Erikoispaperin käyristymisen pienentäminen mittapysyvyyttä parantamalla

Diplomityössä on tutkittu Tervakoski Oy:n PK8:lla valmistettavan irrokepaperin mittapy-syvyysongelmaa. Tämä ilmenee asiakkaan jatkojalostusprosesseissa esim. silikonointi- ja liimausvaiheissa paperin huonona ajettavuutena. Työ pohjautuu PK8:lla suoritettavien tehdasmittakaavaisten koeajojen prosessiolosuhteiden ja mittapysyvyyttä kuvaavien analyysien tulosten tarkasteluun. Työn kirjallisuusosassa kerrotaan silikonointi- ja laminointiprosessin vaatimuksista irrokepaperille. Mittapysyvyyden teoreettista taustaa lähestytään puukuidun sorptio-ominaisuuksien tarkastelulla. Osassa perehdytään mm. paperin mittapysyvyyteen ja käyristymiseen vaikuttaviin eri tekijöihin. Osio sisältää myös katsauksen paperin mittapysyvyyden ja käyristymisen eri mittausmenetelmistä. Työn kokeellisessa osassa tarkastellaan PK8:n prosessiolosuhteiden vaikutuksia mittapysy- vyyden tasoon. Kokeellinen osa sisältää neljä tehdasmittakaavaista koeajosarjaa ja 23 eri koepistettä, joiden tarkoituksena on löytää PK8:lle mittapysyvyyden kannalta parhaimmat mahdolliset olosuhteet muiden laatuarvojen kärsimättä. Koesarjojen muuttujina on käytetty kuivatusviirojen kireyttä, konesuuntaista vetojännitystä sekä suihkusuhteen ja jauhatusasteen muutoksia. Lisäksi paperin käyristymiseen pyrittiin vaikuttamaan PK8:lla toispuoleisella kuivatuksella ja erilliskostutuskoneen toispuoleisella kostutusvesimäärällä. Koesarjojen prosessiolosuhteiden ja analyysitulosten perusteella PK8:lla muutettiin ajotapamallia jo työn kuluessa. Kokeellisen osan loputtua PK8:n tuotantolinjalle määriteltiin uusi ajotapamalli. PK8:n tuotantolinjalla valmistettavan glassiinin poikkisuuntainen kuivatuskutistuma aleni eräässä koesarjassa prosessiolosuhteiden muutosten myötä noin 13 %. Mittapysy-vyyttä kuvaavat kosteuslaajentuma, märkämuodonmuutos ja käyristyminen paranivat keskimäärin 11 %. Uuden ajotapamallin myötä PK8:n valmistaman irrokepaperin laatutaso on noussut, jolloin on jo nyt havaittu, että glassiinin ajettavuus on selkeästi parantunut asiakkaan jatkojalostusprosesseissa.

Kuivumiskutistuman yhteys massaseosten ominaisuuksien synergiseen käyttäytymiseen

