The Role of Surfactant Properties of Extractants in Hydrometallurgical LiquidLiquid Extraction Processes

The amphiphilic nature of metal extractants causes the formation of micelles and other microscopic aggregates when in contact with water and an organic diluent. These phenomena and their effects on metal extraction were studied using carboxylic acid (Versatic 10) and organophosphorus acid (Cyanex 272) based extractants. Special emphasis was laid on the study of phase behaviour in a pre neutralisation stage when the extractant is transformed to a sodium or ammonium salt form. The pre neutralised extractants were used to extract nickel and to separate cobalt and nickel. Phase diagrams corresponding to the pre neutralisation stage in a metal extraction process were determined. The maximal solubilisation of the components in the system water(NH3)/extractant/isooctane takes place when the molar ratio between the ammonia salt form and the free form of the extractant is 0.5 for the carboxylic acid and 1 for the organophosphorus acid extractant. These values correspond to the complex stoichiometry of NH4A•HA and NIi4A, respectively. When such a solution is contacted with water a microemulsion is formed. If the aqueous phase contains also metal ions (e.g. Ni²+), complexation will take place on the microscopic interface of the micellar aggregates. Experimental evidence showing that the initial stage of nickel extraction with pre neutralised Versatic 10 is a fast pseudohomogeneous reaction was obtained. About 90% of the metal were extracted in the first 15 s after the initial contact. For nickel extraction with pre neutralised Versatic 10 it was found that the highest metal loading and the lowest residual ammonia and water contents in the organic phase are achieved when the feeds are balanced so that the stoichiometry is 2NH4+(org) = Nit2+(aq). In the case of Co/Ni separation using pre neutralised Cyanex 272 the highest separation is achieved when the Co/extractant molar ratio in the feeds is 1 : 4 and at the same time the optimal degree of neutralisation of the Cyanex 272 is about 50%. The adsorption of the extractants on solid surfaces may cause accumulation of solid fine particles at the interface between the aqueous and organic phases in metal extraction processes. Copper extraction processes are known to suffer of this problem. Experiments were carried out using model silica and mica particles. It was found that high copper loading, aromacity of the diluent, modification agents and the presence of aqueous phase decrease the adsorption of the hydroxyoxime on silica surfaces.

Spray coating technique asa surface treatment for woodcontaining paper grades

The objective of this work was to introduce the emerging non-contacting spray coating process and compare it to the existing coating techniques. Particular emphasis was given to the details of the spraying process of paper coating colour and the base paper requirements set by the new coating method. Spraying technology itself is nothing new, but the atomisation process of paper coating colour is quite unknown to the paper industry. The differences between the rheology of painting and coating colours make it very difficult to utilise the existing information from spray painting research. Based on the trials, some basic conclusion can be made:The results of this study suggest that the Brookfield viscosity of spray coating colour should be as low as possible, presently a 50 mPas level is regarded as an optimum. For the paper quality and coater runnability, the solids level should be as high as possible. However, the graininess of coated paper surface and the nozzle wear limits the maximum solids level to 60 % at the moment. Most likelydue to the low solids and low viscosity of the coating colour the low shear Brookfield viscosity correlates very well with the paper and spray fan qualities. High shear viscosity is also important, but yet less significant than the low shear viscosity. Droplet size should be minimized and besides keeping the brrokfield viscosity low that can be helped by using a surfactant or dispersing agent in the coating colour formula. Increasing the spraying pressure in the nozzle can also reduce the droplet size. The small droplet size also improves the coating coverage, since there is hardly any levelling taking place after the impact with the base paper. Because of the lack of shear forces after the application, the pigment particles do not orientate along the paper surface. Therefore the study indicates that based on the present know-how, no quality improvements can be obtained by the use of platy type of pigments. The other disadvantage of them is the rapid deterioration of the nozzle lifetime. Further research in both coating colour rheology and nozzle design may change this in the future, but so far only round shape pigments, like typically calcium carbonate is, can be used with spray coating. The low water retention characteristics of spray coating, enhanced by the low solids and low viscosity, challenge the base paper absorption properties.Filler level has to be low not to increase the number of small pores, which have a great influence on the absorption properties of the base paper. Hydrophobic sizing reduces this absorption and prevents binder migration efficiently. High surface roughness and especially poor formation of the base paper deteriorate thespray coated paper properties. However, pre-calendering of the base paper does not contribute anything to the finished paper quality, at least at the coating colour solids level below 60 %. When targeting a standard offset LWC grade, spraycoating produces similar quality to film coating, but yet blade coating being on a slightly better level. However, because of the savings in both investment and production costs, spray coating may have an excellent future ahead. The porousnature of the spray coated surface offers an optimum substrate for the coldset printing industry to utilise the potential of high quality papers in their business.

