Modeling of fireside deposit formation in two industrial furnaces

Fireside deposits can be found in many types of utility and industrial furnaces. The deposits in furnaces are problematic because they can reduce heat transfer, block gas paths and cause corrosion. To tackle these problems, it is vital to estimate the influence of deposits on heat transfer, to minimize deposit formation and to optimize deposit removal. It is beneficial to have a good understanding of the mechanisms of fireside deposit formation. Numerical modeling is a powerful tool for investigating the heat transfer in furnaces, and it can provide valuable information for understanding the mechanisms of deposit formation. In addition, a sub-model of deposit formation is generally an essential part of a comprehensive furnace model. This work investigates two specific processes of fireside deposit formation in two industrial furnaces. The first process is the slagging wall found in furnaces with molten deposits running on the wall. A slagging wall model is developed to take into account the two-layer structure of the deposits. With the slagging wall model, the thickness and the surface temperature of the molten deposit layer can be calculated. The slagging wall model is used to predict the surface temperature and the heat transfer to a specific section of a super-heater tube panel with the boundary condition obtained from a Kraft recovery furnace model. The slagging wall model is also incorporated into the computational fluid dynamics (CFD)-based Kraft recovery furnace model and applied on the lower furnace walls. The implementation of the slagging wall model includes a grid simplification scheme. The wall surface temperature calculated with the slagging wall model is used as the heat transfer boundary condition. Simulation of a Kraft recovery furnace is performed, and it is compared with two other cases and measurements. In the two other cases, a uniform wall surface temperature and a wall surface temperature calculated with a char bed burning model are used as the heat transfer boundary conditions. In this particular furnace, the wall surface temperatures from the three cases are similar and are in the correct range of the measurements. Nevertheless, the wall surface temperature profiles with the slagging wall model and the char bed burning model are different because the deposits are represented differently in the two models. In addition, the slagging wall model is proven to be computationally efficient. The second process is deposit formation due to thermophoresis of fine particles to the heat transfer surface. This process is considered in the simulation of a heat recovery boiler of the flash smelting process. In order to determine if the small dust particles stay on the wall, a criterion based on the analysis of forces acting on the particle is applied. Time-dependent simulation of deposit formation in the heat recovery boiler is carried out and the influence of deposits on heat transfer is investigated. The locations prone to deposit formation are also identified in the heat recovery boiler. Modeling of the two processes in the two industrial furnaces enhances the overall understanding of the processes. The sub-models developed in this work can be applied in other similar deposit formation processes with carefully-defined boundary conditions.

S-metolachlor efficacy on the control of Brachiaria decumbens, Digitaria horizontalis, and Panicum maximum in mechanically green harvested sugarcane

The aim of this study was to assess the efficacy of S-metolachlor applied in pre-emergence conditions for the control of Brachiaria decumbens, Digitaria horizontalis, and Panicum maximum in sugar cane mechanically harvested without previous burning of the crop (green harvest) with the crop residue either left or not on the soil surface. The experiments were established in the field according to a randomized complete block design with four repetitions in a 7 x 2 split-plot scheme. In the plots, five herbicide treatments were studied (S-metolachlor at 1.44, 1.92, and 2.40 kg ha-1, clomazone at 1.20 kg ha-1, and isoxaflutole at 0.188 kg ha-1), and two control treatments with no herbicide application. In the subplots, the presence or absence of sugar cane crop residue on the soil surface was evaluated. S-metolachlor efficacy was not hampered by either 14 or 20 t ha-1 of sugar cane crop residue on the soil surface. When sugar cane crop residue was covering the soil surface, S-metolachlor at a rate of 1.44 kg ha-1 resulted in weed control similar at their larger rates, where as without the presence of crop residue, S-metolachlor controlled B. decumbens, D. horizontalis, and P. maximum at the rates of 1.92, 1.44, and 1.92 kg ha-1, respectively. The herbicides clomazone and isoxaflutole were effective for the studied species, independently of the crop residue covering the soil surface. S-metolachlor caused no visible injury symptoms to the sugar cane plant. Clomazone and isoxaflutole caused visible injuries to the sugar cane plant. None of the herbicides negatively affected the number of viable culms m² or the culm height and diameter.

