Epäpuhtauksien poistaminen sinkkisulfaattiliuoksista käyttäen selektiivisiä ioninvaihtimia

Diplomityössä on tutkittu kuparin, koboltin, nikkelin ja kadmiumin poistamista sinkkisulfaattiliuoksista käyttäen uusia silikarunkoisia kelatoivia erotusmateriaaleja. Vertailukohteena on käytetty perinteisiä kaupallisia polymeerirunkoisia kelatoivia ioninvaihtohartseja. Laboratoriokokeissa selvitettiin erotusmateriaalien adsorptio- ja ioninvaihto-ominaisuuksia tasapaino- ja kolonnikokeilla. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittiin olosuhteissa, jotka vastaavat prosessisyklin eri vaiheita. Metallien adsorptiomekanismien selvittämiseksi erotusmateriaaleille tehtiin happo-emäs ja sulfaattititraukset. Tasapainokokeet osoittivat, että silikarunkoisilla erotusmateriaaleilla saatiin kupari erotettua väkevistä sinkkisulfaattiliuoksista polymeerirunkoisia kelatoivia ioninvaihtohartseja paremmin. Tutkituilla erotusmateriaaleilla ja ioninvaihtohartseilla ei havaittu merkittävää selektiivisyyttä koboltille, nikkelille tai kadmiumille sinkin ja kuparin läsnä ollessa. Kolonnikokeilla yritettiin löytää paras esikäsittely-lataus-eluointisykli kuparin talteenottoon väkevistä sinkkisulfaattiliuoksista silikarunkoisilla erotusmateriaaleilla. Kolonnikokeissa esikäsittely tehtiin laimealla NaOH:lla, jonka jälkeen petiin syötettiin hapanta sinkkisulfaattiliuosta. Eluointi onnistui hyvin laimealla rikkihapolla. Kolonnikokeiden tulokset osoittivat, että kupari on mahdollista erottaa väkevistä sinkkisulfaattiliuoksista. Silikarunkoisten erotusmateriaalien kemiallista kestävyyttä tutkittaessa havaittiin materiaalien kestävän hyvin happoja ja 60 oC:en lämpötilaa. Sitä vastoin alkaalisissa olosuhteissa tapahtui silikan liukenemista. Tutkituilla erotusmateriaaleilla havaittiin kuparin sitoutumista sekä ioninvaihtomekanismin avulla että sitoutuneena neutraalina suolana.

Suodatuskalvojen toimivuuden arviointi paperiteollisuuden sovelluksissa

Työn tavoitteena oli etsiä vaihtoehtoja paperiteollisuuden kiertovesien ja pastapitoisten jätevesien suodatusprosesseissa tällä hetkellä käytössä oleville kalvoille. Työssä pyrittiin myös määrittämään tekijöitä, joiden avulla voitaisiin ennustaa polymeerikalvon käyttäytymistä erilaisissa paperiteollisuuden kalvosovelluksissa. Työn kirjallisessa osassa tarkasteltiin polymeerikalvojen ominaisuuksia, jotka vaikuttavat kalvojen käyttäytymiseen suodatusprosesseissa. Työssä esiteltiin myös tavallisimmat kalvomateriaalit ja polymeerikalvojen valmistustavat sekä paperiteollisuuden kalvosovelluksia. Paperiteollisuuden kalvosuodatussovellukset eroavat toisistaan huomattavasti toimintaolosuhteiltaan ja käyttötarkoituksiltaan. Tästä johtuen on hankalaa löytää yhteisiä tekijöitä, joiden perusteella voitaisiin ennustaa kalvon käyttäytymistä eri sovelluksissa. Kalvon hydrofiilisyyden todettiin kuitenkin vaikuttavan positiivisesti suodatustapahtumaan useissa sovelluksissa. Kokeellisessa osassa verrattiin erilaisten polymeerikalvojen ja referenssikalvojen toimintaa happaman kirkkaan suodoksen ja pastapitoisen veden suodatuksessa. Kirkkaan suodoksen suodatuskokeet tehtiin UPM-Kymmene Oy:n Kaukaan tehtailla. Pastapitoista jätevettä mallinnettiin syöttöpanoksilla, jotka tehtiin laimentamalla CTC:n valmistamaa LWC-pastaa. Suodatukset tehtiin CR 200/1- ja CR 550/10 -suodattimilla. Kirkkaan suodoksen suodatuksissa käytettiin referenssikalvona regeneroidusta selluloosasta ja pastapitoisen veden suodatuksessa aromaattisesta polyamidista valmistettua kalvoa. Kirkkaan suodoksen koesuodatusten perusteella todettiin, ettei minkään vertailtavan ultrasuodatuskalvon suodatuskapasiteetti ollut yhtä korkea kuin referenssikalvon. Referenssikalvon toiminta suodatuksessa oli myös vakaata syötön laadun muutoksista huolimatta. Todennäköisesti referenssikalvon erittäin hydrofiilinen luonne tekee siitä vertailtavia kalvoja sopivamman kirkkaan suodoksen suodatukseen. Pastapitoisen veden suodatustulosten perusteella referenssikalvolle löytyi useita potentiaalisia korvaajia. Näistä parhaan kalvon valitseminen edellyttää kuitenkin jatkotutkimuksia. SEM-analyysituloksista huomattiin, että tietyntyyppinen kalvorakenne parantaa kalvon toimintaa pastapitoisen veden suodatuksessa.

