Polttomoottorivoimalan energiatehokkuuden parantaminen hukkalämpövirtojen sähköksi muunnolla

Tämä diplomityö on osa FCEP hankeen Lappeenrannan teknillisessä yliopistossa tehtävää tutkimusta polttomoottoreiden energiatehokkuuden parantamisesta. Työn tavoitteena on saada tutkimustietoa polttomoottoreiden hukkalämpövirtojen hyödyntämisestä sähköntuotannossa. Tavoitteena on kartoittaa polttomoottorin hukkalämpövirtojen sähköksi muunnon potentiaalia valituilla menetelmillä ja tekniikoilla. Työssä tarkasteltavaksi moottoriksi valittiin DF- monipolttoainemoottori. DF-moottorin polttoaineena voidaan käyttää joko kaasua tai polttoöljyä. Laskennat suoritettiin moottorin valmistajan antamien hukkalämpövirtojen arvojen ja moottorin lämpötaseen avulla. Laskennan perusperiaatteena oli vesihöyryprosessin ja ORC-prosessien vertailu pakokaasulämmön hyödyntämisessä sekä matalalämpöisten hukkalämpövirtojen hyödyntäminen ORC-prosesseilla. Lisäksi työssä tutkittiin korkealla painesuhteella ja korkealla hyötysuhteella toimivan turboahtimen vaikutusta hukkalämpövirroista saatavaan tehoon. Diplomityössä tarkasteltiin moottorin lämpötaseen mukaisten arvojen lisäksi moottorin parametrien muuttamisen vaikutusta hukkalämpövirroista saatavaan tehoon. Moottorin parametrien muuttamisen vaikutusta moottorin akselitehoon tai moottorin lämpötaseeseen ei kuitenkaan tämän tutkimuksen puitteissa tarkasteltu. Työssä saatiin arvokasta tietoa polttomoottoreiden hukkalämpövirtojen muuntamisesta sähköksi eri menetelmillä sekä moottorin energiatehokkuuden parantamisesta.

Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.

Lujien hitsattavien terästen käyttäytyminen -60 °C:ssa

Opinnäytetyö on osa Arctic Materials Technologies Development -projektia, jonka tavoitteena on kehittää perusteita arktisten alueiden sovelluksiin suunnittelun ja valmistuksen kannalta. Arktisella alueella sijaitsee useita potentiaalisia öljy- ja maakaasuesiintymiä, joiden hyödyn-täminen tulee vuosi vuodelta kannattavammaksi ilmaston lämpenemisestä johtuvan merijään heikkenemisen vuoksi. Alin suunnittelulämpötila arktisilla alueilla on -60 °C, mikä aiheuttaa haasteita sekä materiaalinvalinnalle että hitsaukselle. Ferriittisillä teräksillä esiintyy lämpötilasta riippuvaa sitkeyden vaihtelua, jota kutsutaan transi-tiokäyttäytymiseksi. Lämpötilan laskiessa teräksen iskusitkeys sekä murtumissitkeys laske-vat. Arktisissa sovelluskohteissa käytetään yleisesti niukkaseosteisia, mikroseostettuja hie-noraeteräksiä, joille on ominaista erinomaiset sitkeys-, lujuus- sekä hitsattavuusominaisuudet vaativissakin olosuhteissa. Lujat termomekaanisesti valssatut ja nuorrutetut hienoraeteräkset kattavat myötölujuusluokat 355…700 MPa. Tutkimuksissa on saatu vaihtelevia tuloksia ma-teriaalien isku- ja murtumissitkeydestä -60 °C:ssa. Erityisesti sitkeysominaisuudet hitsiaineen ja muutosvyöhykkeen alueiden välillä ovat vaihtelevia. Pienemmällä lämmöntuonnilla ja seostetuilla lisäaineilla saavutetaan kuitenkin pääsääntöisesti parempia sitkeysarvoja. Asiku-laarinen ferriitti sekä alabainiitti ovat toivottavia mikrorakenteita liitoksessa, niiden pienen raekoon johdosta.