Diplomityön tavoitteena oli selvittää kuivumiskutistuman yhteyttä massojen synergiseen käyttäytymiseen. Kirjallisuusosassa on pohdittu kuitujen, kuitujen koostumuksen ja massaseosten ominaisuuksien vaikutusta kuivumiskutistumiseen. Lisäksi on pohdittu erilaisten kuivatustapojen vaikutusta kuivumiskutistuman suuruuteen ja SC-paperin mekaanisiin ominaisuuksiin. Kokeellisessa osassa valmistettiin kiertovedellä seosarkkeja. Massoina seoksissa käytettiin hioketta, TMP:tä ja kahta eri valmistajan sellua, jotka molemmat koostuivat kuusesta ja männystä. Seosarkkeja kuivattiin vapaasti, estetysti ja siten, että arkkia vedettiin konesuunnassa 2 % ja siten, että arkin annettiin kutistua konesuunnassa 2 %. Vapaasti kutistuneista arkeista mitattiin kuivumiskutistuma, käyttäen mahdollisimman tarkkaa menetelmää, jotta saatiin selville kunkin massaseoksen ja puhtaan massan kutistumapotentiaali. Kokeellisen osan mittaustulosten perusteella työssä pohdittiin kuivumiskutistumisen yhteyttä massojen synergiseen käyttäytymiseen. Tuloksista käy ilmi, että kuivumiskutistumalla on yhteys massaseosten synergiseen käyttäytymiseen. Kuivumiskutistuma vaikuttaa eniten selluilla, joilla on suurin kutistumispotentiaali. Arkin kuivuessa, kuitujen kutistuessa, rikkoutuu arkissa jo syntyneitä sidoksia heikentäen mm. vetolujuutta. Sidoksien rikkoutuminen ilmenee selvästi valonsironnan kasvamisena, mutta myös palstautumislujuuden huonontumisena, joka kertoo sidosten vähentymisestä. Selluosuuden kasvattaminen vaikuttaa useimpien arkin ominaisuuksia huonontaen ja siis synergiaa huonontaen. Puhtaita massoja vertaillessa puhtailla selluilla on useimpien ominaisuuksien kohdalla huonoimmat suhteellisesti saavutetut lujuudet, joten selluista ei saada kaikkea lujuuspotentiaalia, mikä taas näkyy selvästi selluosuuden kasvaessa suurempana poikkeamina additiivisesti lasketuista lujuuksista. Mekaanisilla massoilla, joilla on pienempi kuivumiskutistuma, ei vaikutus ole niin voimakas kuin selluilla ja puhtaat mekaaniset massat säilyttävätkin ominaisuutensa paremmin kuin sellut.

Characterization of the chemical composition of the essential oils from Annona emarginata (Schltdl.) H. Rainer 'terra-fria' and Annona squamosa L.

The objective of this study was to characterize the chemical composition of the essential oil from the leaves of Annona emarginata (Schltdl.) H. Rainer 'terra-fria' and Annona squamosa L. The species were grown in a greenhouse for 18 months, which nutrient solution was applied weekly; the plants were then harvested and the leaves dried to extract the essential oil. The essential oil was analyzed by gas chromatography and mass spectrometry to study its chemical profiles. Eleven substances were found in the essential oil of A. emarginata, primarily (E)-caryophyllene (29.29%), (Z)-caryophyllene (16.86%), γ-muurolene (7.54%), α-pinene (13.86%), and tricyclene (10.04%). Ten substances were detected in the oil from A. squamosa, primarily (E)-caryophyllene (28.71%), (Z)-caryophyllene (14.46%), α-humulene (4.41%), camphene (18.10%), α-pinene (7.37%), β-pinene (8.71%), and longifolene (5.64%). Six substances were common to both species: (E)-caryophyllene, (Z)-caryophyllene, α-humulene, camphene, α-pinene, and β-pinene.

Metsähakkeen jalostusarvon nostaminen eri kuivausmenetelmillä

The thesis was made for Hyötypaperi Oy. To the business activity of the company belongs the recycling of materials and carry out for re-use and the manufacture of solid biofuels and solid recovered fuels. Hyötypaperi Oy delivers forest chips to its partner incineration plants by day and night though the year. The value of the forest chips is based on its percentage of dry material. It is important to dry forest chips well before its storage in piles and delivering to incineration plants. In the thesis was examed the increasing of the degree of refinement of forest chips by different drying methods. In the thesis was examined four different drying methods of the forest chips. The methods were field-, plate-, platform- and channel drying. In the channel drying was used a mechanical blower and the other drying methods were based on the weather conditions. By all drying methods were made test dryings during the summer 2007. In the thesis was examined also the economical profitableness of the field- and channel drying. The last examination in the thesis was measuring of the forest chips’s humidity by humidity measuring equipment of sawn timber during November 2007. The field drying on the surface of asphalt is the only method of drying, which is used by Hyötypaperi Oy in its own production. There do not exist earlier properly examined facts of any drying methods of forest chips, because the drying of forest chips is a new branch. By field- and platform drying achieved lower humidity of forest chips than by plate drying. The object by using the humidity measuring equipment was to be informed of the humidity of forest chips. At present the humidity will find out after 24 hours when the sample of humidity quantity has been dried in the oven. The Lappeenranta University of Technology had the humidity measuring equipment of sawn timber. The values of humidity measured by the equipment from the sample of forest chips were 2 – 9 percent lower than the real values of humidity specified by drying in oven.