Fractionation of wood hydrolysate by ultrafiltration membranes at high temperature

Ultrafiltration (UF) is already used in pulp and paper industry and its demand is growing because of the required reduction of raw water intake and the separation of useful compounds from process waters. In the pulp and paper industry membranes might be exposed to extreme conditions and, therefore, it is important that the membrane can withstand them. In this study, extractives, hemicelluloses and lignin type compounds were separated from wood hydrolysate in order to be able to utilise the hemicelluloses in the production of biofuel. The performance of different polymeric membranes at different temperatures was studied. Samples were analysed for total organic compounds (TOC), lignin compounds (UV absorption at 280 nm) and sugar. Turbidity, conductivity and pH were also measured. The degree of fouling of the membranes was monitored by measuring the pure water flux before and comparing it with the pure water flux after the filtration of hydrolysate. According to the results, the retention of turbidity was observed to be higher at lower temperature compared to when the filtrations were operated at high temperature (70 °C). Permeate flux increased with elevated process temperature. There was no detrimental effect of temperature on most of the membranes used. Microdyn-Nadir regenerated cellulose membranes (RC) and GE-Osmonics thin film membranes seemed to be applicable in the chosen process conditions. The Polyethersulphone (NF-PES-10 and UH004P) and polysulphone (MPS-36) membranes used were highly fouled, but they showed high retentions for different compounds.

Suodatuskalvon puhdistaminen UV-valolla tai ultraäänellä aktivoidulla titaanidioksidilla

Kalvotekniikan suurin ongelma on edelleen kalvon likaantuminen, jonka tuloksena kalvon erotuskyky voi muuttua ja liuoksen vuo kalvon läpi pientyä huomattavasti. Kalvotekniikan teollisissa sovelluksissa kalvojen puhdistus on yksi tärkeimmistä pääkohdista, sillä se määrittää kalvon käyttöikää ja käyttötehokkuutta. Yleisimmin käytetyn kemiallisen pesun tuloksena muodostuu hävitettävä pesuliuos, joka sisältää sekä kemikaaleja, että kalvosta poistetun lian. Työssä on tutkittu kalvon puhdistusta ultravioletti-valo- tai ultraäänikäsittelyssä titaanidioksidin läsnäollessa. Menetelmien mahdollisina etuina ovat kalvosta poistetun lian hajotus harmittomiksi komponenteiksi ja mahdollisesti kalvon pienempi kuluminen pesussa. Työn kirjallisuusosassa on käsitelty orgaanisten ja epäorgaanisten aineiden hajottamista ultraviolettivalon tai ultraäänikäsittelyn avulla titaanidioksidin läsnäollessa sekä olosuhteiden vaikutusta menetelmien tehokkuuteen. Tämän lisäksi työssä on keskitytty polymeerikalvojen UV-valo- ja ultraäänikäsittelykestävyyteen. Kokeellisessa osassa on tutkittu UV-valo- ja ultraäänikäsittelyjen sopivuutta liatun PVDF-kalvon puhdistukseen titaanidioksidin läsnäollessa. Tavoitteena oli liatun kalvon permeabiliteetin palautus puhtaan kalvon tasolle käsittelyn avulla. Kalvon kestävyyttä on myös tutkittu. Tämän työn perusteella tutkittuja menetelmiä ei voida soveltaa tarkistettavan PVDF-kalvon puhdistukseen, ainakaan testeissä käytetyissä olosuhteissa, sillä kalvon ominaisuudet muuttuvat käsittelyissä.

