The thesis treatise can be divided in three major parts as A, B and C respectively.Part A constitutes the concept and objectives of the plasma treatment for textiles. Itincludes a technical overview, the principle and the recent developments in plasmatypes for textiles.Part B, provides an overview on plasma technology to its interaction with thesubstrate. The part describes the surface modification phenomenon i.e. physical andchemical interaction and the highlights the effects yields from it.Part C, constitute a bibliographic analysis on the application of this technology totextiles. Various paper and patents and cited to provide an overview on key aspects ofthe scientific research, commercial technology, and information on manufacturerswhich are being taken place to date. The section followed then critical dichotomyappraisal on the plasma technology in the field.All the citation, are thoroughly questioned and evaluated before own use of thematerial in this study. Also, the citation has been taken from reliable sources. In orderto increase the reliability of the material comparison between sources is done / Program: Magisterutbildning i textilteknologi

Three different fine-particles (lanthanum fluoride nanoparticles, cerium oxide nanoparticles and zinc borate submicron particles) were modified and tested on the purpose of study the effects of surface modified fine-particles when they used as lubricant additives in liquid paraffin. The modified fine-particles were examined and characterised by a FT-IR spectroscopy and a zeta-potential measurer. The tribological performances of surface modified fine-particles were invalided by a pin-on-disc test rig under various experimental environments. The worn surfaces on post-tested pin were analysed by AFM, SEM and a nano-indentation tester. The results indicated Hexadecyltrimethoxysilane (HS) modified lanthanum fluoride nanoparticles and HS modified cerium oxide nanoparticles all shown better dispersibility than unmodified lanthanum fluoride nanoparticles and unmodified cerium oxide nanoparticles in liquid paraffin (LP). HS modified lanthanum fluoride nanoparticles and HS modified cerium oxide nanoparticles also have been approved that they can improve the tribological properties of LP significantly under various working conditions. The formation of tribo-films on the worn scar is the key mechanism of friction and wear reduction. On the other hand, surface modified zinc borate submicron particles have not demonstrated great potential as an oil lubricant additive under various working conditions. HS, as a particle surface modifier, could improve the performance of fine-particle oil lubricant additives impressively. The positive effects of HS on both dispersibility and tribological performance of surface modified fine-particles were observed.

Synthetic membranes have a high separation efficiency, small footprint, low energy consumption and ease of operation, making them an attractive alternative to traditional separation operations. For this reason, membranes have been extensively studied for the treatment and recycling of bitumen-containing wastewaters. Such wastewaters include petroleum produced water, residual pipeline cleaning solutions and contaminated water from oil spills. Ceramic membranes are preferred in these applications over polymeric membranes because they are highly resistant to solvents and can be operated at high temperatures over a wide range of pH. Fine clays and silicates, coated with bitumen, are significant foulants for membrane filtration systems. These foulants possess acidic, basic and amphoteric groups, leading to the presence of both positive and negative surface charges. Ceramic membranes in aqueous media have a pH dependent surface charge. It was hypothesized that these surface charges are responsible for the high fouling of ceramic membranes that is observed when treating wastewaters containing bituminous fines. The overall objective of this research was to reduce fouling and increase the lifetime of ceramic membranes in treating oil sands produced water; an example of a wastewater containing bituminous fines. This goal was achieved through the surface modification of the ceramic membrane’s selective layer, as well as by the implementation of a novel in-place steam regeneration technique. All membrane filtration tests were performed with field samples of oil sands produced water that were supplied to CanmetMINING (NRCan) by three Canadian oil sands companies. Organosilanes are silicon-based monomers that can possess a wide array of chemical functionality due to their organic moieties. They are capable of reacting with oxide surfaces, and have seen extensive use as surface modification agents for ceramic membranes in various applications. To maintain desirable hydrophilic properties without surface charges, highly hydrophilic and non-ionic polyethylene oxide (PEO) based organosilanes were identified. These PEO-silanes were then used to modify ceramic membranes of several different selective layer materials, and the thermal stability of the silane layer was studied using FTIR, SEM, zeta potential and contact angle measurements. The modification procedure with PEO-silanes was first applied to lab-scale membrane disks, and subsequently to commercial scale multilumen membrane tubes that were tested in a pilot-scale system at CanmetMINING. Results obtained from both sets of experiments were promising and demonstrate that ceramic membranes can be surface modified in a way that successfully renders them fouling resistant to the bituminous fines present in these wastewaters. Upon surface modification, foulants were more readily released from the membrane surface, resulting in an enhanced flux and separation performance. A novel steam regeneration technique was also applied as a means of bituminous fouling alleviation. This technique was tested in the CanmetMINING pilot-scale system and consisted of periodically injecting steam into the membrane lumen feed channels during operation. Direct steam injection rapidly heated foulant cake layers, and water droplets in the saturated steam caused surface abrasions that ultimately resulted in the scouring of bitumen away from the membrane surface. Membrane fluxes when steam regeneration was active were up to 4 times higher when compared to tests where only traditional permeate backflushing was used. The fouling remediation techniques developed in this work have broad potential applicability in ceramic membrane filtration systems aimed at treating all wastewaters containing bituminous compounds, such as process waters in general and contaminated water from oil spills.