Rasvankestävät paperit ja kartongit

Rasvankestävyydellä tarkoitetaan sitä, että materiaali hylkii tai kestää rasvaa tietyn ajan läpäisemättä sen pintaa. Rasvankestäviä papereita ja kartonkeja löytyy kaikkialta. Erilaiset ruuanvalmistuspaperit, kuten esimerkiksi leivinpaperi ja voipaperi, ovat rasvankestäviä. Myös pakkauksissa käytetään paljon rasvankestäviä papereita ja kartonkeja. Rasvankestäviltä tuotteilta vaaditaan erilaisia ominaisuuksia riippuen niiden käyttötarkoituksesta. Pakkausmateriaaleilta vaaditaan esimerkiksi lujuutta ja kestävyyttä fyysistä rasitusta, valoa, hajuja ja mikrobeja vastaan. Ruuanvalmistusmateriaaleilta vaaditaan puolestaan lujuutta ja kestävyyttä lämpöä, kosteutta ja fyysistä rasitusta vastaan. Rasvankestäviltä papereilta vaaditaan rasvankestävyyden lisäksi hyvää vetolujuutta, märkälujuutta ja hyviä optisia ominaisuuksia. Neliömassan tulee asettua 20─80 g/m2 välille ja metallipitoisuudet eivät saa olla liian korkeat. Myös tuotteiden kierrätettävyys on nostanut asemaansa viimeaikoina. Tuotteen tuotannon ja itse tuotteen ympäristöystävällisyys ovat todella arvostettuja kuluttajan, tuottajan, Suomen, EU:n ja koko maailman näkökulmista. Jotta tuotteesta saadaan rasvankestävää, vaaditaan siltä erilaisia barrier-ominaisuuksia. Rasvankestävällä paperilla vaaditaan hyviä barrier-ominaisuuksia esimerkiksi rasvan, ilman, veden, vesihöyryn sekä hapen läpäisevyyksissä. Rasvankestäviä papereita ja kartonkeja voidaan valmistaa kemiallisilla ja mekaanisilla tavoilla. Happokäsittely ja fluorokemikaalien lisääminen ovat kemiallisia tapoja, kun taas sellun jauhaminen pitkään matalassa lämpötilassa on mekaaninen tapa valmistaa rasvankestävää paperia. Näiden tapojen lisäksi rasvankestäviä papereita voidaan tehdä erilaisten pinnoitusten avulla. Erilaiset muovit ovat yleisemmin käytettyjä pinnoitemateriaaleja. Esimerkiksi PE- ja PET-päällysteet ovat käytettyjä rasvankestävissä tuotteissa. Viime aikoina on kehitetty paljon erilaisia biomateriaaleja, joista voidaan tehdä rasvankestävä pinnoite. Lipideistä, hydrokolloideista ja erilaisista komposiiteista voidaan luoda uusien tekniikoiden avulla rasvankestäviä pinnoitteita. Rasvankestävyydestä voidaan saada jonkinlainen käsitys WVTR-asteen, Cobb-arvon ja kontaktikulman mittausten avulla. Rasvankestävyyttä voidaan myös mitata erilaisten standarditestien avulla. TAPPI:lla, ISO:lla ja ASTM:llä on useita erilaisia standardeja. Lähes kaikissa rasvankestävyysstandardeissa tuloksen saaminen perustuu visuaaliseen havaintoon, mikä aiheuttaa välillä hankaluuksia tulosten luotettavuuteen, koska tuloksen määrittää ihmissilmä, ja kaikilla testin tekijöillä on erilainen silmä, joka aistii eri tavalla.