Fractionation of Wood Extracts

The aim of this thesis was to fractionate wood extracts into pure fractions using membrane technology, to observe membrane behaviour in solvents and to study the effect of conditioning on membrane performance. Four different wood extracts were used in the performed filtrations. In the literature part, the focus was on the effect of different solvent properties on polymeric membranes, especially on their retention and flux. Solute properties, such as shape, polarity and charge, were examined. Transport models, membrane stability and ways to improve the stability, when solvents were filtered, were also discussed. The experimental part consisted of a series of filtrations, where the effect of the wood extracts and solvent concentration on solute retention was observed. Polymeric and ceramic membranes were tested under different conditions and the solute analyses were performed with GC and GC-MS. It was discovered that it is possible to fractionate wood extracts using membrane technology to some extent, but more research must be done to understand the mechanisms behind the various interactions between the solvent and the membrane. Conditioning was also considered as an important part of the membrane pre-treatment.

Ultrasuodatuskalvojen valinta, likaantuminen ja puhdistus entsyymiliuosten suodatuksessa

Ultrasuodatus on tehokas entsyymiliuosten konsentrointi- ja puhdistusmenetelmä. Prosessin ongelmana on kuitenkin kalvojen likaantumisesta johtuva suodatuksen aikainen vuon pienentyminen ja kalvojen hankala puhdistaminen. Oikeilla kalvovalinnoilla ja optimaalisilla pesustrategioilla voidaan suodatus- ja pesuaikoja lyhentää ja nain parantaa suodatusprosessin tehokkuutta ja tuotteen laatua. Työn kirjallisessa osassa on käsitelty entsyymiliuosten ja polymeerikalvojen suodatusprosessiin vaikuttavia ominaisuuksia. Työssä on esitelty myös pesuaineiden ja pesukemikaalien ominaisuuksia sekä pesuprosessiin vaikuttavia tekijöitä. Työn kokeellinen osa koostui kahdesta osasta. Työn ensimmäisessä osassa etsittiin entsyymiliuosten ultrasuodatusprosessiin sopivaa kalvoa vertailemalla kalvojen permeabiliteetteja, hydrofiilisyytta, varausta ja peseytyvyyttä. Suodatuksissa käytettiin kahta Roal Oy:n tuottamaa entsyymiliuosta ja suodatukset tehtiin DSS Labstak M20-laitteistolla. Työn toisen osan tarkoituksena oli etsiä entsyymiliuosten suodatuksessa käytettävien kalvojen likaantumisen syyt sekä tehokas puhdistusaine kalvojen pesuun. Tehokasta pesuainetta etsittiin liotuskokeilla ja laboratoriomittakaavan poikkivirtauslaitteistolla. Analysointeja tehtiin muun muassa FTIR- spektroskoopilla, vuomittauksilla, pyyhkäisyelektronimikroskoopilla ja kontaktikulmamittauksilla. Entsyymiliuosten suodatuksiin sopivan kalvon etsinnässä testattujen kalvojen välillä oli suuria eroja niin permeabiliteeteissa kuin likaantumisessa ja puhdistumisessa, mutta mikään kalvoista ei erottunut ylivoimaisesti parhaaksi. Pesuaineista kaupalliset membraanien puhdistukseen tarkoitetut emäksiset pesuaineet osoittautuivat tehokkaimmiksi lian poistajiksi.

