Abstract Fouling in papermaking causes major economic drawbacks due to downtime of process and paper quality defects. The surface fouling is a complex phenomenon in a paper making process, which is affected by several interconnected factors such as process environment changes from wet to dry with increasing temperature along with the variety of sticky materials present in paper raw materials. These impurities, such as waxes, coating binders, hot melts and pressure-sensitive adhesives have a tendency to attach to the surfaces of machinery during paper production and cause surface fouling. The focus of this thesis was on the mechanisms of sticking and surface fouling on a paper machine surfaces caused by problematic sticky organic materials. The sticking potential of six styrene–butadiene latices varying in carboxylation degree, crosslinking density and viscoelasticity and one polyacrylate pressure sensitive adhesive were studied using a cylindrical probe tack method under dry and aqueous conditions. Sticking potential was measured using low and high energy surfaces as an adherent. Also a new practical method for the on-site evaluation of nonstick properties of cylinder coating materials was developed. This method enables monitoring the condition of the coating during its life cycle and also provides the opportunity to compare the performance of different drying cylinder coating materials. The research performed clearly showed that low viscoelastic modulus of latex increases sticking tendency. The results also showed that presence of water can either increase or decrease adhesion depending on the moisture content ant the physic-chemical properties of sticky materials. A low surface energy coating strongly decreases sticking compared to a high energy surface and have a lower susceptibility to fouling in the dry environment. In aqueous conditions, the use of high-energy surfaces decreases adhesion of latices due to their strong interaction with water. Also, the results indicated that carboxylation decreases sticking potential of latex in both dry and aqueous environments. / Tiivistelmä Paperikoneiden likaantuminen aiheuttaa suuria tuotannollisia menetyksiä johtuen tuotantoprosessin katkoksista ja paperin laadun ongelmista. Paperikoneen pintojen likaantuminen on monimutkainen prosessi, johon vaikuttavat monet toisistaan riippuvat tekijät ja siten likaantumisilmiötä on vaikea hallita. Paperin raaka-aineet voivat sisältää epäpuhtauksia, kuten vahoja, kuumasulate- ja tarraliimoja, jotka tarttuvat paperikoneen pintoihin aiheuttaen niiden likaantumista. Lisäksi paperin prosessiympäristö muuttuu märästä kuivaan valmistusprosessin edetessä ja lämpötilan kasvaa samanaikaisesti. Tässä väitöskirjassa on kuvattu paperikoneen pintojen likaantumisen mekanismeja ja erityisesti orgaanisten lika-aineiden tarttumista. Tutkimuksessa selvitettiin probe tack -menetelmää käyttäen kuuden erilaisen styreeni-butadieenilateksin ja polyakrylaattitarraliiman tarttuvuutta matalan ja korkean pintaenergian pinnoilla sekä kuivissa että märissä olosuhteissa. Työhön oli valittu latekseja, joiden karboksylointiaste, ristisilloitustiheys ja viskoelastiset ominaisuuden olivat erilaisia. Lisäksi väitöskirjatyössä kehitettiin paikan päällä suoritettava mittausmenetelmä paperikoneen kuivaussylinterien pinnoitteen puhtaana pysyvyyden määrittämiseksi. Tällä menetelmällä voidaan mitata pinnoitteiden kuntoa niiden elinkaaren aikana ja myös vertailla erilaisia pinnoitteita keskenään. Tutkimuksen tulokset osoittivat, että styreeni-butadieenilateksien matala kimmokerroin lisää niiden tarttumista paperikoneen pinnoille. Veden läsnäolo voi joko lisätä tai vähentää tarttumista riippuen veden määrästä ja lika-aineiden fysiokemiallisista ominaisuuksista. Myös paperikoneen pinnoitteen pintaenergia vaikuttaa tarttuvuuteen. Paperikoneen pinnoitteiden pieni pinta-energia vähentää tarttumista kuivissa olosuhteissa, kun taas korkean pintaenergian pinnoitteet vähentävät lateksien tarttuvuutta vesiolosuhteissa. Lisäksi lateksien karboksylointi vähentää niiden tarttumista sekä kuivissa että märissä olosuhteissa.