Biopolttoaineiden on-line -laadunmittauksen hyödyt energiantuotannossa

Biopolttoaineet ovat tärkeä energianlähde suomalaisessa energiantuotannossa. Biopoltto- aineille on kuitenkin ominaista laadun vaihtelevuus. Yksi tärkeimmistä laatutekijöistä on kosteus, joka vaikuttaa myös polttoaineen energiasisältöön. Laatutekijät puolestaan vai- kuttavat polttoainekäsittelyyn, polttoprosessiin ja koko laitoksen hyötysuhteeseen. Tämän työn tarkoituksena oli tutkia voisiko biopolttoaineiden online-laadunmittaus tuoda lisäarvoa energiantuotantolaitokselle. Esimerkkinä käytettiin yhtä online-laadunmittaus- sovellusta, InrayFuel-röntgenmittausjärjestelmää. Sillä voidaan seurata biopolttoaineiden kosteutta ja polttoaineen sisältämiä vierasaineita. Työssä on laadittu kustannusanalyysi, jolla pyritään selvittämään, onko nykyisen kertaluontoisen mittausmenetelmän korvaami- nen jatkuvatoimisella kannattavaa. Esimerkkilaitoksena on Etelä-Savon Energian Pur- sialan voimalaitos, jossa röntgenmittausjärjestelmään on testattu. Saatujen tulosten mukaan investoiminen esimerkkimittausjärjestelmään maksaisi itsensä takaisin alle vuodessa. Kun laitoksella pystytään seuraamaan polttoaineen laatua jatkuva- toimisesti, laadunhallinta paranee ja sitä kautta voidaan saavuttaa kustannussäästöjä. Polt- toaineesta johtuvat häiriötilanteet vähenevät, polttoaine on mahdollista optimoida edulli- semmaksi polton kannalta ja poltto-olosuhteita voidaan säätää paremmin, jolloin päästöt vähenevät ja hyötysuhde kasvaa. Työssä käytetty laskenta analysoi kuitenkin hyvin ylei- sellä tasolla, sillä käytössä ei ollut laitoksen omaa taselaskentajärjestelmää. Laskenta siis sisältää paljon oletuksia. Tämän ja rohkaisevien tulosten vuoksi tutkimusta jatkuvatoimi- sen laadunmittauksen hyödyistä kannattaa tehdä enemmän.

Suunnittelulla ja ruo´on hyötykäytöllä tehokkuutta rantojen hoitoon : Tuloksia ja kokemuksia VELHO-hankkeesta