Characteristics of Flowing Film

Työssä tutkittiin uutta teknologiaa pigmenttipäällystykseen. Tämä tekniikka on yleisesti tunnettua eräillä muilla teollisuudenaloilla. Kirjallisuustutkimuksessa on esitelty prosessia ja sen eri osatekijöitä sekä muilla aloilla tunnettuja prosessimuuttujia. Päällystyspastojen ja päällystettävien pintojen teoriaa on selvitetty uuden tekniikan ja pigmenttipäällystyksen valossa. Uuden tekniikan perusmekanismeja tutkittiin kokeellisessa osassa. Valuvan nestefilmin stabiilisuutta tutkittiin minimivirtauksen avulla. Stabiilisuustutkimuksen suorittamiseen käytettiin apuna Taguchi-matriisia DOE-ohjelmalla (Design of Experiments). Kokeiden perusteella minimivirtauksen kannalta päällystyspastalle edullisempi koostumus on kalsiumkarbonaatti- kuin kaoliinipasta. Sideaineella on pienempi osuus lateksia ja polyvinyylialkoholia parempi. Suurempi osuus pinta-aktiivista ainetta ja matala pastan kuiva-ainepitoisuus ovat suositeltuja. Tehokas ilmanpoisto päällystyspastasta on myös tärkeää lopullisen tuloksen kannalta. Koekoneella ajetuissa päällystyskokeissa havaittiin valuvan filmin ominaisuuksien tärkeys. Pienetkin kaasumäärät päällystyspastassa häiritsivät lopullisen päällysteen laatua. Päällystyspastan ilmanpoisto on avainasemassa erityisesti kun päällystetään suurella nopeudella pieniä päällystemääriä. Koeajoissa havaittiin kaikki kirjallisuudessa esitellyt rajoittavat tekijät. Kokeissa päällystettiin 400-1600 m/min nopeudella 5-20 g/m² päällystemääriä. Olosuhteet stabiilille nestefilmille vaativat edelleen kehitystä suurella nopeudella päällystettäessä. Päällysteen eroavaisuuksia verrattiin teräpäällystysmenetelmiin. Terä-päällystyksellä saadaan sileä mutta epätasaisesti peittävä pinta kun taas uuden tekniikan päällyste mukailee päällystettävän alustan topografiaa. Tasapaksun päällysteen etuna on hyvä peittävyys jo pienellä päällystemäärällä.

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.

Adsorptive removal of harmful organic compound from aqueous solutions

Adsorption is one of the most commonly used methods in water treatment processes. It is attractive due to it easy operation and the availability of a wide variety of commercial adsorbents. This doctoral thesis focuses on investigating and explaining the influence of external phase conditions (temperature, pH, ionic strength, acidity, presence of cosolutes) on adsorption phenomena. In order to cover a wide range of factors and phenomena, case studies were chosen from various fields where adsorption is applied. These include the adsorptive removal of surface active agents (used in cleaning chemicals, for example) from aqueous effluents, the removal of hormones (estradiol) from drinking water, and the adsorption of antibiotics onto silica. The latter can beused to predict the diffusion of antibiotics in the aquatic system if they are released into the environment. Also the adsorption of living cells on functionalized polymers to purify infected water streams was studied. In addition to these examples, the adsorptive separation of harmful compounds from internal water streams within a chemical process was investigated. The model system was removal of fermentation inhibitors from lignocelluloses hydrolyzates. The detoxification of the fermentation broth is an important step in the manufacture of bioethanol from wood, but has not been studied previously in connection with concentrated acid hydrolyzates. New knowledge on adsorption phenomena was generated for all of the applications investigated. In most cases, the results could be explained by combining classical theories for individual phenomena. As an example, it was demonstrated how liquid phase aggregation could explain abnormal-looking adsorption equilibrium data. In addition to the fundamental phenomena, also process performance was of interest. This aspect is often neglected in adsorption studies. It was demonstrated that adsorbents should not be selected for a target application based on their adsorption properties only, but regeneration of the spent adsorbent must be considered. It was found that using a suitable amount of organic co-solvent in the regeneration can significantly improve the productivity of the process.