Characterisation of Laser Beam and Paper Material Interaction

It is known already from 1970´s that laser beam is suitable for processing paper materials. In this thesis, term paper materials mean all wood-fibre based materials, like dried pulp, copy paper, newspaper, cardboard, corrugated board, tissue paper etc. Accordingly, laser processing in this thesis means all laser treatments resulting material removal, like cutting, partial cutting, marking, creasing, perforation etc. that can be used to process paper materials. Laser technology provides many advantages for processing of paper materials: non-contact method, freedom of processing geometry, reliable technology for non-stop production etc. Especially packaging industry is very promising area for laser processing applications. However, there are only few industrial laser processing applications worldwide even in beginning of 2010´s. One reason for small-scale use of lasers in paper material manufacturing is that there is a shortage of published research and scientific articles. Another problem, restraining the use of laser for processing of paper materials, is colouration of paper material i.e. the yellowish and/or greyish colour of cut edge appearing during cutting or after cutting. These are the main reasons for selecting the topic of this thesis to concern characterization of interaction of laser beam and paper materials. This study was carried out in Laboratory of Laser Processing at Lappeenranta University of Technology (Finland). Laser equipment used in this study was TRUMPF TLF 2700 carbon dioxide laser that produces a beam with wavelength of 10.6 μm with power range of 190-2500 W (laser power on work piece). Study of laser beam and paper material interaction was carried out by treating dried kraft pulp (grammage of 67 g m-2) with different laser power levels, focal plane postion settings and interaction times. Interaction between laser beam and dried kraft pulp was detected with different monitoring devices, i.e. spectrometer, pyrometer and active illumination imaging system. This way it was possible to create an input and output parameter diagram and to study the effects of input and output parameters in this thesis. When interaction phenomena are understood also process development can be carried out and even new innovations developed. Fulfilling the lack of information on interaction phenomena can assist in the way of lasers for wider use of technology in paper making and converting industry. It was concluded in this thesis that interaction of laser beam and paper material has two mechanisms that are dependent on focal plane position range. Assumed interaction mechanism B appears in range of average focal plane position of 3.4 mm and 2.4 mm and assumed interaction mechanism A in range of average focal plane position of 0.4 mm and -0.6 mm both in used experimental set up. Focal plane position 1.4 mm represents midzone of these two mechanisms. Holes during laser beam and paper material interaction are formed gradually: first small hole is formed to interaction area in the centre of laser beam cross-section and after that, as function of interaction time, hole expands, until interaction between laser beam and dried kraft pulp is ended. By the image analysis it can be seen that in beginning of laser beam and dried kraft pulp material interaction small holes off very good quality are formed. It is obvious that black colour and heat affected zone appear as function of interaction time. This reveals that there still are different interaction phases within interaction mechanisms A and B. These interaction phases appear as function of time and also as function of peak intensity of laser beam. Limit peak intensity is the value that divides interaction mechanism A and B from one-phase interaction into dual-phase interaction. So all peak intensity values under limit peak intensity belong to MAOM (interaction mechanism A one-phase mode) or to MBOM (interaction mechanism B onephase mode) and values over that belong to MADM (interaction mechanism A dual-phase mode) or to MBDM (interaction mechanism B dual-phase mode). Decomposition process of cellulose is evolution of hydrocarbons when temperature is between 380- 500°C. This means that long cellulose molecule is split into smaller volatile hydrocarbons in this temperature range. As temperature increases, decomposition process of cellulose molecule changes. In range of 700-900°C, cellulose molecule is mainly decomposed into H2 gas; this is why this range is called evolution of hydrogen. Interaction in this range starts (as in range of MAOM and MBOM), when a small good quality hole is formed. This is due to “direct evaporation” of pulp via decomposition process of evolution of hydrogen. And this can be seen can be seen in spectrometer as high intensity peak of yellow light (in range of 588-589 nm) which refers to temperature of ~1750ºC. Pyrometer does not detect this high intensity peak since it is not able to detect physical phase change from solid kraft pulp to gaseous compounds. As interaction time between laser beam and dried kraft pulp continues, hypothesis is that three auto ignition processes occurs. Auto ignition of substance is the lowest temperature in which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. Three auto ignition processes appears in range of MADM and MBDM, namely: 1. temperature of auto ignition of hydrogen atom (H2) is 500ºC, 2. temperature of auto ignition of carbon monoxide molecule (CO) is 609ºC and 3. temperature of auto ignition of carbon atom (C) is 700ºC. These three auto ignition processes leads to formation of plasma plume which has strong emission of radiation in range of visible light. Formation of this plasma plume can be seen as increase of intensity in wavelength range of ~475-652 nm. Pyrometer shows maximum temperature just after this ignition. This plasma plume is assumed to scatter laser beam so that it interacts with larger area of dried kraft pulp than what is actual area of beam cross-section. This assumed scattering reduces also peak intensity. So result shows that assumably scattered light with low peak intensity is interacting with large area of hole edges and due to low peak intensity this interaction happens in low temperature. So interaction between laser beam and dried kraft pulp turns from evolution of hydrogen to evolution of hydrocarbons. This leads to black colour of hole edges.