Activity of daptomycin- and vancomycin-loaded poly-epsilon-caprolactone microparticles against mature staphylococcal biofilms.

The aim of the present study was to develop novel daptomycin-loaded poly-epsilon-caprolactone (PCL) microparticles with enhanced antibiofilm activity against mature biofilms of clinically relevant bacteria, methicillin-resistant Staphylococcus aureus (MRSA) and polysaccharide intercellular adhesin-positive Staphylococcus epidermidis. Daptomycin was encapsulated into PCL microparticles by a double emulsion-solvent evaporation method. For comparison purposes, formulations containing vancomycin were also prepared. Particle morphology, size distribution, encapsulation efficiency, surface charge, thermal behavior, and in vitro release were assessed. All formulations exhibited a spherical morphology, micrometer size, and negative surface charge. From a very early time stage, the released concentrations of daptomycin and vancomycin were higher than the minimal inhibitory concentration and continued so up to 72 hours. Daptomycin presented a sustained release profile with increasing concentrations of the drug being released up to 72 hours, whereas the release of vancomycin stabilized at 24 hours. The antibacterial activity of the microparticles was assessed by isothermal microcalorimetry against planktonic and sessile MRSA and S. epidermidis. Regarding planktonic bacteria, daptomycin-loaded PCL microparticles presented the highest antibacterial activity against both strains. Isothermal microcalorimetry also revealed that lower concentrations of daptomycin-loaded microparticles were required to completely inhibit the recovery of mature MRSA and S. epidermidis biofilms. Further characterization of the effect of daptomycin-loaded PCL microparticles on mature biofilms was performed by fluorescence in situ hybridization. Fluorescence in situ hybridization showed an important reduction in MRSA biofilm, whereas S. epidermidis biofilms, although inhibited, were not eradicated. In addition, an important attachment of the microparticles to MRSA and S. epidermidis biofilms was observed. Finally, all formulations proved to be biocompatible with both ISO compliant L929 fibroblasts and human MG63 osteoblast-like cells.

Non-wood massojen vedenpoiston arvioiminen märkäpuristuksessa

Yksivuotisten kasvien (non-wood) kuitua verrataan usein lehtipuukuituihin. Käytetyimpiä non-wood kasveja ovat vehnän olki, bambu, järviruoko ja bagassi. Non-wood massan erottaa puumassasta kuitenkin korkea silikaattipitoisuus sekä parenkyymisolupitoisuus, joka antaa massalle korkean hienoainepitoisuuden. Tämä yhdessä korkean hemiselluloosapitoisuuden ja lyhyen kuidun pituuden kanssa heikentävät voimakkaasti non-wood massan vedenpoisto-ominaisuuksia. Non-wood kuidulla voidaan korvata lehtipuumassaa hienopapereissa. Non-wood kuitu antaa paperille hyvän opasiteetin, korkean valonsirontakertoimen sekä sileän painopinnan. Massaan lisättävä pitkäkuituinen havupuumassa parantaa ajetta¬vuutta paperikoneella ja helpottaa massan vedenpoistoa. Non-wood massan vedenpoistoa voidaan tehostaa esimerkiksi poistamalla osa hienoaineesta, käyttämällä non-wood massalle sopivaa keittotapaa sekä käyttämällä märkä¬puristuksessa pitkänippityyppistä puristinratkaisua. Myös non-wood kuidun kuivaaminen parantaa vedenpoistoa. Tässä tutkimuksessa kirjallisuusosassa keskityttiin yleisimpiin paperin valmistuksessa käytettäviin non-wood kuidun lähteisiin, märkäpuristuksen teoriaan ja tapoihin tehostaa vedenpoistoa. Kokeellisessa osassa tutkittiin vehnänolkimassan käyttäytymistä märkäpuristuksessa erilaisten ominaisuuksien pohjalta. Tutkimuksen kohteena oli non-wood massan keittotapa (hapan/alkali), hienoainepitoisuus, silikaattipitoisuus sekä kuivattu/kuivaamaton kuitu. Vertailun vuoksi tutkimuksessa oli mukana myös yksi järviruokomassa. Tuloksista huomataan, että non-wood massan vedenpoistoon vaikuttaa hienoainepitoisuus, kuidun kuivaus sekä massan valmistustapa. Järviruokomassan veden¬poisto on tehokkaampaa kuin vehnänolkimassan paremman kuitu¬koostumuksensa takia. Jos hienopaperimassassa korvataan lehtipuumassaa non-wood kuidulla maksimissaan 40 %, massan vedenpoistoa voidaan hyvin arvioida erilaisten suotautuvuusmittojen, kuten freeneksen, vedenpidätyskyvyn ja suotautumisajan, avulla.