Pinta-aktiiviaineiden vaikutus kuitulinjan toimintaan

Työssä tutkittiin kahden eri pinta-aktiiviaineen A ja B käytön vaikutusta kahdella eri kuitulinjalla. Molempien pinta-aktiiviaineiden pääfunktiona oli vaikuttaa nes-teen pintajännitykseen, jolloin nesteen tunkeutumisnopeus kuitumatriisiin ja kui-tujen huokosiin paranee. Lisäksi pinta-aktiiviaineilla A ja B oli kyky stabiloida nesteeseen liuenneita uuteainekomponentteja, jolloin uudelleensaostumisen riski pienenee. Koeajoilla pyrittiin vaikuttamaan happidelignifiointivaiheen uuteainetasoihin, alkali- ja happiannoksiin sekä kappareduktioon. Lisäksi tarkasteltiin annostelun vaikutusta kuitulinjan pesurien toimintaan, uuteainetasojen kehittymiseen koko kuitulinjalla sekä valkaisun kemikaalikulutukseen. Työssä kokeiltiin myös pinta-aktiiviaineen B vaikutusta EOP-vaiheen uuteainetasoon. Työn kirjallisuusosassa perehdyttiin puun uuteaineisiin ja niiden käyttäytymiseen kuitulinjalla, pinta-aktiiviaineisiin, pesun teoriaan sekä kuitulinjan kemikaaliannosteluihin vaikuttaviin tekijöihin. Molemmissa koeajoissa pinta-aktiiviaineet A ja B annosteltiin massan joukkoon juuri ennen happivaihetta. EOP-vaiheeseen pinta-aktiiviaine B annostelu tehtiin D0-vaiheen pesurin jälkeiseen massaan. Asetoniuutemääritykset tehtiin massasta ennen happivaihetta, happivaiheen jälkeen ja valkaistulle massalle sekä pinta-aktiiviaine B koeajon yhteydessä EOP-vaiheen jälkeen. Pinta-aktiiviaineiden käytöllä havaittiin olevan positiivinen vaikutus kuitulinjan asetoniuutetasojen kehittymisessä. Verrattuna referenssijaksoon, oli happivaiheen alkali- ja happiannokset pienemmät pinta-aktiiviaineiden käytön aikana ilman, että saavutettu kappareduktio heikkeni. Pesurien toiminnan kannalta pinta-aktiiviaineiden käytöllä oli myönteisiä vaikutuksia pesutehokkuuden ja pesun ta-saisuuden kannalta. Lisäksi havaittiin valkaisussa merkittävä muutos D0- ja D1-vaiheiden klooridioksiveden käytössä ja EOP-vaiheen alkaliannoksessa.