Matalalämpötilaisen hukkalämmön hyödyntäminen kaukolämmön tuotannossa

Työ käsittelee tekniikoita, joilla voidaan hyödyntää matalalämpötilaisia hukkalämpöjä kaukolämmöntuotannossa. Työ esittelee lämpöpumpputekniikkaa, jolla hukkalämmön lähteestä tulevaa lämpöä voidaan lämpötilaltaan nostaa kaukolämpöverkon tarpeita vastaavaksi. Työssä käsitellään lämpöpumppujen kylmäaineita ja niiden soveltuvuutta eri lämpötila-alueisiin. Lisäksi käsitellään hyödyntämisen taloudellisuutta ja ympäristövaikutuksia. Taloudellisuudessa käsitellään investointi- ja käyttökustannukset ja pohditaan niiden pohjalta tuotteiden kaukolämpö- ja kaukokylmähinnoittelua asiakkaille. Työ myös tarkastelee hankkeen kokonaiskannattavuutta Mäntsälän Sähkölle. Kannattavuuslaskelmissa toteutetaan herkkyystarkastelu suurimpien muuttujien osalta. Työ tarkastelee yhdistetyn kylmän- ja lämmöntuotannon soveltuvuutta Mäntsälän keskustan kaukolämpöverkon ja Kapulin kaukolämpöverkon alueelle. Soveltuvuutta tarkastellaan Suomessa ja maailmalla toteutettujen referenssien pohjalta.

Työkoneiden dieselmoottoreiden hyötysuhteen parantaminen lämmöntalteenoton avulla

Tämä diplomityö on osa Lappeenrannan teknillisessä yliopistossa tehtävää tutkimusta polttomoottoreiden energiatehokkuuden parantamisessa. Työn tavoitteena on saada tutkimustietoa polttomoottoreiden hukkalämpövirtojen hyödyntämisestä sähköntuotannossa. Tavoitteena on muodostaa näkemys Mikro-ORC energiamuuntimen mahdollisuuksista ja reunaehdoista osana työkoneluokan (150 kW… 400 kW) dieselmoottorikokonaisuutta, erityisesti maataloussektorilla. Työssä tarkasteltaviksi moottoreiksi valittiin kaksi eri AGCO Sisu Powerin dieselmoottoria. Laskennat suoritettiin moottorin valmistajan antamien hukkalämpövirtojen arvojen perusteella. Laskennan perusperiaatteena oli tutkia ORC-prosessin tuottamaa lisäsähkötehoa hyödyntämällä pakokaasujen lämpöenergiaa korkea-, keski- ja matalalämpötiloissa. Työssä vertailtiin kahden eri kiertoaineen prosessihyötysuhdetta, saatava sähkötehoa sekä prosessin sisäisiä parametreja. Lisäksi työssä tutkittiin ORC-prosessin laskentaa suunnittelupisteessä (design) ja suunnittelupisteen ulkopuolella (off-design), prosessisuureiden optimointia ja lämmönsiirtimien mitoitusta. Diplomityössä tarkasteltiin moottorin energiataseen mukaisten arvojen lisäksi moottorin parametrien muuttamisen vaikutusta hukkalämpövirroista saatavan tehoon. Työssä saatiin arvokasta tietoa polttomoottoreiden hukkalämpövirtojen muuntamisesta sähköksi ORC:lla sekä moottorin energiatehokkuuden parantamisesta.

