than 330 chilling hours (CH) of constant cold in 'Castel Gala' and less than 618 CH in 'Royal Gala'. A daily 15°C-temperature cycle did not affect the endodormancy process. Heat waves during endodormancy resulted in an increased CH to achieve bud requirements. The negative effect of high temperature depended on the lasting of this condition. Chilling was partly cancelled during dormancy when the heat wave lasted 36 continuous hours or more. Therefore, budburst prediction models need adjustments, mainly for regions with mild and irregular winters, such as those of Southern Brazil.

Procedures for evaluating the tolerance of cassava genotypes to postharvest physiological deterioration

Abstract: The objective of this work was to define procedures to assess the tolerance of cassava genotypes to postharvest physiological deterioration (PPD) and to microbial deterioration (MD). Roots of six cassava genotypes were evaluated in two experiments, during storage under different environmental conditions: high temperature and low soil moisture; or low temperature and high soil moisture. Roots were treated or not with fungicide (carbendazim) before storage. Genotype reactions to MD and PPD were evaluated at 0, 2, 5, 10, 15, 20, and 30 days after harvest (DAH), in the proximal, medial, and distal parts of the roots. A diagrammatic scale was proposed to evaluate nonperipheral symptoms of PPD. Fungicide treatment and root position did not influence PPD expression; however, all factors had significant effect on MD severity. Genotypes differed as to their tolerance to PPD and MD. Both deterioration types were more pronounced during periods of higher humidity and lower temperatures. The fungicide treatment increased root shelf life by reducing MD severity up to 10 DAH. Whole roots showed low MD severity and high PPD expression up to 10 DAH, which enabled the assessment of PPD without significant interference of MD symptoms during this period.

Vaihtokenttämagnetometrin suunnittelu ja rakentaminen

Tämän työn tavoitteena oli suunnitella ja rakentaa vaihtokenttämagnetometri, jolla voidaan tutkia näytteen magneettisia ominaisuuksia eri lämpötiloissa ja eri taajuuksilla. Menetelmänä käytettiin keskinäisinduktiotekniikkaa, joka on hyvin yleinen tapa tutkia aineen magneettista suskeptibiliteettiä. Magnetometriä ohjataan LabVIEW:lla tehdyllä käyttöliittymällä, joka suunniteltiin yksinkertaiseksi ja helpoksi käyttää. Ohjelma sisältää ohjeet, jotka auttavat parametrien ja toimintojen valinnoissa. LabVIEW:lla ohjataan askelmoottoria, näytteen lämmitintä, lämpötilan mittausta ja lukitusvahvistinta, jolta mittaustulokset saadaan. Laitteen testauksessa käytettiin korkean lämpötilan suprajohdetta YBa2Cu3O6+x, koska sillä saadaan aikaan suurisignaali. Mittaukset tehtiin nestemäisen typen lämpötilassa kahdella eri taajuuden arvolla. Laite antoi oikeanlaisen signaalin ulos eli todettiin laitteen toimivan. Laite toimii hyvin korkeammilla taajuuksilla. Mentäessä hyvin matalille taajuuksille, lukitusvahvistin ei pystynyt lukittumaan, eikä siis siten antanut oikeanlaisia tuloksia.

Maakaasun kuumailmapolton teoria ja koelaitteiston suunnittelu

Tässä diplomityössä on tarkasteltu maakaasun kuumailmapolton teoriaa ja suunniteltu koelaitteisto. Työn alkuosassa on käsitelty maakaasun ominaisuuksia kuumailmapolton polttoaineena. Lisäksi on vertailtu kuumailmapolttoa perinteiseen polttoon. Teoreettinen tarkastelu on painottunut kuumailmapolton toiminnallisiin vaatimuksiin, joiden perusteella koelaitteisto on suunniteltu. Uuden koelaitteiston lähtökohtana on ollut Lappeenrannan teknillisen yliopiston voimalaitostekniikan laboratorion polttolaitteisto, johon on suunniteltu ja rakennettu kuumailmapolton edellyttämät muutokset. Koelaitteistolla tehtäviä maakaasun kuumailmapolttokokeita varten on laadittu koesuunnitelma, mutta koepolttoja ei tämän diplomityön puitteissa ole tehty. Laitteiston toiminta-arvoja on tarkasteltu esimerkkilaskulla, jossa käsitellään tyypillistä maakaasun kuumailmapolton koetilannetta.