Chelating Adsorbents in Purification of Hydrometallurgical Solutions

In this thesis, equilibrium and dynamic sorption properties of weakly basic chelating adsorbents were studied to explain removal of copper, nickel from a concentrated zinc sulfate solution in a hydrometallurgical process. Silica-supported chelating composites containing either branched poly(ethyleneimine) (BPEI) or 2-(aminomethyl)pyridine (AMP) as a functional group were used. The adsorbents are commercially available from Purity Systems Inc, USA as WP-1® and CuWRAM®, respectively. The fundamental interactions between the adsorbents, sulfuric acid and metal sulfates were studied in detail and the results were used to find the best conditions for removal of copper and nickel from an authentic ZnSO4 process solution. In particular, the effect of acid concentration and temperature on the separation efficiency was considered. Both experimental and modeling aspectswere covered in all cases. Metal sorption is considerably affected by the chemical properties of the studied adsorbents and by the separation conditions. In the case of WP-1, acid affinity is so high that column separation of copper, nickel and zinc has to be done using the adsorbent in base-form. On the other hand, the basicity of CuWRAM is significantly lower and protonated adsorbent can be used. Increasing temperature decreases the basicity and the metals affinity of both adsorbents, but the uptake capacities remain practically unchanged. Moreover, increasing temperature substantially enhances intra-particle mass transport and decreases viscosities thus allowing significantly higher feed flow rates in the fixed-bed separation. The copper selectivity of both adsorbents is very high even in the presence of a 250-fold excess of zinc. However, because of the basicity of WP-1, metal precipitation is a serious problem and therefore only CuWRAM is suitable for the practical industrial application. The optimum temperature for copper removal appears to be around 60 oC and an alternative solution purification method is proposed. The Ni/Zn selectivity of both WP-1 and CuWRAM is insufficient for removal of the very small amounts of nickel present in the concentrated ZnSO4 solution.

Lämpötilan vaikutus kuparin ja nikkelin kolonnierotuksessa kelatoivalla adsorbentilla

Sinkin valmistuksessa pitää sinkkirikasteesta poistaa epäpuhtausmetallit ennen elektrolyysiä. Nykyisin epäpuhtauksien poistamiseksi käytetään sementointimene-telmiä. Sementointi voisi olla mahdollista korvata kelatoivalla adsorbentilla suori-tettavalla erotuksella, jonka etuja ovat selektiivisyys ja ympäristöystävällisyys. Työn tarkoituksena on tutkia lämpötilan vaikutusta kelatoivalla adsorbentilla teh-tävään nikkelin ja kuparin kolonnierotukseen. Kolonnierotuksessa lämpötila voi vaikuttaa sekä liuoksen että adsorbentin fysi-kaalisiin, kemiallisiin ja sähkökemiallisiin ominaisuuksiin. Näiden vaikutusten johdosta voivat esimerkiksi erotuksen stoikiometria, kinetiikka tai toimintaolosuh-teet muuttua. Tässä työssä lämpötilan vaikutusta kolonnierotukseen tutkittiin rik-kihapon ja erotusmateriaalin välisillä kinetiikkakokeilla sekä synteettisellä CuSO4-liuoksella ja autenttisella ZnSO4-liuoksella tehdyillä kolonniajoilla. Työssä käytetyn erotusmateriaalin runko on silikapolyamiini ja sen funktionaali-sena ryhmänä toimii 2-aminometyylipyridiini. Lämpötilan ollessa 60 °C havaittiin erotusmateriaalin ja rikkihapon asettuvan tasapainoon kolme kertaa nopeammin kuin 25 °C:ssa. Lämpötilan nostamisella edelleen 90 °C:een ei havaittu olevan merkittävää vaikutusta tasapainon saavuttamisen nopeuteen. Kuparin läpäisykäyrän havaittiin jyrkentyvän lämpötilan noston vaikutuksesta niin autenttisella ZnSO4-liuoksella kuin synteettisellä CuSO4-liuoksella. Tämän oletettiin johtuvan kinetiikan nopeuden kasvusta sekä autenttisella liuoksella myös viskositeetin pienenemisestä. Lämpötilan vaikutuksesta on mahdollista käsitellä autenttista ZnSO4-liuosta 90 °C:ssa noin 3,5-kertaa enemmän kuin 25 °C:ssa, siten että liuoksesta saadaan poistettua lähes kaikki kupari. Nikkelin havaittiin lä-päisevän kolonnin kaikissa lämpötiloissa lähes välittömästi. Tästä syystä tutkittu erotusmateriaali ei sovellu nikkelin ja kuparin samanaikaiseen erottamiseen tutki-tusta autenttisesta ZnSO4-liuoksesta.