Characterization of Leaf-Type Ferredoxin-NADP+ Oxidoreductase (FNR) Isoforms in Arabidopsis thaliana

Life on earth is based on sunlight, which is captured in chemical form by photosynthetic reactions. In the chloroplasts of plants, light reactions of photosynthesis take place at thylakoid membranes, whereas carbon assimilation reactions occur in the soluble stroma. The products of linear electron transfer (LET), highly-energetic ATP molecules, and reducing power in the form of NADPH molecules, are further used in the fixation of inorganic CO2 molecules into organic sugars. Ferredoxin-NADP+ oxidoreductase (FNR) catalyzes the last of the light reactions by transferring electrons from ferredoxin (FD) to NADP+. In addition to LET, FNR has been suggested to play a role in cyclic electron transfer (CET), which produces ATP without the accumulation of reducing equivalents. CET is proposed to occur via two putative routes, the PGR5- route and the NDH-route. In this thesis, the leaf-type FNR (LFNR) isoforms LFNR1 and LFNR2 of a model organism, Arabidopsis thaliana, were characterized. The physiological roles of LFNRs were investigated using single and double mutant plants. The viability of the single mutants indicates functionality of both isoforms, with neither appearing to play a specific role in CET. The more severe phenotype of low-temperature adapted fnr2 plants compared to both wild-type (WT) and fnr1 plants suggests a specific role for LFNR2 under unfavorable growth conditions. The more severe phenotype of the fnr1 x fnr2 (F1 generation) plants compared to single mutants reflects down-regulated photosynthetic capacity, whereas slightly higher excitation pressure indicates mild over-excitation of electron transfer chain (ETC). However, induction of CET and various photoprotective mechanisms enable adaptation of fnr1 x fnr2 plants to scarcity of LFNR. The fnr1 fnr2 plants (F2 generation), without detectable levels of LFNR, were viable only under heterotrophic conditions. Moreover, drought stress induced acceleration of the rate of P700 + re-reduction in darkness was accompanied by a concomitant up-regulation of the PGR5-route specific components, PGR5 and PGRL1, demonstrating the induction of CET via the PGR5-route. The up-regulation of relative transcriptional expression of the FD1 gene indicates that the FD1 isoform may have a specific function in CET, while no such role could be defined for either of the LFNR isoforms. Both the membrane-bound and soluble LFNR1 and LFNR2 each appear as two distinct spots after 2D-PAGE with different isoelectric points (pIs), indicating the existence of post-translational modifications (PTMs) which do not determine the membrane attachment of LFNR. The possibility of phosphorylation and glycosylation PTMs were excluded, but all four LFNR forms were shown to contain acetylated lysine residues as well as alternative N-termini. N-terminal acetylation was shown to shift the pI of both LFNRs to be more acidic. In addition, all four LFNR forms were demonstrated to interact both with FD1 and FD2 in vitro

Insights into the role of hydration in protein structure and stability obtained through hydrostatic pressure studies

A thorough understanding of protein structure and stability requires that we elucidate the molecular basis for the effects of both temperature and pressure on protein conformational transitions. While temperature effects are relatively well understood and the change in heat capacity upon unfolding has been reasonably well parameterized, the state of understanding of pressure effects is much less advanced. Ultimately, a quantitative parameterization of the volume changes (at the basis of pressure effects) accompanying protein conformational transitions will be required. The present report introduces a qualitative hypothesis based on available model compound data for the molecular basis of volume change upon protein unfolding and its dependence on temperature.