The mediterranean diet pattern and its main components are associated with lower plasma concentrations of tumor necrosis factor receptor 60 in patients at high risk for cardiovascular disease

Adherence to aMediterranean diet (MD) is associated with a reduced risk of coronary heart disease. However, themolecular mechanisms involved are not fully understood. The aim of this studywas to compare the effects of 2MD with those of a lowfat- diet (LFD) on circulating inflammatory biomarkers related to atherogenesis. A total of 516 participants included in the PreventionwithMediterraneanDiet Studywere randomized into 3 intervention groups [MD supplementedwith virgin olive oil (MD-VOO); MD supplemented with mixed nuts (MD-Nuts); and LFD]. At baseline and after 1 y, participants completed FFQ and adherence to MD questionnaires, and plasma concentrations of inflammatory markers including intercellular adhesion molecule-1(ICAM-1), IL-6, and 2 TNF receptors (TNFR60 and TNFR80) were measured by ELISA. At 1 y, the MD groups had lower plasma concentrations of IL-6, TNFR60, and TNFR80 (P , 0.05), whereas ICAM-1, TNFR60, and TNFR80 concentrations increased in the LFD group (P , 0.002). Due to between-group differences, participants in the 2 MD groups had lower plasma concentrations of ICAM-1, IL-6, TNFR60, and TNFR80 compared to those in the LFD group (P # 0.028). When participants were categorized in tertiles of 1-y changes in the consumption of selected foods, those in the highest tertile of virgin olive oil (VOO) and vegetable consumption had a lower plasma TNFR60 concentration compared with those in tertile 1 (P,0.02).Moreover, the only changes in consumption thatwere associated with 1-y changes in the geometricmean TNFR60 concentrations were those of VOO and vegetables (P = 0.01). This study suggests that a MD reduces TNFR concentrations in patients at high cardiovascular risk.

Polymorphisms cyclooxygenase-2 -765G>C and interleukin-6 -174G>C are associated with serum inflammation markers in a high cardiovascular risk population and do not modify the response to a Mediterranean diet supplemented with virgin olive oil or nuts

Inflammation is involved in cardiovascular diseases. Some studies have found that the Mediterranean diet (MD) can reduce serum concentrations of inflammation markers. However, none of these studies have analyzed the influence of genetic variability in such a response. Our objective was to study the effect of the -765G.C polymorphism in the cyclooxygenase-2 (COX-2) gene and the -174G.C polymorphism in the interleukin-6 (IL-6) gene on serum concentrations of IL-6, C-reactive protein, intercellular adhesion molecule 1 (ICAM-1) and vascular cell adhesion molecule-1 as well as their influence on the response toa nutritional interventionwithMD.An intervention study ina high cardiovascular riskMediterranean population (314 men and 407 women) was undertaken. Participants were randomly assigned to consume a low-fat control diet or a MD supplementedwith virgin olive oil ornuts.Measureswereobtained at baseline and after a 3-mointervention period.At baseline, the COX-2 -765G.C polymorphismwas associated with lower serum IL-6 (5.85 6 4.82 in GG vs. 4.74 6 4.14 ng/L in C-allele carriers; P ¼ 0.002) and ICAM-1 (265.8 6 114.8 in GG vs. 243.0 6 107.1 mg/L in C-carriers; P ¼ 0.018) concentrations. These differences remained significant aftermultivariate adjustment. The IL-6 -174G.C polymorphism was associatedwith higher (CC vs. G-carriers) serumICAM-1concentrations in bothmenandwomenandwithhigherserumIL-6 concentrations inmen.Following the dietary intervention, no significant gene x diet interactions were found. In conclusion, although COX-2 -765G.C and IL-6 -174G.C polymorphismswere associatedwith inflammation, consuming aMD(either supplemented with virgin olive oil or nuts) reduced the concentration of inflammation markers regardless of these polymorphisms.