Membrane emulsification in preparation of single site catalyst

In the theory part the membrane emulsification was studied. Emulsions are used in many industrial areas. Traditionally emulsions are prepared by using high shear in rotor-stator systems or in high pressure homogenizer systems. In membrane emulsification two immiscible liquids are mixed by pressuring one liquid through the membrane into the other liquid. With this technique energy could be saved, more homogeneous droplets could be formed and the amount of surfactant could be decreased. Ziegler-Natta and single-site catalysts are used in olefin polymerization processes. Nowadays, these catalysts are prepared according to traditional mixing emulsification. More homogeneous catalyst particles that have narrower particle size distribution might be prepared with membrane emulsification. The aim of the experimental part was to examine the possibility to prepare single site polypropylene catalyst using membrane emulsification technique. Different membrane materials and solidification techniques of the emulsion were examined. Also the toluene-PFC phase diagram was successfully measured during this thesis work. This phase diagram was used for process optimization. The polytetrafluoroethylene membranes had the largest contact angles with toluene and also the biggest difference between the contact angles measured with PFC and toluene. Despite of the contact angle measurement results no significant difference was noticed between particles prepared using PTFE membrane or metal sinter. The particle size distributions of catalyst prepared in these tests were quite wide. This would probably be fixed by using a membrane with a more homogeneous pore size distribution. It is also possible that the solidification rate has an effect on the particle sizes and particle morphology. When polymeric membranes are compared PTFE is probably still the best material for the process as it had the best chemical durability.

Rigid Rod Polymer Fillers in Acrylic Denture and Dental Adhesive Resin Systems

Polymeric materials have been used in dental applications for decades. Adhesion of polymeric materials to each other and to the tooth substrate is essential to their successful use. The aim of this series of studies was two-folded. First, to improve adhesion of poly(paraphenylene) based rigid rod polymer (RRP) to other dental polymers, and secondly, to evaluate the usability of a new dentin primer system based on RRP fillers. Poly(paraphenylene) based RRP would be a tempting material for dental applications because of its good mechanical properties. To be used in dental applications, reliable adhesion between RRP and other dental polymers is required. In this series of studies, the adhesion of RRP to denture base polymer and the mechanical properties of RRP-denture base polymer-material combination were evaluated. Also adhesion of BisGMA-TEGDMA-resin to RRP was determined. Different surface treatments were tested to improve the adhesion of BisGMA-TEGDMA-resin to RRP. Results were based on three-point bending testing, Vickers surface hardness test and scanning electron microscope analysis (SEM), which showed that no reliable adhesion between RRP and denture base polymer was formed. Addition of RRP filler to denture base polymer increased surface hardness and flexural modulus but flexural strength decreased. Results from the shear bond strength test and SEM revealed that adhesion between resin and RRP was possible to improve by surface treatment with dichloromethane (DCM) based primer and a new kind of adhesive surface can be designed. The current dentin bonding agents have good immediate bond strength, but in long term the bond strength may decrease due to the detrimental effect of water and perhaps by matrix metalloproteinases. This leads to problems in longevity of restorations. Current bonding agents use organic monomers. In this series of studies, RRP filled dentin primer was tested in order to decrease the water sorption of the monomer system of the primers. The properties of new dentin primer system were evaluated in vitro by comparing it to commercial etch and rinse adhesive system. The results from the contact angle measurements and SEM showed that experimental primer with RRP reinforcement provided similar resin infiltration to dentin collagen and formed the resin-dentin interface as the control primer. Microtensile bond strength test and SEM revealed that in short term water storing, RRP increased bond strength and primer with BMEP-monomer (bis[2-(methacryloyloxy)-ethyl]phosphate) and high solvent concentration provided comparable bonding properties to the commercial control primers. In long term water storing, the high solvent-monomer concentration of the experimental primers decreased bond strength. However, in low solvent-monomer concentration groups, the long-term water storing did not decrease the bond strength despite the existence of hydrophilic monomers which were used in the system. These studies demonstrated that new dentin primer system reached the mechanical properties of current traditional etch and rinse adhesive system in short time water storing. Improved properties can be achieved by further modifications of the monomer system. Studies of the adhesion of RRP to other polymers suggest that adhesion between RRP and other dental polymers is possible to obtain by certain surface treatments.