Varsinais-Suomen ELY-keskuksen toteuttamassa VELHO-hankkeessa kehitettiin kustannustehokkaita ratkaisuja ranta-alueiden umpeenkasvun aiheuttamiin ongelmiin luomalla uusi konsepti ranta-alueiden monikäyttösuunnitteluun, edistämällä järviruo’on hyötykäyttöä ja valmistelemalla esityksiä uuteen maaseudun kehittämisohjelmaan. Tässä julkaisussa esitellään työn tulokset ja johtopäätökset. Hankkeessa laadittiin kolme ranta-alueiden monikäyttösuunnitelmaa: Mynälahden Sarsalanaukko ja Musta-aukko, Oukkulanlahti – Naantalinaukko ja Eurajoen - Luvian rannikko. Suunnitelmissa sovitettiin yhteen ranta-alueiden eri käyttömuotoja ja pyrittiin löytämään optimaalinen verkosto hyötykäyttöön leikattavien ruovikoiden, avoimena pidettävien merenrantaniittyjen ja säilytettävien ruovikoiden välille. Kustannustehokkuuteen pyrittiin kohdentamalla hoitotoimet laajoihin kokonaisuuksiin sekä järviruo’on hyötykäytöllä. Suunnitelmat laadittiin laajassa osallistavassa prosessissa. Hankkeessa laadituissa ranta-alueiden monikäyttösuunnitelmissa esitettiin erilaisia maankäyttötavoitteita ja hoitosuosituksia yli 2000 hehtaarille. Ruovikoiden ja rantaniittyjen lisäksi suunnittelun kohteena olivat myös rantojen läheiset peltoalueet, reunavyöhykkeet ja muut perinnebiotoopit. Hoitotoimilla tavoitellaan alueiden luonnon monimuotoisuuden ja vesien tilan paranemista, maiseman avartumista ja virkistyskäytön helpottumista. Ruovikoiden erilaisia leikkuumenetelmiä (talvileikkuut, vesileikkuut, maaleikkuut) testattiin 90 hehtaarin alalla. Rantaniittyjen kunnostuksessa testattiin maaleikkuun lisäksi ruovikon niittomurskausta. Ruokomassan hyötykäyttökokeissa testattiin kahden eri ruokolaadun eli tuoreen kesäruo’on ja kuivan talviruo’on esikäsittelyä ja hyötykäyttöä energiantuotannossa (poltto, biokaasutus) ja maataloudessa (maanparannusaine, viherlannoite, kuivike, katemateriaali). Maaseudun kehittämisohjelmaan tehtiin esityksiä tukimuotojen kehittämiseksi: rantaniittyjen kunnostuksen lisääminen ja hoidon laadun parantaminen, ruovikoiden vesileikkuut ravinteiden poistajina sekä ruokomassojen käyttö maan orgaanisen aineen lisääjänä. Hankkeen kokemusten mukaan yksi kustannustehokkaimmista hoito- ja käyttöketjuista on ruovikon leikkuu loppukesällä ja siitä kertyvän massan käyttö ranta-alueiden läheisillä pelloilla viherlannoitteena ja maanparannusaineena. Yhden hehtaarin ruovikon kesäleikkuulla poistetaan keskimäärin 80 kg typpeä ja 7 kg fosforia. Vesiensuojelullisten hyötyjen lisäksi leikkuulla parannetaan umpeenkasvusta kärsivien lajien elinoloja, lisätään rantojen vetovoimaisuutta ja edistetään luonnonhoitoyrittäjyyden edellytyksiä. Peltokäytössä käsittelyketju on lyhyt eikä se vaadi pitkiä kuljetusmatkoja. Ruokomassa kierrättää ravinteita takaisin pelloille ja parantaa maan rakennetta. Järviruo’on hyötykäytöllä ei pystytä kattamaan koko leikkuu- ja käyttöketjun kustannuksia. Leikkuusta ja hyötykäytöstä saatavien monien eri aineellisten ja aineettomien ekosysteemipalveluhyötyjen vuoksi toimintaan on tarpeen suunnata yhteiskunnan tukea ja luoda käytännön toteutusta edistäviä tukimuotoja. Kustannustehokkuutta voidaan edelleen parantaa laitteita ja menetelmiä kehittämällä.

Weed Community in a Raw Sugarcane Renovation Area Submitted to Different Soil Managements

The objective of this study was to evaluate the weed community in a raw sugarcane renovation area with three soil managements and peanut sowing in succession. The experiment was conducted during the 2007/08 season on a raw sugarcane area harvested without prior burning in the last five cuts. A randomized block design with treatments arranged in a split plot and arranged in four replications was used. The main treatments consisted of three cropping systems: conventional tillage, minimum tillage and direct planting, and subplots consisted in the absence (resting) or presence of crop rotation with peanuts. After 135 days from planting peanuts and 180 days of sugarcane harvest, the number of weeds m-2 was counted and the shoot dry biomass of the weeds collected was determined. The data were interpreted by analysis of variance and the means were compared by Tukey's test at 5% probability so that phytosociological indices a, b, c e d were calculated. The use of soil conservation tillage and peanut in rotation with sugarcane in the renovation areas is effective in controlling weeds and suppression of weed species difficult to control like Cyperus rotundus, Commelina bengalensis, Urochloa plantaginea, and Digitaria nuda.