Geração eletroquímica do hidreto de selênio em sistema de injeção em fluxo com detecção por espectrometria de absorção atômica com chama Ar-Glp

This paper presents a system for electrochemical hydride generation using flow-injection and atomic absorption spectrometry to determine selenium in biological materials. The electrolytic cell was constructed by assembling two reservoirs, one for the sample and the other for the electrolytic solution separated by a Nafion membrane. Each compartment had a Pt electrode. The sample and electrolyte flow-rates, acidic media, and applied current were adjusted to attain the best analytical performance and ensure the membrane lifetime. The atomisation system used a T quartz tube in an air-LPG flame. The composition of the flame, the observation height, and the argon flow rate used to carry the hydrides were critically investigated. The system allowed to perform thirty determinations per hour with a detection limit of 10 mug L-1 of Se. Relative standard deviations were in general lower than 1.5% for a solution containing 20.0 and 34.0 mug L-1 of Se in a typical sample digest. Accuracy was assessed analysing the certified materials: rice flour (NIST-1568) from National Institute of Standard and Technology and dried fish (MA-A-2), whole animal blood (A-2/1974) from the International Atomic Energy Agency.

Preparação e caracterização de pós cerâmicos de aluminatos de lítio

The preparation of gamma-LiAlO2 by coprecipitation and sol-gel synthesis was investigated. Ceramic powders obtained by coprecipitation synthesis were prepared from aqueous solutions of aluminum and lithium nitrates using sodium hydroxide as precipitant agent. By sol-gel synthesis, the ceramic powders were prepared from hydrolysis of aluminum isopropoxide. The materials obtained by two routes of synthesis were dried at 80ºC and calcined at 550, 750, 950 and 1150ºC. The characterization was done by X-ray diffraction, infrared spectroscopy, emission and absorption atomic spectrometry, helium picnometry, specific surface area (BET method) and scanning electronic microscopy. Mixtures of crystalline phases were obtained by coprecipitation synthesis: 80ºC- LiAl2(OH)7.2H2O + Al(OH)3; 550 and 750ºC- alpha-LiAlO2 + eta-Al2O3; 950 and 1150ºC- gamma-LiAlO2 + LiAl5O8. Chemical analysis showed molar ration Al/Li @ 3. Crystalline single-phases were obtained by sol-gel synthesis above 550ºC: 550ºC-alpha-LiAlO2; 750, 950 and 1150ºC-gamma-LiAlO2. These powders presented molar ration Al/Li @ 1. Thus, gamma-LiAlO2 crystalline phase was obtained at 750ºC by sol-gel synthesis while by coprecipitation synthesis, a mixture of crystalline phases was obtained. These results showed the superiority of the sol-gel synthesis for the preparation of pure gamma-LiAlO2.