Puupolttoaineiden kuivausmenetelmien kartoitus

Työssä kartoitetaan käytössä olevia pilkkeen ja hakkeen keinokuivausmenetelmiä. Lisäksi arvioidaan menetelmien energiankulutusta ja kustannuksia, sekä käydään läpi kuivaajan suunnittelussa huomioon otettavia seikkoja. Työn ohessa on tehty Excel-laskentataulukko, jonka avulla voidaan arvioida lämpöyrittäjyyden kannattavuutta koko tuotantoketju huomioon ottaen. Lopussa tutkitaan kolmen erityyppisen pilkekuivurin käyttöä ja arvioidaan laskentataulukon avulla niiden vaikutuksia pilkeyrittäjän talouteen. Yleisin puupolttoaineiden keinokuivausmenetelmä on kylmäilmakuivaus. Sääriippuvuudesta ja usein epätasaisesta kuivauslaadusta johtuen se soveltuu vain pienimuotoiseen ja sivutoimiseen polttoainetuotantoon. Lisälämmityksellä parannetaan ilman kuivauskykyä, jolloin kuivaus on nopeampaa, loppukosteudet alhaisempia ja vuotuinen käyttöaika pitempi. Lämmitysratkaisun valinta riippuu kuivurin halutusta vuotuisesta käyttöajasta ja tuotantomääristä. Ammattimaiseen ja ympärivuotiseen pilketuotantoon soveltuu parhaiten korkeita, 70 - 90 °C lämpötiloja käyttävä kuivuri. Korkealämpötila-kuivurissa on tärkeää huolehtia riittävästä eristyksestä ja säädellystä ilmanvaihdosta. Suurilla polttopuun tuotantomäärillä kuljetuskustannukset korostuvat. Samalla kasvaa markkinoinnin tarve. Mainonnassa voidaan hyödyntää tehokasta kuivausmenetelmää.

ZnO nanorods for efficient third harmonic UV generation.

ZnO nanorods grown by both high temperature vapour phase transport and low temperature chemical bath deposition are very promising sources for UV third harmonic generation. Material grown by both methods show comparable efficiencies, in both cases an order of magnitude higher than surface third harmonic generation at the quartz-air interface of a bare quartz substrate. This result is in stark contrast to the linear optical properties of ZnO nanorods grown by these two methods, which show vastly different PL efficiencies. The third harmonic generated signal is analysed using intensity dependent measurements and interferometric frequency resolved optical gating, allowing extraction of the laser pulse parameters. The comparable levels of efficiency of ZnO grown by these very different methods as sources for third harmonic UV generation provides a broad suite of possible growth methods to suit various substrates, coverage and scalability requirements. Potential application areas range from interferometric frequency resolved optical gating characterization of few cycle fs pulses to single cell UV irradiation for biophysical studies.