The developmental anatomy of the subterranean system in Mandevilla illustris (Vell.) Woodson and M. velutina (Mart. ex Stadelm.) Woodson (Apocynaceae)

Two species of Mandevilla from the savanna area of São Paulo State, Brazil were studied. These species have been prescribed as folk medicine as infusions or alcoholic extracts of the underground system for treatment of venomous snake bites. To explain the morphological nature of such a system, its ontogeny was described to determine which parts are involved in its formation. In both Mandevilla species examined, the underground system consists of a xylopodium whose basal region joins a tuberous root.

Jätteen kaasutus ja energiakäyttö

Kiinteiden polttoaineiden muuntaminen kaasumaiseen muotoon eli kaasuttaminen herätti jo vuosia sitten tutkijoiden kiinnostusta. Suomessa yleinen mielenkiinto on viimeaikoina keskittynyt edullisempien polttoaineiden kaasuttamiseen ja saatavan tuotekaasun polttamiseen. Lahti Energian uudessa Kymijärvi 2 voimalaitoksessa kaasutetaan puuta ja kierrätyspolttoainetta (REF). Saatava tuotekaasu jäähdytetään ja suodatetaan, jotta epäpuhtaudet saadaan pois tuotekaasusta. Puhdistettu tuotekaasu poltetaan kaasukattilassa korkeilla höyrynarvoilla. Tuotekaasun jäähdyttämistä ei ole paljoa tehty eikä siitä ole juurikaan tieteellistä tutkimusta eikä kokemusta. Tuotekaasun jäähtyessä partikkelit tarttuvat lämpöpinnoille aiheuttaen kerrostumia. Kerrostumat heikentävät lämmönsiirtoa olennaisesti. Tämän työn tarkoitus on tutkia kaasutusprosessia, tuotekaasun jäähdyttimen likaantumista sekä antaa lisätietoja likaantumiseen vaikuttavista tekijöistä.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Sick leave prescribing practices in Finland

Background: Sick leave prescribing is a common task of doctors and being on sick leave results in notable economic consequences to society. However, there appears to be limited research into this field and the factors affecting sick leave prescribing practices of doctors. Aims: To examine the prescribing of sick leave by doctors and dentists, the extent of variation in practices, whether clinician-related factors and local structural factors affect variation, and the economic consequences of varying practices. Materials and methods: Questionnaire studies with 19 or 16 hypothetical patient cases were conducted among 165 primary health care (PHC) physicians, 356 occupational health care (OHC) physicians, 338 surgeons and 1132 dentists. Results: The difference between the lowest and the highest number of sick leave days prescribed for the 19 patient cases was almost four-fold in PHC physicians and surgeons and eight-fold in OHC physicians, which represents a societal cost of tens of thousands of euros. Some dentists did not prescribe sick leave to any of the 16 patient cases, and some prescribed nearly a hundred days altogether. The overall number of sick leave days OHC physicians prescribed was smaller than in PHC physicians. More days of sick leave were prescribed by those working in smaller municipalities than larger population centres. Conclusion: There was considerable variation in the sick leave prescribing practices of Finnish health care professionals. This means that patients may not receive equal social benefits. Sick leave carries considerable economic consequences, and unifying prescribing practices could bring significant cost savings to society.