Runkopaperin imukyvyn optimointi

Diplomityön tarkoituksena oli optimoida laminaatin valmistuksessa käytettävän runkopaperin imukyky niin, että pienemmällä hartsimäärällä saavutetaan vähintään jo olemassa olevat impregointi- ja laminaatin ominaisuudet tai että nykyisellä hartsimäärällä saadaan nopeampi imeytyminen läpi paperirakenteen. Kirjallisuusosassa etsittiin ja selvitettiin erilaisten tekijöiden tai toimintatapojen vaikutukset, joilla voitaisiin muokata paperin imukyky halutulle tasolle. Kirjallisuudesta löydetyistä tekijöistä ja menetelmistä valittiin kokeelliseen osaan tutkittavaksi potentiaalisimmat sekä toteutuskelpoisimmat tavat. Diplomityön kokeellinen osuus koostui kahdesta osasta. Ensimmäisessä vaiheessa kirjallisuudesta löydettyjä menettelyjä testattiin laboratoriomittakaavassa erilaisilla esikokeilla. Työn toisessa vaiheessa suoritettiin pilotpaperikoneella koeajo, jossa tutkittiin tarkemmin esikokeiden menetelmiä, jotka olivat antaneet lupaavia tuloksia. Lisäksi tutkittiin menetelmiä, joita ei esikokeissa kokeiltu, mutta jotka olivat teoreettisesti kiinnostavia. Tulosten perusteella paperin hartsinottokykyä pystyttiin madaltamaan nestemäisen AKD-liiman sekä erään kemikaalin avulla. Hartsin imeytymisnopeutta paperiin pystyttiin kasvattamaan kuidun entsymaattisella käsittelyllä, lämpösarveistamalla sekä käyttämällä erästä pinta-aktiivista ainetta.

Verhopäällystyspastojen analyysimenetelmät

Diplomityön tarkoitus oli selvittää verhopäällystyspastoille sopivia analyysimenetelmiä. Verhopäällystyksessä onnistunut päällystystapahtuma vaatii venymäviskositeetin ja pintajännityksen hyvää hallintaa. Kirjallisuusosassa käsiteltiin verhopäällystystä, verhopäällystyspastojen koostumusta, reologiaa ja pintajännitystä. Kirjallisuusosassa käsiteltiin lisäksi verhopäällystyspastojen reologian ja pintajännityksen mittaamiseen soveltuvia mittausmenetelmiä. Verhopäällystyksen luonteen vuoksi kirjallisuusosassa syvennyttiin venymäviskositeetin ja dynaamisen pintajännityksen mittaamiseen tarkoitettuihin menetelmiin. Kokeellisessa osassa tutkittiin päällystyspastasarjojen reologiaa ja pintajännitystä verhopäällystystä varten. Osaan päällystyspastoista luotiin venymäviskositeettia ja osasta laskettiin pintajännitystä. Venymäviskositeetin mittaamista varten työssä käytettiin ACAV A2 -reometriin liitettyjä teräsreikälevyjä. Dynaamisen pintajännityksen mittaamista varten työssä käytettiin KSV BPA-800P -pintajännitysmittaria. ACAV A2 -reometriin liitettyjen teräsreikälevyjen (reiän sisähalkaisija 0,5 tai 0,7 mm) avulla mitattiin venymäviskositeettia kuvaavia Eulerin lukuarvoja onnistuneesti suurilla kiintoainepitoisuuksilla (50, 60 tai 65 p %). Erikoispaksuntajan määrää lisäämällä onnistuttiin luomaan huomattavaa venymäviskositeettia. Kiintoainepitoisuuden kasvaessa kasvoi myös venymäviskositeetti. Tavanomaisille paksuntajille mitattiin hieman kohonneita venymäviskositeetteja verrattuna referenssipäällystyspastaan. Pigmenttikoostumuksella (kalsiumkarbonaatti/kaoliini) ei näyttänyt olevan vaikutusta venymäviskositeettiin, tai vaikutus oli suhteellisen pieni. Dynaamisen pintajännityksen mittaamista varten käytössä ollut KSV BPA-800P -pintajännitysmittari ei toiminut luotettavasti, vaikka näytteitä laimennettiin. Kiintoainepitoisuudessa 10 p-% olleilla laimennoksilla saavutettiin analysoinnin kannalta parhaat tulokset. Tuloksista saatiin kuitenkin viitteitä, että kyseinen mittari voisi olla potentiaalinen menetelmä dynaamisen pintajännityksen mittaamiseksi.