Pressure-assisted cold denaturation of hen egg white lysozyme: the influence of co-solvents probed by hydrogen exchange nuclear magnetic resonance

COSY proton nuclear magnetic resonance was used to measure the exchange rates of amide protons of hen egg white lysozyme (HEWL) in the pressure-assisted cold-denatured state and in the heat-denatured state. After dissolving lysozyme in deuterium oxide buffer, labile protons exchange for deuterons in such a way that exposed protons are substituted rapidly, whereas "protected" protons within structured parts of the protein are substituted slowly. The exchange rates k obs were determined for HEWL under heat treatment (80ºC) and under high pressure conditions at low temperature (3.75 kbar, -13ºC). Moreover, the influence of co-solvents (sorbitol, urea) on the exchange rate was examined under pressure-assisted cold denaturation conditions, and the corresponding protection factors, P, were determined. The exchange kinetics upon heat treatment was found to be a two-step process with initial slow exchange followed by a fast one, showing residual protection in the slow-exchange state and P-factors in the random-coil-like range for the final temperature-denatured state. Addition of sorbitol (500 mM) led to an increase of P-factors for the pressure-assisted cold denatured state, but not for the heat-denatured state. The presence of 2 M urea resulted in a drastic decrease of the P-factors of the pressure-assisted cold denatured state. For both types of co-solvents, the effect they exert appears to be cooperative, i.e., no particular regions within the protein can be identified with significantly diverse changes of P-factors.

Design of automatic control system for the precipitation of bromelain from the extract of pineapple wastes

In this work, bromelain was recovered from ground pineapple stem and rind by means of precipitation with alcohol at low temperature. Bromelain is the name of a group of powerful protein-digesting, or proteolytic, enzymes that are particularly useful for reducing muscle and tissue inflammation and as a digestive aid. Temperature control is crucial to avoid irreversible protein denaturation and consequently to improve the quality of the enzyme recovered. The process was carried out alternatively in two fed-batch pilot tanks: a glass tank and a stainless steel tank. Aliquots containing 100 mL of pineapple aqueous extract were fed into the tank. Inside the jacketed tank, the protein was exposed to unsteady operating conditions during the addition of the precipitating agent (ethanol 99.5%) because the dilution ratio "aqueous extract to ethanol" and heat transfer area changed. The coolant flow rate was manipulated through a variable speed pump. Fine tuned conventional and adaptive PID controllers were on-line implemented using a fieldbus digital control system. The processing performance efficiency was enhanced and so was the quality (enzyme activity) of the product.

Germination of cotton seed in relation to temperature

The effect of constant temperature on the germination rate and percentage of two cotton seed lots was determined using a thermogradient plate. A gradient of 10 ºC to 40 ºC was established across the plate so that temperatures changed 2 ºC for each 5 cm increment in length, resulting in sixteen different temperature treatments. The optimal temperature zone for germination was 28 ºC to 30 ºC. As temperature decreased from the optimal zone, the rate of germination also decreased but germination percentages during the 10-day period were significantly lower only below 20 ºC. As temperature increased above the optimal zone, the rate of germination decreased and the percentage of germination sharply decreased above 32 ºC - 34 ºC. As expected, high quality cotton seed performed better than medium quality seed for a low temperature range (16 ºC to 22 ºC), but the most intriguing results were observed for the high temperatures range (36 ºC to38 ºC). The germination of medium quality cotton seed was consistently higher than for high quality seed, especially at 38 ºC after the second day of evaluation. This response has not been reported in the literature and further research is needed to better understand the germination physiology of cotton seed at high temperatures.