Järeiden puutuotteiden erikoiskuivaus

Tutkimuksessa selvitettiin kuumakuivauksen vaikutusta hirsiraaka-aineen ominaisuuksiin, käyttökelpoisia kuivauskaavoja sekä lämpötilatasoja. Kokeissa kuivattiin kuorittuja pyöreitä mäntytukkeja 130-180° C:n maksimilämpötilassa, sekä pelkaksi sahattuja hirsiaihioita 115-140° C:n maksimilämpötilassa. Kuivauksissa pyrittiin mahdollisimman lyhyeen aikaan laadun siitä kuitenkaan kärsimättä. Laadussa kiinnitettiin erityisesti huomiota sisä- ja pintahalkeamiin sekä värimuutoksiin. Korkeita lämpötiloja käytettäessä kuivausaika oli huomattavasti nopeampi kuin lämminilmakuivauksessa. Koekuivaukset kestivät 1-4 vuorokautta, kun vastaavaa puutavaraan lämminilmakuivaus kestää 7-20 vuorokautta. Korkeimmilla lämpötiloilla suoritetuissa kokeissa koekappaleisiin muodostui paljon pieniä halkeamia kun taas alhaisemmilla lämpötiloilla halkeamien kappalemäärä väheni, mutta lähes joka kappaleessa oli vähintään yksi suuri (yli 5 mm leveä) halkeama. Sisähalkeamien määrä oli pyöreillä tukeilla suoritetuissa kokeissa kohtuullisen pieni. Pelkaksi sahatuilla aihioilla sitä vastoin sisähalkeamien määrä oli huomattavasti suurempi. Vain 100 mm x 175 mm aihioilla onnistuttiin yhdessä kuivauksessa pitämään sisähalkeaminen pienenä. Kuumakuivaus aiheuttaa väistämättä värimuutoksia puuhun. Mitä korkeammilla lämpötiloilla ja pidemmillä kaavoilla kuivataan sitä enemmän väri tummenee. Värin vaikutus lopputuotteessa riippuu kuitenkin käyttökohteesta ja asiakkaan mieltymyksistä. Tutkimuksen perusteella varsinkin pyöreiden tukkien kuumakuivaus näyttää onnistuvan laadul-lisesti hyvin ja huomattavasti lämminilmakuivausta nopeammin. Pelkaksi sahattujen hirsiaihioiden kuivauksessa prosessin hallinta havaittiin vaikeaksi ja toimivien kaavojen kehittäminen vaatii jatkotutkimuksia.

Kalvoerotusprosessin esikäsittely

Työn tavoitteena oli tutkia kiertoveden puhdistamiseen käytetyn kalvosuodatuksen esikäsittelymenetelmien vaikutusta ultrasuodatukseen. Suodatettava vesi oli kierrätyskuitua käyttävän paperikoneen kiekkosuotimen kirkassuodosta. Koeajon loppuosassa käytettiin biokirkassuodosta. Paperitehtaassa oli suljettu vesikierto. Pilot-laitteistona käytettiin Metso PaperChemin OptiFilter CR550/40 ultrasuodatusyksikköä. Testatut kalvot olivat C30 kalvoja. Suodatuksissa seurattiin esikäsittelymenetelmien vaikutusta permeaatin määrään ja laatuun. Ultrasuodatus tehtiin sekä ilman esikäsittelyä että lamelliselkeytin esikäsittelynä. Esikäsittelykemikaalina käytettiin talkkia. Ultrasuodatuksissa havaittiin, että suodatuslämpötilalla oli suora vaikutus kapasiteettiin. Lämpötila vaikutti lineaarisesti kirkassuodoksen ja biokirkassuodoksen permeaattivuohon. Lämpötila nostettiin 55oC:een suodatuslämpötilasta 35 – 40oC. Korkeassa lämpötilassa kirkassuodos oli kapasiteetiltaan suurempi kuin biokirkassuodos. Konsentrointiajoista nähtiin, että ultrasuodatuksen syötön konsentraatioaste vaikutti kirkassuodoksen permeaattivuohon. Syötön konsentraatioastetta lisättäessä kapasiteetti laski. Konsentrointiajoja vertailtaessa havaitaan, että ilman esikäsittelyä vuo laski konsentroitaessa nopeammin kuin suodatuksissa, joissa käytettiin esikäsittelyä. Lamelliselkeyttimellä ja talkilla esikäsitelty suodatus laski kapasiteettia vähiten. Konsentraatioasteen nostaminen lisäsi konsentraatin kemiallista hapenkulutusta. Konsentraatin viskositeetti nousi konsentraatioastetta lisättäessä. Analyysitulosten perusteella saadaan ultrasuodatuskalvoille tyypilliset reduktiot. COD-reduktio oli 10 – 30 %, anionisuuden 40 – 70 % ja värin 80 – 90 %. Vuon kanssa korreloivat pH, uuteaine, ligniini, viskositeetti ja hemiselluloosat.