Hydroksihappojen erotus mustalipeästä nanosuodatuksella

Hydroksihapoille on olemassa useita käyttömahdollisuuksia teollisuudessa, joten niiden hyödyntäminen sellunvalmistuksen sivuvirrasta eli mustalipeästä on suuren kiinnostuksen kohteena. Tässä työssä selvitettiin, onko hydroksihappojen erotus ja puhdistus mustalipeästä mahdollista nanosuodatuksella. Kokeellisessa osassa suodatettiin emäksisen mustalipeän lisäksi hapotettua ja jäähdytyskiteytettyä mustalipeää, johon oli lisätty liuotinta. Mustalipeäsuodatuksissa käytettiin viittä erilaista nanosuodatusmembraania (Microdyn Nadir® NP010 ja NP030, Dow Chemical Company NF-90, Woongjin Chemical NE-70 sekä Ge-Osmonics Desal 5 DK). Kirjallisuusosassa käsiteltiin puun sisältämien yhdisteiden kemiallista koostumusta, sellun valmistuksen pääperiaatteita, mustalipeän ja hydroksihappojen ominaisuuksia sekä hydroksihappojen käyttömahdollisuuksia. Lisäksi tarkasteltiin erilaisia hydroksihappojen erotusmenetelmiä, nanosuodatuksen teoriaa ja prosessiin sopivan membraanin valintakriteerejä. Työn kokeellisessa osassa tutkittiin emäksisen mustalipeän monivaiheisen nanosuodatuksen tehokkuutta hydroksihappojen erotuksessa. Hapotetun ja jäähdytyskiteytetyn mustalipeän suodatuskokeissa tutkittiin erityyppisten membraanien erotuskykyä sekä syötön liuotinlisäyksen vaikutusta hydroksihappojen erottumiseen. Lisäksi tarkasteltiin membraanien kestävyyttä ja foulaantumista suodatusolosuhteissa. Työn tulokset osoittivat, että hydroksihappoja voidaan fraktioida mustalipeästä nanosuodatuksella. Hydroksihappojen fraktiointiin vaikuttaa merkittävästi mustalipeässä käytetyn liuottimen läsnäolo sekä suodatuspaine. Lisäksi koetulosten perusteella havaittiin, että monivaiheisella nanosuodatuksella hydroksihapot läpäisevät membraanin ja permeaattiin saavutetaan puhtaampi happojae.

EDTA- and DTPA-functionalized silica gel and chitosan adsorbents for the removal of heavy metals from aqueous solutions

Adsorbents functionalized with chelating agents are effective in removal of heavy metals from aqueous solutions. Important properties of such adsorbents are high binding affinity as well as regenerability. In this study, aminopolycarboxylic acid, EDTA and DTPA, were immobilized on the surface of silica gel, chitosan, and their hybrid materials to achieve chelating adsorbents for heavy metals such as Co(II), Ni(II), Cd(II), and Pb(II). New knowledge about the adsorption properties of EDTA- and DTPA-functionalizedadsorbents was obtained. Experimental work showed the effectiveness, regenerability, and stability of the studied adsorbents. Both advantages and disadvantages of the adsorbents were evaluated. For example, the EDTA-functionalized chitosan-silica hybrid materials combined the benefits of the silica gel and chitosan while at the same time diminishing their observed drawbacks. Modeling of adsorption kinetics and isotherms is an important step in design process. Therefore, several kinetic and isotherm models were introduced and applied in this work. Important aspects such as effect of error function, data range, initial guess values, and linearization were discussed and investigated. The selection of the most suitable model was conducted by comparing the experimental and simulated data as well as evaluating the correspondence between the theory behind the model and properties of the adsorbent. In addition, modeling of two-component data was conducted using various extended isotherms. Modeling results for both one- and twocomponent systems supported each other. Finally, application testing of EDTA- and DTPA-functionalized adsorbents was conducted. The most important result was the applicability of DTPA-functionalized silica gel and chitosan in the capturing of Co(II) from its aqueous EDTA-chelate. Moreover, these adsorbents were efficient in various solution matrices. In addition, separation of Ni(II) from Co(II) and Ni(II) and Pb(II) from Co(II) and Cd(II) was observed in two- and multimetal systems. Lastly, prior to their analysis, EDTA- and DTPA-functionalized silica gels were successfully used to preconcentrate metal ions from both pure and salty waters