Matalalämpötilaisten jätelämpövirtojen hyödyntäminen lämpöpumpuilla: Case Energiaväylä

Hyvinkään Sahanmäen teollisuusalueella tarkastellaan mahdollisuutta hyödyntää Saint Gobain Isoverin lasivillatehtaalla syntyvää ylijäämälämpöä alueen yritysten lämmittämiseen. Hukkalämpöä on tarkoitus ottaa talteen lauhduttamalla savukaasuihin sitoutunutta vesihöyryä ja siirtää lauhtumisessa vapautuva lämpö matalalämpötilaiseen verkkoon, Energiaväylään. Verkkoon liittyviin kohteisiin asennetaan lämpöpumput, joiden avulla kohteet hyödyntävät verkosta saatavaa lämpöä. Työssä lasketaan Energiaväylästä potentiaalisesti saatava lämpöteho ja sen riittävyys asiakkaille. Lasketaan myös lämpö- ja painehäviöt sekä pumppauskustannukset. Lisäksi määritetään verkkoon liittyvien yritysten saavuttamat kustannussäästöt perustuen niiden lämpöenergiankulutukseen, sekä hankkeen kokonaiskannattavuus. Työ ei kuvaa todellista tilannetta tarkasti, vaan perustuu lukuisiin oletuksiin ja arvioihin. Työn tuloksia voidaan hyödyntää kannattavuuden arvioinnissa, mutta niiden perusteella ei voida tehdä investointipäätöksiä. Tehtyjen oletuksien perusteella kohteet saavuttaisivat yhteensä noin 1,22 milj. euron vuosittaiset säästöt vaihtamalla maakaasulämmityksen Energiaväylään. Hanke on mahdollisesti kannattava viiden vuoden takaisinmaksuajalla. Kannattavuus riippuu kuitenkin oleellisesti lämpöpumppujen asennuskustannuksista, jotka tulee arvioida erikseen kullekin kohteelle.

The effects of temperature on nickel tocicity in goldfish (carassius auratus L.)

Although it is widely assumed that temperature affects pollutant toxicity, few studies have actually investigated this relationship. Moreover, such research as has been done has involved constant temperatures; circumstances which are rarely, if ever, actually experienced by north temperate, littoral zone cyprinid species. To investigate the effects of temperature regime on nickel toxicity in goldfish (Carassius auratus L.), 96- and 240-h LCSO values for the heavy metal pollutant, nickel (NiCI2.6H20), were initially determined at 2DoC (22.8 mg/L and 14.7 mg/L in artificially softened water). Constant temperature bioassays at 10°C, 20°C and 30°C were conducted at each of 0, 240-h and 96-h LCSO nickel concentrations for 240 hours. In order to determine the effects of temperature variation during nickel exposure it was imperative that the effects of a single temperature change be investigated before addressing more complex regimes. Single temperature changes of + 10°C or -10°C were imposed at rates of 2°C/h following exposures of between 24 hand 216 h. The effects of a single temperature change on mortality, and duration of toxicant exposure at high and low temperatures were evaluated. The effects of fluctuating temperatures during exposure were investigated through two regimes. The first set of bioassays imposed a sinewave diurnal cycle temperature (20.±.1DOC) throughout the 10 day exposure to 240-h LeSO Ni. The second set of investigations approximated cyprinid movement through the littoral zone by imposing directionally random temperature changes (±2°C at 2-h intervals), between extremes of 10° and 30°C, at 240-h LC50 Ni. Body size (i.e., total length, fork length, and weight) and exposure time were recorded for all fish mortalities. Cumulative mortality curves under constant temperature regimes indicated significantly higher mortality as temperature and nickel concentration were increased. At 1DOC no significant differences in mortality curves were evident in relation to low and high nickel test concentrations (Le., 16 mg/L and 20 mg/L). However at 20°C and 30°C significantly higher mortality was experienced in animals exposed to 20 mg/L Ni. Mortality at constant 10°C was significantly lower than at 30°C with 16 mg/L and was significantly loWer than each of 2DoC and 39°C tanks at 20 mg/L Ni exposure. A single temperature shift from 20°C to 1DoC resulted in a significant decrease in mortality rate and conversely, a single temperature shift from 20°C to 30°C resulted in a significant increase in mortality rate. Rates of mortality recorded during these single temperature shift assays were significantly different from mortality rates obtained under constant temperature assay conditions. Increased Ni exposure duration at higher temperatures resulted in highest mortality. Diurnally cycling temperature bioassays produced cumulative mortality curves approximating constant 20°C curves, with increased mortality evident after peaks in the temperature cycle. Randomly fluctuating temperature regime mortality curves also resembled constant 20°C tanks with mortalities after high temperature exposures (25°C - 30°C). Some test animals survived in all assays with the exception of the 30°C assays, with highest survival associated with low temperature and low Ni concentration. Post-exposure mortality occurred most frequently in individuals which had experienced high Ni concentrations and high temperatures during assays. Additional temperature stress imposed 2 - 12 weeks post exposure resulted in a single death out of 116 individuals suggesting that survivors are capable of surviving subsequent temperature stresses. These investigations suggest that temperature significantly and markedly affects acute nickel toxicity under both constant and fluctuating temperature regimes and plays a role in post exposure mortality and subsequent stress response.