Anxiogenic-like effect of acute and chronic fluoxetine on rats tested on the elevated plus-maze

The selective serotonin reuptake inhibitor fluoxetine (FLX) is widely prescribed for depression and anxiety-related disorders. On the other hand, enhanced serotonergic transmission is known to be classically related to anxiety. In this study, the effects of acute (5.0 mg/kg) and chronic (5.0 mg/kg, 22 days) FLX were investigated in both food-deprived and non-deprived rats tested in the elevated plus-maze. Significant main effects of the three factors (drug, food condition and administration regimen) were observed, but no interaction between them. The administration of either acute or chronic FLX resulted in an anxiogenic effect, as detected by a significant reduction in the percentage of time spent in the open arms and in the percentage of open arm entries. Food deprivation yielded an anxiolytic-like profile, probably related to changes in locomotor activity. The administration regimen resulted in an anxiolytic profile in chronically treated rats, as would be expected after 22 days of regular handling. The anxiogenic action of acute FLX is consistent with both its neurochemical and clinical profile. The discrepancy between the anxiogenic profile of chronic FLX and its therapeutic uses is discussed in terms of possible differences between the type of anxiety that is measured in the plus-maze and the types of human anxiety that are alleviated by fluoxetine.

A simple HPLC-fluorescence method for the measurement of R,S-sotalol in the plasma of patients with life-threatening cardiac arrhythmias

R,S-sotalol, a ß-blocker drug with class III antiarrhythmic properties, is prescribed to patients with ventricular, atrial and supraventricular arrhythmias. A simple and sensitive method based on HPLC-fluorescence is described for the quantification of R,S-sotalol racemate in 500 µl of plasma. R,S-sotalol and its internal standard (atenolol) were eluted after 5.9 and 8.5 min, respectively, from a 4-micron C18 reverse-phase column using a mobile phase consisting of 80 mM KH2PO4, pH 4.6, and acetonitrile (95:5, v/v) at a flow rate of 0.5 ml/min with detection at lex = 235 nm and lem = 310 nm, respectively. This method, validated on the basis of R,S-sotalol measurements in spiked blank plasma, presented 20 ng/ml sensitivity, 20-10,000 ng/ml linearity, and 2.9 and 4.8% intra- and interassay precision, respectively. Plasma sotalol concentrations were determined by applying this method to investigate five high-risk patients with atrial fibrillation admitted to the Emergency Service of the Medical School Hospital, who received sotalol, 160 mg po, as loading dose. Blood samples were collected from a peripheral vein at zero, 0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 6.0, 8.0, 12.0 and 24.0 h after drug administration. A two-compartment open model was applied. Data obtained, expressed as mean, were: CMAX = 1230 ng/ml, TMAX = 1.8 h, AUCT = 10645 ng h-1 ml-1, Kab = 1.23 h-1, a = 0.95 h-1, ß = 0.09 h-1, t(1/2)ß = 7.8 h, ClT/F = 3.94 ml min-1 kg-1, and Vd/F = 2.53 l/kg. A good systemic availability and a fast absorption were obtained. Drug distribution was reduced to the same extent in terms of total body clearance when patients and healthy volunteers were compared, and consequently elimination half-life remained unchanged. Thus, the method described in the present study is useful for therapeutic drug monitoring purposes, pharmacokinetic investigation and pharmacokinetic-pharmacodynamic sotalol studies in patients with tachyarrhythmias.

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.

New families of highly efficient, halogen-free flame retardants for polypropylene (PP)