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

Astringent Food Compounds and Their Interactions with Taste Properties

Astringency is traditionally thought to be induced by plant tannins in foods. Because of this current research concerning the mechanism of astringency is focused on tannin‐protein interactions and thus on precipitation, which may be perceived by mechanoreceptors. However, astringency is elicited by a wide range of different phenolic compounds, as well as, some non‐phenolic compounds in various foods. Many ellagitannins or smaller compounds that contribute to astringent properties do not interact with salivary proteins and may be directly perceived through some receptors. Generally, the higher degree of polymerization of proanthocyanidins can be associated with more intense astringency. However, the astringent properties of smaller phenolic compounds may not be directly predicted from the structure of a compound, although glycosylation has a significant role. The astringency of organic acids may be directly linked to the perception of sourness, and this increases along with decreasing pH. Astringency can be divided into different sub‐qualities, including even other qualities than traditional mouth‐drying, puckering or roughing sensations. Astringency is often accompanied by bitter or sour or both taste properties. The different sub‐qualities can be influenced by different astringent compounds. In general, the glycolysation of the phenolic compound results in more velvety and smooth mouthdrying astringency. Flavonol glycosides and other flavonoid compounds and ellagitannins contribute to this velvety mouthdrying astringency. Additionally, they often lack the bitter properties. Proanthocyanidins and phenolic acids elicit more puckering and roughing astringency with some additional bitter properties. Quercetin 3‐O‐rutinoside, along with other quercetin glycosides, is among the key astringent compounds in black tea and red currants. In foods, there are always various other additional attributes that are perceived at the same with astringency. Astringent compounds themselves may have other sensory characteristics, such as bitter or sour properties, or they may enhance or suppress other sensory properties. Components contributing to these other properties, such as sugars, may also have similar effects on astringent sensations. Food components eliciting sweetness or fattiness or some polymeric polysaccharides can be used to mask astringent subqualities. Astringency can generally be referred to as a negative contributor to the liking of various foods. On the other hand, perceptions of astringent properties can vary among individuals. Many genetic factors that influence perceptions of taste properties, such as variations in perceiving a bitter taste or variations in saliva, may also effect the perception of astringency. Individuals who are more sensitive to different sensations may notice the differences between astringent properties more clearly. This may not have effects on the overall perception of astringency. However, in many cases, the liking of astringent foods may need to be learned by repetitive exposure. Astringency is often among the key sensory properties forming the unique overall flavour of certain foods, and therefore it also influences whether or not a food is liked. In many cases, astringency may be an important sub‐property suppressed by other more abundant sensory properties, but it may still have a significant contribution to the overall flavour and thus consumer preferences. The results of the practical work of this thesis show that the astringent phenolic compounds are mostly located in the skin fractions of black currants, crowberries and bilberries (publications I–III). The skin fractions themselves are rather tasteless. However, the astringent phenolic compounds can be efficiently removed from these skin fractions by consecutive ethanol extractions. Berries contain a wide range of different flavonol glycosides, hydroxycinnamic acid derivatives and anthocyanins and some of them strongly contribute to the different astringent and bitterness properties. Sweetness and sourness are located in the juice fractions along with the majority of sugars and fruit acids. The sweet and sour properties of the juice may be used to mask the astringent and bitterness properties of the extracts. Enzymatic treatments increase the astringent properties and fermented flavour of the black currant juice and decrease sweetness and freshness due to the effects on chemical compositions (IV). Sourness and sweetness are positive contributors to the liking of crowberry and bilberry fractions, whereas bitterness is more negative (V). Some astringent properties in berries are clearly negative factors, whereas some may be more positive. The liking of berries is strongly influenced by various consumer background factors, such as motives and health concerns. The liking of berries and berry fractions may also be affected by genetic factors, such as variations in the gene hTAS2R38, which codes bitter taste receptors (V).

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.