Unusual bismuth-containing surface layers of III-V compound semiconductors

The understanding and engineering of bismuth (Bi) containing semiconductor surfaces are signi cant in the development of novel semiconductor materials for electronic and optoelectronic devices such as high-e ciency solar cells, lasers and light emitting diodes. For example, a Bi surface layer can be used as a surfactant which oats on a III-V compound-semiconductor surface during the epitaxial growth of IIIV lms. This Bi surfactant layer improves the lm-growth conditions if compared to the growth without the Bi layer. Therefore, detailed knowledge of the properties of the Bi/III-V surfaces is needed. In this thesis, well-de ned surface layers containing Bi have been produced on various III-V semiconductor substrates. The properties of these Bi-induced surfaces have been measured by low-energy electron di raction (LEED), scanning-tunneling microscopy and spectroscopy (STM), and synchrotron-radiation photoelectron spectroscopy. The experimental results have been compared with theoretically calculated results to resolve the atomic structures of the studied surfaces. The main ndings of this research concern the determination of the properties of an unusual Bi-containing (2×1) surface structure, the discovery and characterization of a uniform pattern of Bi nanolines, and the optimization of the preparation conditions for this Bi-nanoline pattern.

Reverse osmosis membrane surface modification: effects on membrane performance

The aim of this thesis was to study the surface modification of reverse osmosis membranes by surfactants and the effect of modification on rejection and flux. The surfactants included anionic and nonionic surfactants. The purpose of membrane modification was to improve pure water permeability with increasing salt rejection. The literature part of the study deals with the basic principles of reverse osmosis technology and factors affecting the membrane performance. Also the membrane surface modification by surfactants and their influence on membrane’s surface properties and efficiency (permeability and salt rejection) were discussed. In the experimental part of the thesis two thin-film composite membranes, Desal AG and LE-4040, were modified on-line with three different surfactants. The effects of process parameters (pressure, pH, and surfactant concentration) on surface modification were also examined. The characteristics of the modified membranes were determined by measuring the membranes’ contact angle and zeta potentials. The zeta potential and contact angle measurements indicate that the surfactants were adsorbed onto the both membranes. However, the adsorption did not effect on membrane’s pure water permeability and salt rejection. Thereby, the surface modification of the Desal AG and LE-4040 membranes by surfactants was not able to improve the membrane’s performance.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Ultrasonic and Electrokinetic Remediation of Low Permeability Soil Contaminated with Persistent Organic Pollutants

Electrokinetics has emerged as a potential technique for in situ soil remediation and especially unique because of the ability to work in low permeability soil. In electrokinetic remediation, non-polar contaminants like most organic compounds are transported primarily by electroosmosis, thus the process is effective only if the contaminants are soluble in pore fluid. Therefore, enhancement is needed to improve mobility of these hydrophobic compounds, which tend to adsorb strongly to the soil. On the other hand, as a novel and rapidly growing science, the applications of ultrasound in environmental technology hold a promising future. Compared to conventional methods, ultrasonication can bring several benefits such as environmental friendliness (no toxic chemical are used or produced), low cost, and compact instrumentation. It also can be applied onsite. Ultrasonic energy applied into contaminated soils can increase desorption and mobilization of contaminants and porosity and permeability of soil through developing of cavitation. The research investigated the coupling effect of the combination of these two techniques, electrokinetics and ultrasonication, in persistent organic pollutant removal from contaminated low permeability clayey soil (with kaolin as a model medium). The preliminary study checked feasibility of ultrasonic treatment of kaolin highly contaminated by persistent organic pollutants (POPs). The laboratory experiments were conducted in various conditions (moisture, frequency, power, duration time, initial concentration) to examine the effects of these parameters on the treatment process. Experimental results showed that ultrasonication has a potential to remove POPs, although the removal efficiencies were not high with short duration time. The study also suggested intermittent ultrasonication over longer time as an effective means to increase the removal efficiencies. Then, experiments were conducted to compare the performances among electrokinetic process alone and electrokinetic processes combined with surfactant addition and mainly with ultrasonication, in designed cylinders (with filtercloth separating central part and electrolyte parts) and in open pans. Combined electrokinetic and ultrasonic treatment did prove positive coupling effect compared to each single process alone, though the level of enhancement is not very significant. The assistance of ultrasound in electrokinetic remediation can help reduce POPs from clayey soil by improving the mobility of hydrophobic organic compounds and degrading these contaminants through pyrolysis and oxidation. Ultrasonication also sustains higher current and increases electroosmotic flow. Initial contaminant concentration is an essential input parameter that can affect the removal effectiveness.