The driving forces for current research of flame retardants are increased fire safety in combination with flame retardant formulations that fulfill the criteria of sustainable production and products. In recent years, important questions about the environmental safety of antimony, and in particular, brominated flame retardants have been raised. As a consequence of this, the current doctoral thesis work describes efforts to develop new halogen-free flame retardants that are based on various radical generators and phosphorous compounds. The investigation was first focused on compounds that are capable of generating alkyl radicals in order to study their role on flame retardancy of polypropylene. The family of azoalkanes was selected as the cleanest and most convenient source of free alkyl radicals. Therefore, a number of symmetrical and unsymmetrical azoalkanes of the general formula R-N=N-R’ were prepared. The experimental results show that in the series of different sized azocycloalkanes the flame retardant efficacy decreased in the following order: R = R´= cyclohexyl > cyclopentyl > cyclobutyl > cyclooctanyl > cyclododecanyl. However, in the series of aliphatic azoalkanes compounds, the efficacy decreased as followed: R = R´= n-alkyl > tert-butyl > tert-octyl. The most striking difference in flame retardant efficacy was observed in thick polypropylene plaques of 1 mm, e.g. azocyclohexane (AZO) had a much better flame retardant performance than did the commercial reference FR (Flamestab® NOR116) in thick PP sections. In addition, some of the prepared azoalkane flame retardants e.g. 4’4- bis(cyclohexylazocyclohexyl) methane (BISAZO) exhibited non-burning dripping behavior. Extrusion coating experiments of flame retarded low density polyethylene (LDPE) onto a standard machine finished Kraft paper were carried out in order to investigate the potential of azoalkanes in multilayer facings. The results show that azocyclohexane (AZO) and 4’4-bis (cyclohexylazocyclohexyl) methane (BISAZO) can significantly improve the flame retardant properties of low density polyethylene coated paper already at 0.5 wt.% loadings, provided that the maximum extrusion temperature of 260 oC is not exceeded and coating weight is kept low at 13 g/m2. In addition, various triazene-based flame retardants (RN1=N2-N3R’R’’) were prepared. For example, polypropylene samples containing a very low concentration of only 0.5 wt.% of bis- 4’4’-(3’3’-dimethyltriazene) diphenyl ether and other triazenes passed the DIN 4102-1 test with B2 classification. It is noteworthy that no burning dripping could be detected and the average burning times were very short with exceptionally low weight losses. Therefore, triazene compounds constitute a new and interesting family of radical generators for flame retarding of polymeric materials. The high flame retardant potential of triazenes can be attributed to their ability to generate various types of radicals during their thermal decomposition. According to thermogravimetric analysis/Fourier transform infrared spectroscopy/MS analysis, triazene units are homolytically cleaved into various aminyl, resonance-stabilized aryl radicals, and different CH fragments with simultaneous evolution of elemental nitrogen. Furthermore, the potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R’ as a new group of halogen-free flame retardants for polypropylene films have been investigated. According to the DIN 4102- 1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene films at already very low concentrations of 0.5 wt.%. For the disulfide family, the highest FR activity was recorded for 5’5’-dithiobis (2-nitrobenzoic acid). Very low values for burning length (53 mm) and burning time (10 s) reflect significantly increased fire retardant performance of this disulfide compared to other compounds in this series as well as to Flamestab® NOR116. Finally, two new, phosphorus-based flame retardants were synthesized: P’P-diphenyl phosphinic hydrazide (PAH) and melamine phenyl phosphonate (MPhP). The DIN 4102-1 test and the more stringent UL94 vertical burning test (UL94 V) were used to assess the formulations ability to extinguish a flame once ignited. A very strong synergistic effect with azoalkanes was found, i.e. in combination with these radical generators even UL94 V0 rate could be obtained.

Stiffness based trajectory planning and feedforward based vibration suppression control of parallel robot machines