Thermodynamic properties and Debye-Waller factor of fee materials

We have calculated the equation of state and the various thermodynamic properties of monatomic fcc crystals by minimizing the Helmholtz free energy derived in the high temperature limit for the quasiharmonic theory, QH, and the lowest-order (cubic and quartic), 'A2, anharmonic terms of the perturbation theory, PT. The total energy in each case is obtained by adding the static energy. The calculation of the thermal properties was carried out for a nearest-neighbour central-force model of the fcc lattice by means of the appropriate thermodynamic relations. We have calculated the lattice constant, the thermal expansion, the coefficient of volume expansion, the specific heat at constant volume and at constant pressure, the isothermal and adiabatic bulk moduli, and the Griineisen parameter, for the rare-gas solids Kr and Xe, and gold. Morse potential and modified Morse potential were each used to represent the atomic interaction for the three fcc materials. For most of the calculated thermodynamic properties from the QH theory, the results for Kr and Xe with the modified Morse potential show an improvement over the results for the Morse potential when compared with the experimental data. However, the results of the 'A 2 equation of state with the modified Morse potential are in good agreement with experiment only in the case of the specific heat at constant volume and at constant pressure. For Au we have calculated the lattice contribution from the QH and 'A 2 PT and the electronic contribution to the thermal properties. The electronic contribution was taken into account by using the free electron model. The results of the thermodynamic properties calculated with the modified Morse potential were similar to those obtained with the Morse potential. U sing the minimized equation of state we also calculated the Mossbauer recoilless fraction for Kr and Xe and the Debye-Waller factor (DWF) for Pb, AI, eu, Ag, and Au. The Mossbauer recoilless fraction was obtained for the above two potentials and Lennard-Jones potential. The L-J potential gives the best agreement with experiment for Kr. No experimental data exists for Xe. At low temperature the calculated DWF results for Pb, AI, and eu show a good agreement with experimental values, but at high temperature the experimental DWF results increase very rapidly. For Ag the computed values were below the expected results at all temperatures. The DWF results of the modified Morse potential for Pb, AI, eu and Ag were slightly better than those of the Morse potential. In the case of Au the calculated values were in poor agreement with experimental results. We have calculated the quasiharmonic phonon dispersion curves for Kr, Xe, eu, Ag, and Au. The calculated and experimental results of the frequencies agree quite well for all the materials except for Au where the longitudinal modes show serious discrepancies with the experimental results. In addition, the two lowest-order anharmonic contributions to the phonon frequency were derived using the Green's function method. The A 2 phonon dispersion curves have been calculated only for eu, and the results were similar to those of the QH dispersion curves. Finally, an expression for the Griineisen parameter "( has been derived from the anharmonic frequencies, and calculated for these materials. The "( results are comparable with those obtained from the thermodynamic definition.