The emergence of microneedle (MN) technologies offers a route for a pain free, straightforward and efficient way of transdermal drug delivery, but technological barriers still exist which pose significant challenges for manufacture of MN systems with high volume outputs at low cost. The main aim of this research was to develop new ways for MN manufacture primarily using micro-injection moulding processes with high performance engineering thermoplastics. During the moulding process these polymeric melts will be subjected to extreme stress and temperature gradients and detailed material characterisation combined with in-line monitoring is desirable to optimise the moulding parameters and will help in achieving sharp microneedles with acceptable quality. Hence high shear rheology of these selected materials was performed at wall shear rates carried out in excess of 107 s-1 over a range of temperatures to predict the flow behaviour of polymer melts at such high shear strain rates. This information was fed into injection moulding simulation software tools (Moldflow) to assist the MN production process design. The optimal design was then used to produce a full 3D solid model of the injection mould and mould insert. Furthermore various design of experiments were conducted considering input parameters such as injection pressure, injection speed, melt temperature, filling time and mould cavity temperature. Response variables including product quality and data acquired from the cavity pressure and temperature transducers were used to optimise the manufacturing process. The moulded MNs were geometrically assessed using a range of characterisation techniques such as atomic force microscopy, confocal microscopy and scanning electron microscopy. An attempt to make hollow MNs was performed and encountered many challenges like partial cavity filling and part ejection during processing. Studies were carried out to understand the problem and identified the major problem was in tool design and improvements to the moulding tool design were recommended. Plasma treatment and mechanical abrasion were employed to increase the surface energy of the moulded polymer surfaces with the aim of enhancing protein adsorption. Sample surface structures before and after treatment were studied using AFM and surface energies have been obtained using contact angle measurement and calculated using Owens-Wendt theory. Adsorption performance of bovine serum albumin and release kinetics for each sample set was assessed using a Franz diffusion cell. Results indicate that plasma treatment significantly increases the surface energy and roughness resulting in better adsorption and release of BSA. To assist design-optimisation and to assess performance, a greater understanding of MN penetration behaviour is required. Contact stiffness, failure strength and creep behaviour were measured during compression tests of MN against a steel surface, and in-vitro penetration of MNs into porcine skin. The MN penetration process into porcine skin was imaged using optical coherence tomography. Finally, a finite element model of skin was established to understand the effect of tip geometry on penetration. The output of findings from this research will provide proof of concept level development and understanding of mechanisms of MN penetration and failure, facilitating design improvements for micro-injection moulded polymeric MNs.

Dans les systèmes anaérobies de traitement d'eaux usées, la biomasse microbienne complexe incluant archées et bactéries peut être maintenue au sein du procédé par l'adhésion aux supports solides sous forme de biofilm. Le but de ce travail est d'évaluer l'impact des propriétés des matériaux supports sur l'adhésion et la colonisation du consortium méthanogène. Différents matériaux (le polyéthylène, le polypropylène, le chlorure de polyvinyle, l'acrylonitrile butadiène styrène, le polycarbonate, le verre borosilicaté, l'acier inoxydable 304L et Bioflow 30 ®) sont décrits en termes de topographie par la détermination de rugosité et en termes d'énergie de surface par la mesure d'angle de contact. Le biofilm est évalué quantitativement et les structures communautaires bactériennes et archéennes sont observées grâce à l'analyse moléculaire à différents stades de sa mise en place. L'adhésion d'un consortium méthanogène sur les matériaux après deux heures de contact dans un réacteur annulaire rotatif révèle que les communautés adhérées diffèrent de l'inoculum, y compris en termes de proportion archées/bactéries. Ce résultat a un impact significatif sur le démarrage de digesteurs anaérobie car les tendances observées sont confirmées pendant l'établissement du biofilm actif. La mise en oeuvre de différents matériaux dans des réacteurs à lit fixe a permis de montrer que les populations d'archées des biofilms sont spécifiques au matériau et indépendantes de l'inoculum. / In anaerobic wastewater treatment systems, the complex microbial biomass including Archeae and Bacteria may be retained as a biofilm by attachment to solid supports. The aim of this study is to evaluate the impact of support material properties on adhesion and colonization. Various substrata (polyethylene, polypropylene, polyvinyl chloride, acrylonitrile butadiene styrene, polycarbonate, borosilicate glass, stainless steel 304L and Bioflow 30®) are described in terms of topography by determinating of roughness and in terms of surface energy by contact angle measurement. Adhesion is quantified and the bacterial and archaeal community structure are assessed by molecular analysis in various stages of the biofilm development. Adhesion of a methanogenic consortium on these substrata Is measured after two hours of contact in a rotating annular reactor. The result reveals that the adhered communities were different from the parent inocula, including the Archeae/Bacteria ratio. This result has a significant impact on the start-up of anaerobic digesters because the observed tendencies are confirmed during the establishment of the active biofilm. Start-up of anaerobic fixed-bed reactors using different substrata showed that Archeae populations in the biofilms are specific to each of the material and independent of the inoculum.