The dissertation proposes two control strategies, which include the trajectory planning and vibration suppression, for a kinematic redundant serial-parallel robot machine, with the aim of attaining the satisfactory machining performance. For a given prescribed trajectory of the robot's end-effector in the Cartesian space, a set of trajectories in the robot's joint space are generated based on the best stiffness performance of the robot along the prescribed trajectory. To construct the required system-wide analytical stiffness model for the serial-parallel robot machine, a variant of the virtual joint method (VJM) is proposed in the dissertation. The modified method is an evolution of Gosselin's lumped model that can account for the deformations of a flexible link in more directions. The effectiveness of this VJM variant is validated by comparing the computed stiffness results of a flexible link with the those of a matrix structural analysis (MSA) method. The comparison shows that the numerical results from both methods on an individual flexible beam are almost identical, which, in some sense, provides mutual validation. The most prominent advantage of the presented VJM variant compared with the MSA method is that it can be applied in a flexible structure system with complicated kinematics formed in terms of flexible serial links and joints. Moreover, by combining the VJM variant and the virtual work principle, a systemwide analytical stiffness model can be easily obtained for mechanisms with both serial kinematics and parallel kinematics. In the dissertation, a system-wide stiffness model of a kinematic redundant serial-parallel robot machine is constructed based on integration of the VJM variant and the virtual work principle. Numerical results of its stiffness performance are reported. For a kinematic redundant robot, to generate a set of feasible joints' trajectories for a prescribed trajectory of its end-effector, its system-wide stiffness performance is taken as the constraint in the joints trajectory planning in the dissertation. For a prescribed location of the end-effector, the robot permits an infinite number of inverse solutions, which consequently yields infinite kinds of stiffness performance. Therefore, a differential evolution (DE) algorithm in which the positions of redundant joints in the kinematics are taken as input variables was employed to search for the best stiffness performance of the robot. Numerical results of the generated joint trajectories are given for a kinematic redundant serial-parallel robot machine, IWR (Intersector Welding/Cutting Robot), when a particular trajectory of its end-effector has been prescribed. The numerical results show that the joint trajectories generated based on the stiffness optimization are feasible for realization in the control system since they are acceptably smooth. The results imply that the stiffness performance of the robot machine deviates smoothly with respect to the kinematic configuration in the adjacent domain of its best stiffness performance. To suppress the vibration of the robot machine due to varying cutting force during the machining process, this dissertation proposed a feedforward control strategy, which is constructed based on the derived inverse dynamics model of target system. The effectiveness of applying such a feedforward control in the vibration suppression has been validated in a parallel manipulator in the software environment. The experimental study of such a feedforward control has also been included in the dissertation. The difficulties of modelling the actual system due to the unknown components in its dynamics is noticed. As a solution, a back propagation (BP) neural network is proposed for identification of the unknown components of the dynamics model of the target system. To train such a BP neural network, a modified Levenberg-Marquardt algorithm that can utilize an experimental input-output data set of the entire dynamic system is introduced in the dissertation. Validation of the BP neural network and the modified Levenberg- Marquardt algorithm is done, respectively, by a sinusoidal output approximation, a second order system parameters estimation, and a friction model estimation of a parallel manipulator, which represent three different application aspects of this method.

Biohiilen teknillistaloudelliset käyttömahdollisuudet meesauuneissa

Diplomityön tavoitteena oli tutkia biohiilen teknillisiä ja taloudellisia käyttömahdollisuuksia meesauunien polttoaineena. Suomessa meesauunit käyttävät polttoaineinaan yleensä maakaasua ja polttoöljyä. Näiden polttoaineiden käytön korvaamisessa ja vähentämisessä halvemmilla biopolttoaineilla on saatavilla suuret säästöt ja päästöjen vähennykset. Työssä keskityttiin erityisesti tutkimaan biohiilen mahdollisia polttotapoja, biohiilen polton tuottamien vierasaineiden määrää ja biohiilen käytön taloudellista kannattavuutta meesauunien polttoaineena. Työn pohjalta voidaan sanoa, että biohiilen käyttö meesauunien polttoaineena on mahdollista ja kannattavaa. Biohiiltä voidaan käyttää polttoaineena meesauuneissa samoilla polttotavoilla, mitä on käytetty sellu- ja sementtiteollisuudessa polttamaan biohiilen kaltaisia polttoaineita. Biohiilen polton tuottamien vierasaineiden määrä on samaa suuruusluokkaa kuin puun pölypolton tuottamien vierasaineiden määrä. Vierasaineiden pitoisuuksia voidaan hallita avaamalla kemikaalikiertoa. Biohiilen kanssa kilpaileviin puun pölypolttoon ja kaasutukseen nähden biohiilelle löydettiin etuja.