Food Safety Testing: Rapid Molecular Methods for Chemical and Biological Hazards

The central goal of food safety policy in the European Union (EU) is to protect consumer health by guaranteeing a high level of food safety throughout the food chain. This goal can in part be achieved by testing foodstuffs for the presence of various chemical and biological hazards. The aim of this study was to facilitate food safety testing by providing rapid and user-friendly methods for the detection of particular food-related hazards. Heterogeneous competitive time-resolved fluoroimmunoassays were developed for the detection of selected veterinary residues, that is coccidiostat residues, in eggs and chicken liver. After a simplified sample preparation procedure, the immunoassays were performed either in manual format with dissociation-enhanced measurement or in automated format with pre-dried assay reagents and surface measurement. Although the assays were primarily designed for screening purposes providing only qualitative results, they could also be used in a quantitative mode. All the developed assays had good performance characteristics enabling reliable screening of samples at concentration levels required by the authorities. A novel polymerase chain reaction (PCR)-based assay system was developed for the detection of Salmonella spp. in food. The sample preparation included a short non-selective pre-enrichment step, after which the target cells were collected with immunomagnetic beads and applied to PCR reaction vessels containing all the reagents required for the assay in dry form. The homogeneous PCR assay was performed with a novel instrument platform, GenomEra^™, and the qualitative assay results were automatically interpreted based on end-point time-resolved fluorescence measurements and cut-off values. The assay was validated using various food matrices spiked with sub-lethally injured Salmonella cells at levels of 1-10 colony forming units (CFU)/25 g of food. The main advantage of the system was the exceptionally short time to result; the entire process starting from the pre-enrichment and ending with the PCR result could be completed in eight hours. In conclusion, molecular methods using state-of-the-art assay techniques were developed for food safety testing. The combination of time-resolved fluorescence detection and ready-to-use reagents enabled sensitive assays easily amenable to automation. Consequently, together with the simplified sample preparation, these methods could prove to be applicable in routine testing.

Degradação e estabilização do diclofenaco em nanocápsulas poliméricas

The parameters which affect the degradation and stabilization of diclofenac in suspensions of nanocapsules and of the corresponding spray-dried powders were investigated. Formulations were subjected to 14 months of storage at room temperature. In addition, a study of the degradation of diclofenac was carried out by exposing the formulations or mixtures (drug and adjuvants) to UVC wavelengths. The presence of Epikuron 170® in a concentration higher than 3.06 mg/mL stabilizes the drug, avoiding its reduction or degradation. The degradation products were isolated, analyzed by gas chromatography-mass spectrometry, and identified as 2-(2',6'-dichlorophenyl)aminobenzyl alcohol and N-(2',6'-dichlorophenyl)anthranilylaldehyde.

Determinação de arsênio em águas contaminadas usando fluorescência de raios-X por energia dispersiva

This work proposes a simple, fast and inexpensive method to determine As in natural waters, using X-ray fluorescence. 50 µL of each sample containing 100 mg L-1 of yttrium as internal standard were deposited over a 2.5 µm thickness MylarTM film. The samples were dried at 50 °C for 2 h. X-ray spectra were obtained using an EDXRF apparatus. The accuracy was determined by analyte addition/recovery and by comparison with Hydride Generation Atomic Absorption Spectrometry (HG AAS). A recovery of about 100% was obtained and the results were in good agreement with HG AAS. The method showed a relative standard deviation of 6.8% and a detection limit of 10.5 µg L-1 of As.

Microesferas de quitosana reticuladas com tripolifosfato utilizadas para remoção da acidez, ferro(III) e manganês(II) de águas contaminadas pela mineração de carvão

Considerable attention has been paid to chitosan and derivatives as efficient adsorbents of pollutants such as metal ions and dyes in aqueous medium. Nevertheless, no report can be found on the remedial actions of chitosan microspheres crosslinked with tripolyphosphate to control acidity, iron (III) and manganese (II) contents in wastewaters from coal mining. In this work, chitosan microspheres crosslinked with tripolyphosphate were used for the neutralization of acidity and removal of Fe (III) and Mn (II) from coal mining wastewaters. The study involved static and dinamic methods. The neutralization capacity of the surface of the static system was 395 mmol of H3O+ per kilogram of microspheres, higher than that of the dynamic one (223 mmol kg-1). The removal of Fe(III) in wastewater was of 100% and that of Mn(II) was 90%.

Preparação de amostra de fígado bovino e estudo de micro homogeneidade para a determinação de Cd E Pb por espectrometria de absorção atômica com atomização eletrotérmica e amostragem direta de sólido

This work describes a systematic study for bovine liver sample preparation for Cd and Pb determination by solid sampling electrothermal atomic absorption spectrometry. Samples were prepared using different procedures: (1) drying in a household microwave oven followed by drying in a stove at 60 ºC until constant mass, and (2) freeze-drying. Ball and cryogenic mills were used for grinding. Particle size, sample size and micro sample homogeneity were investigated. All prepared samples showed good homogeneity (He < 10) even for low sample mass, but samples dried in a microwave oven/stove and ground in a ball mill presented the best homogeneity.