La ténacité et l’énergie de surface de fracture de verres, de vitrocéramiques et de composites à matrice en verre ont été étudiées. Tout d'abord, un test de flexion bi-axiale (configuration anneau/anneau) a été réalisé sur des verres de silice et des verre-à-vitres avec différentes conditions de surface afin d’identifier la relation entre le défaut de surface, la résistance et la ténacité du verre. Ensuite, trois méthodes d’expérimentation ont été mises en œuvre, principalement la méthode de poutre de flexion à pré-entaille droit (SEPB), la méthode de la poutre entaillée en chevron (CNB) et la méthode de la poutre avec indentations Vickers (VIF), afin de déterminer la ténacité de quatre verres produits industriellement et de déterminer les avantages et les inconvénients des différents méthodes sélectionnées. La méthode qui est apparue la plus fiable et auto-cohérente, la méthode SEPB (Single Edge Precrack Beam), a été appliquée à la détermination de la ténacité de nombreux verres et vitrocéramiques, afin d’étudier l’influence de la composition et de la microstructure sur les caractéristiques de fissuration (KIC et énergie de fissuration, γ). Enfin, l’influence de la température et de l'environnement sur la ténacité a été étudiée à l'aide de la méthode SEPB. Deux verres d'oxyde ont été testés à des températures élevées et avec une vitesse de charge de 10 MPa∙√m/s, une température de transition de 1,11Tg a été trouvée. Quatre autres verres d'oxyde ont été testés en environnement inerte et les mêmes valeurs de ténacité ont été obtenues à partir de deux vitesses de charge (100 fois) différentes. / Fracture toughness and fracture surface energy of commercial and laboratory glasses, glass-ceramics and glass matrix composites have been studied. First, bi-axial bending test (RoR configuration) was performed on fused silica and window float glasses with different surface conditions to identify the relationship between the surface flaw, the strength and fracture toughness. After, three experiment methods, mainly single-edge precracked beam (SEPB), chevron-notched beam (CNB) and Vickers indentation fracture (VIF) were performed to determine the fracture toughness of four commercial known glasses and to determine the advantages and inconveniences of the different selected methods. The method that is appeared as the most reliable and self-consistent, the SEPB (Single Edge Precrack Beam) method, was applied to determine the toughness of the large amount of glasses and glass-ceramics, to study the influence of the composition and the microstructure on the characteristics of cracking (KIC and fracture energy, γ). Last but not least, the influence of the temperature and environment on the fracture toughness was studied by means of the SEPB method. Two oxide glasses were tested in elevated temperatures and with the loading rate of 10 MPa∙√m/s, a transition temperature of 1.11Tg was found. Four other oxide glasses were tested in the inert environment and the same fracture toughness values were obtained from (100 times) two different cross-head speeds.

Content: The present work attempts to analyze the surface and physical properties of leathers finished with cationic and anionic finishing chemicals. The contact angles of liquid drops resting on the leather surface have been used to evaluate surface energy, acidity, basicity components of the surface energy, polarity and work of adhesion. Contact angle values have been measured for chrome tanned and conventionally retanned crust and finished leather made by varying pigment and binder combinations. The wettability of finished leather has been correlated with the contact angle values: the higher the contact angle value the lesser is the wetting observed. Complete wetting can be obtained when the contact angle value is zero i.e. the drop of liquid spreads spontaneously on the surface and partial wetting is obtained when the contact angle value is in between 0and 900. Acrylic binders with different film forming properties, protein, polyurethane and butadiene binders have been combined to prepare different finish formulations.The results have been correlated with wet and dry rub fastness, finish adhesion, vamp flexing value, water vapour permeability and water proofness. It has been observed that when the surface of leather is coated with acrylic binder the contact angle value due to polar solvents(water) , non polar solvents(hexadecane) and moderately polar (DMSO) and methyl iodide show that as the thickness of coating increases, the contact angle value decreases for the base coat and sharply increases when top coat is applied. Top coats have the ability to increase the contact angle and they improve the performance properties of leather such as water resistance, fastness, finish adhesion etc. Cationic and anionic finishing formulations have been compared to study their effect in modifying the surface of finished leather based on contact angle values, wet and dry fastness to circular rubbing and water resistance. It has been observed that leathers finished using anionic finishing technique shows better wet rub fastness and water resistance effect compared to cationic finishing technique. Take-Away: The effect of number of top coats on water contact angle value were determined ,and the experiment showed that the value were decreased gradually at the beginning of the coat because the top coats are water based so during the coating process the hydrophobic nature of the surface of chrome tanned leather have decreased. The experimental result from contact angle value showed that coating with pigments and binders have increased the contact angle value compared to the control crust. It has been observed that leathers finished using anionic finishing technique shows better wet rub fastness and water resistance effect compared to cationic finishing technique.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) show great potential for the future electronics, optoelectronics and energy applications. But, the studies unveiling their interactions with the host substrates are sparse and limits their practical use for real device applications. We report the facile nano-scratch method to determine the adhesion energy of the wafer scale MoS2 atomic layers attached to the SiO2/Si and sapphire substrates. The practical adhesion energy of monolayer MoS2 on the SiO2/Si substrate is 7.78 J/m2. The practical adhesion energy was found to be an increasing function of the MoS2 thickness. Unlike SiO2/Si substrates, MoS2 films grown on the sapphire possess higher bonding energy, which is attributed to the defect-free growth and less number of grain boundaries, as well as less stress and strain stored at the interface owing to the similarity of Thermal Expansion Coefficient (TEC) between MoS2 films and sapphire substrate. Furthermore, we calculated the surface free energy of 2D MoS2 by the facile contact angle measurements and Neumann model fitting. A surface free energy ~85.3 mJ/m2 in few layers thick MoS2 manifests the hydrophilic nature of 2D MoS2. The high surface energy of MoS2 helps explain the good bonding strength at MoS2/substrate interface. This simple adhesion energy and surface energy measurement methodology could further apply to other TMDs for their widespread use.

M. Tech. (Department of Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / The developed oil-water separation membranes used in membrane technology are currently inefficient due to their poor morphological and topographical properties during nanoparticle coating. Researchers have developed different wettable membrane surfaces using jet spray coating. Most of these developed membranes are inadequate due to poor morphological and topographical properties normally observed as clusters, creating a rougher membrane surface that hinders wettability. This has resulted in the existing membrane fouling and degradation during the oil/water separation process and again due to different responses to corrosion and rusting. In the current study, membrane clusters were minimised on the ceramic membranes to create a smoother surface, improving membrane wettability. These clusters were minmised at optimal coating force, optimal coating distance and optimal coating angle. Part one of the study was to model and simulate different parameters that decreased clusters using the jet-spray coating. A theoretical model was derived from the first principles and all the external and internal forces that impact membrane clusters were considered during the model derivation. These forces are the force due to applied pressure from the spray gun, the force of nano-particles, the force of viscosity, the upward force on solid wall due to nanoparticles, the downward force on solid wall due to nanoparticles and the reaction force on the solid wall due to nanoparticles. The tools of stochastic theory and the concept of fluid dynamics were used in the modelling process. The total coating force from the jet spray gun nozzle was increased from 0,2x107 kN to 2,4x107 kN, which gave optimal coating force. The coating distance from the jet spray gun nozzle to the membrane surface was increased from 10 mm to 24 mm, which gave optimal coating distance. The jet spray angle in the spray region was also increased from 1⁰ to 9⁰ with reference from the vertical axis to the membrane surface, which gave optimal coating angle. This lead to optimal spread of nanoparticles on the membrane surface thus resulting to optimal cluster minimisation during the coating process. This decreased cluster sizes during nanoparticle coating, resulting in a smooth membrane surface, thus leading to lowered surface energy on the membrane. Part two of the study was to fabricate the ceramic membrane with fewer clusters on the surface for improved wettability using the jet-spray coating. It was important to produce the ceramic membrane surfaces with minimised membrane clusters by considering the optimal parameters revealed to minimise these membrane clusters during coating. Nanoparticle coating was performed under a controlled laboratory environment, and the optimal parameters that were studied to minimise membrane clusters were revealed. These parameters are coating force, coating distance and coating angle. More coating rounds were applied on ceramic samples and clusters were minimised during these coating rounds. The coated samples were analyzed by a scanning electron microscope and the nanoparticles on the membrane surfaces were characterised for optimal performance during oil-water separation. The scattering, orientation, morphology, spatial distribution, surface roughness, surface smoothness, contact angles, surface density of the particles, pore size network, mean size of the coated nanoparticle on the membrane surface after different coating rounds were characterised and analysed to minimise membrane cluster during nanoparticle coating. It was shown that more clusters were observed in 1st LP, 2nd LP, 3rd LP and 4th LP coating rounds when compared to 1st HP, 2nd HP, 3rd HP and 4th HP coating rounds. It was also shown that material surface roughness increased the formation of clusters in membrane surface as more clusters were observed in rough membrane surface when compared to the smooth membrane surface. The microstructure revealed a smoother membrane surface where membrane clusters were minimised. Part three of the study was to compare the newly designed ceramic membrane with the previously designed ceramic membrane from previous the literature. The correlation was done on the experimental results obtained in this study with the experimental results obtained from the previous literature. Different coating rounds were performed from the current study and the previous literature to design nanostructured ceramic membranes with fewer clusters on the surface. The results in the last coating round in this study, revealed a smooth membrane with a homogeneous substrate with fewer clusters and small sizes compared to other coating rounds.

High latitude and altitude ecosystems are currently undergoing rapid and unprecedented warming in response to anthropogenically induced climate change. Subarctic, alpine regions are particularly vulnerable to increases in air temperature and changing precipitation regimes, which have caused cascading hydrological and ecological impacts. In addition to changing flow regimes, thawing permafrost, and declining glaciers, widespread changes in vegetation composition, density and distribution have been observed across northern regions. Specifically, treeline is advancing with increasing latitude and altitude and shrubs are increasing in height, extent, and density. Despite widespread documentation of this northern greening, few field-based studies have evaluated the hydrological implications of these changes. Quantification of total evapotranspiration (ET) across a range of vegetation gradients is essential for predicting water yield, yet challenging in cold alpine catchments due to heterogeneous land cover. Direct field-level measurements of transpiration (T) and evaporative partitioning across subarctic, alpine ecosystems and species are rare, yet essential to assess sensitivities and hydrological response to changing climate drivers. This thesis presents six years of surface energy balance components and ET dynamics and two years of sap flux measurements and critical zone stable water isotope sampling at three sites along an elevational gradient in a subarctic, alpine catchment near Whitehorse, Yukon Territory, Canada. These sites span a gradient of thermal and vegetation regimes, providing a space-for-time comparison for future ecosystem shifts: 1) a low-elevation boreal white spruce forest (~12-20 m), 2) a mid-elevation subalpine taiga comprised of tall, dense willow (Salix) and birch (Betula) shrubs (~1-3 m) and 3) a high-elevation subalpine taiga with short, sparse shrub cover (< 0.75 m) and moss, lichen, and bare rock. We utilize both mass flux measurements and stable water isotopes to evaluate the timing, magnitude, sensitivities, and sources of plant water uptake across these vegetation covers. Total ET decreased and interannual variability increased with elevation, with mean May to September ET totals of 349 (±3) mm at the forest, 249 (±10) mm at the tall, dense shrub site, and 240 (± 26) mm at the short, sparse shrub site. The shrub sites exhibited similar ET losses over 6 years despite differences in shrub height and abundance, although daily rates were higher at the tall shrub site in the peak growing season. From May to September, ET:R ratios were the highest and most variable at the forest (2.19 ± 0.37) and similar at the tall, dense shrub (1.22 ± 0.09) and short, sparse shrub (1.14 ± 0.05) sites. In the mid-growing season, mean T rates were greater at the dense shrub site (2.0 ± 0.75 mm d-1) than the forest (1.47 ± 0.52 mm d-1). During this time, T:ET was lower at the forest (0.48) than at the tall, dense shrub site (0.80). During the growing season between the two years, 2020 was considerably wetter and cooler than 2019. At the tall shrub site, during the mid-growing season (July 1-Aug 15), T dropped considerably in 2020 (-26%), as T was suppressed during the short, wet growing season. In contrast, T at the forest was only moderately suppressed (-3%) between years in this same period. Evapotranspiration was more strongly controlled by air temperature during the early and late season at the forest, while ET at the shrub site was more sensitive to warmer temperatures in the mid-growing season. At the shrub sites, ET was energy limited with no observed soil moisture limitation on T. While 2H and 18O of volume weighted precipitation became more depleted with elevation, the opposite was true in xylem water, where 2H and 18O became more enriched with elevation. Plant water uptake was more reflective of snow water at the forest site than both shrub sites, particularly early in the year and during dry periods. Near-surface bulk soil water had more negative lc-excess at the forest throughout the season and with depth, highlighting increased contributions from soil evaporation. This study combined direct measurements of sap flux, ET, and critical zone isotopes to provide new details on multi-year plant-soil-water dynamics, critical zone water cycling, and species-specific plant water uptake patterns in seasonally frozen soils, which have not previously been reported in cold regions. Our results suggest that advances in treeline will increase overall ET and lower interannual variability; however, the large growing season water deficit and stable water isotope signature at the forest indicates strong reliance on soil moisture from late fall and snowmelt recharge and the potential for plant water stress. Differences between the shrub species were apparent in the sap flux and stable isotope measurements, highlighting the need to further evaluate species specific responses and feedbacks when predicting hydrological fluxes across subarctic ecosystems. Overall, our results suggest that predicted changes in vegetation type and structure in northern regions will have a considerable impact on water partitioning and will vary in a complex way in response to changing precipitation timing, phase and magnitude. / Thesis / Candidate in Philosophy

Yes / Numerical simulation of wet granulation in a continuous granulator is carried out using Discrete Element Method (DEM) to discover the possibility of formation of seeded granules in a continuous process with the aim of reducing number of experimental trials and means of process control. Simple and scooped drum granulators are utilized to attain homogenous seeded granules in which the effects of drum rotational speed, particles surface energy, and particles size ratio are investigated. To reduce the simulation time a scale-up scheme is designed in which a dimensionless number (Cohesion number) is defined based on the work of cohesion and gravitational potential energy of the particles. Also a mathematical/numerical method along with a MATLAB code is developed by which the percentage of surface coverage of each granule is predicted precisely. The results show that use of continuous granulator is promising provided that a high level of shear is considered in the granulator design, e.g. it is observed that using baffles inside the drum granulators is essential for producing seeded granules. It is observed, moreover, that the optimum surface energy for scooped granulator with rotational speed of 50 rpm is 3 J/m2 which is close to the number predicted by Cohesion number. It is also shown that increasing the seed/fine size ratio enhances the seeded granulation both quantitatively (60% increase in seeds surface coverage) and qualitatively (more homogeneous granules).

<p dir="ltr">We investigate the surface diffusion flow of smooth curves with anisotropic surface energy.</p><p dir="ltr">This geometric flow is the H−1-gradient flow of an energy functional. It preserves the area</p><p dir="ltr">enclosed by the evolving curve while at the same time decreases its energy. We show the</p><p dir="ltr">existence of a unique local in time solution for the flow but also the existence of a global in</p><p dir="ltr">time solution if the initial curve is close to the Wulff shape. In addition, we prove that the</p><p dir="ltr">global solution converges to the Wulff shape as t → ∞. In the current setting, the anisotropy</p><p dir="ltr">is not too strong so that the Wulff shape is given by a smooth curve. In the last section, we</p><p dir="ltr">formulate the corresponding problem when the Wulff shape exhibits corners.</p>