This thesis investigates the application of plasma immersion ion implantation (PIII) to polymers. PIII requires that a high negative potential be applied to the surface of the material while it is immersed in a plasma. This presents a problem for insulating materials such as polymers, since the implanting ions carry charge to the surface, resulting in a charge accumulation that effectively neutralises the applied potential. This causes the plasma sheath at the surface to collapse a short time after the potential is applied. Measurements of the sheath dynamics, including the collapsing sheath, are performed using an electric probe. The results are compared to theoretical models of the plasma sheath based on the Child-Langmuir law for high voltage sheaths. The theoretical model predicts well the sheath dynamics for conductive substrates. For insulating substrates the model can account for the experimental observations if the secondary electron coefficient is modified, justified on the basis of the poly-energetic nature of the implanting ions. If a conductive film is applied to the insulator surface the problem of charge accumulation can be avoided without compromising the effectiveness of PIII. The requirement for the film is that it be conductive, yet transparent to the incident ions. Experimental results are presented which confirm the effectiveness of the method. Theoretical estimates of the surface potential show that a film of the order of 5nm thickness can effectively circumvent the charge accumulation problem. Efforts to produce and characterise such a film form the final two chapters of this thesis. The optimal thickness is determined to be near the percolation threshold, where a marked increase in conductivity occurs. Spectroscopic ellipsometry is shown to be an excellent method to determine the film thickness and percolation threshold non-invasively. Throughout this work cathodic vacuum arcs are used to deposit thin films and as a source of metal plasmas. The design and construction of a pulsed cathodic vacuum arc forms a significant part of this thesis. Investigations of the cathode spots and power supply requirements are presented.

<p>Quantum dots are inorganic nanocrystals of semiconductor metals that have unique light emitting properties. Due to their tunable and narrow emission profile, broad absorption spectra, resistance to photobleaching and high level of brightness they have emerged as inorganic fluorophores and numerous applicabilities for in vitro, in situ as well as in vivo studies are present. The chemical nature of the quantum dot surface needs to be altered in order to make the inorganic nanoparticles applicable to biological systems. Water soluble and biocompatible particles that limit unspecific binding to proteins can be obtained through functionalization of the surface coating with appropriate molecules.</p><p> </p><p>In this pilot study, two surface modification strategies were performed upon two commercially available quantum dots in order to attach the zwitterionic molecules L-cysteine and thiolated sulfobetaine methacrylate, both shown to create non-fouling and biocompatible surfaces.</p><p> </p><p>A biphasic exchange method was successfully used to perform ligand exchange of Qdot® ITK™ Organic Quantum Dots (QD-Organic) in order to exchange the structurally unknown, native lipophilic coating to one consisting of the amino acid L-cysteine (QD-Cysteine). The quantum dots transferred from the organic to the aqueous phase after the natively hydrophobic coating was changed to the hydrophilic L-cysteine. A characteristic mass fragment of protonated trioctylphosphine oxide (TOPO) was found for QD-Organic, using TOF-SIMS, suggesting TOPO is a part of the native coating. Further, the mentioned mass fragment was no longer present after the exchange. The C (1s) XPS-spectrum showed a new peak for carboxylic carbon, characteristic for L-cysteine, and expected changes in elemental composition were consistent with measured changes for all relevant elements. Large amounts of buffer remained after purification, suggesting the purification protocol needs further evaluation. Traces of the native coating were found in the C (1s) XPS-spectrum for QD-Cysteine, indicating not all ligands were exchange.    <em></em></p><p> </p><p>Additionally, a strategy for surface functionalization of Qdot® 655 ITK™ amino (PEG) quantum dots (QD-PEG-NH₂) with L-cysteine and thiolated sulfobetaine methacrylate was outlined and performed, using Michael addition and the heterobifunctional linker 3-Maleimidobenzoic acid <em>N</em>-hydroxysuccinimide ester. Unfortunately, no indications of successful attachment of the linker to the quantum dot have been found, neither by TOF-SIMS nor XPS, and thus functionalization with L-cysteine and tSBMA was not achieved. In theory, the proposed coupling chemistry used during the pilot study is promising, but further experiments are needed to obtain a successful and optimized protocol for the functionalization. <strong></strong></p>

We have investigated a series of molecular and polymeric approaches for generating adherent thin films that impart anti-fouling characteristics to oxide surfaces. These films incorporate oligo- or poly(ethylene glycol) moieties that are expressed in high density in the near-surface region. In our molecular approach, oligo(ethylene glycol)-terminated n-alkyl-trichlorosilanes, RO(CH₂CH₂O)₃(CH₂)₁₁SiCl₃, have been designed so to spontaneously adsorb onto oxide surfaces and produce densely packed films. Another strategy uses a surface initiated polymerization to generate reactive anchored polymer chains that are then chemically modified to incorporate oligo(ethylene glycol) units. Lastly, a comb copolymer comprising a poly(acrylic acid) backbone and different grafting ratios of a linear poly(ethylene oxide-r-propylene oxide) chain has been prepared that adsorbs onto surfaces and forms a poly(ethylene glycol)-exposing film in single step. These surface coatings provide varying levels of protein and cellular resistance that can be related to molecular-scale elements of their surface structure. / Singapore-MIT Alliance (SMA)

The need for safe and functional implants has led to anincreased demand for improved biomaterials. The performance invivo depends on the interaction between the biologicalsurrounding and the surface of the material. By tailoring thesurface of a material with suitable bulk properties,biomaterials with an ability to interact with the biologicalsystem in a specific and controlled way are obtained. Siliconeelastomers have been used as biomaterials for several decades,but it is widely recognized that they are difficult to modifyby the conventional methods used for organic polymers due tothe partly inorganic structure of silicone. This thesis presents a strategy to obtain siliconebiomaterials by covalent coupling of molecules to the surfaceusing silicon chemistry. The first step is to introduce Si-Hgroups onto the surface of silicone elastomers by plasmatreatment. The second step is to react a terminal double bondof a molecule with the formed Si-H group by a catalyzedhydrosilylation reaction. The coupled molecule may eitherprovide the desired properties itself, or have a functionalitythat is able to couple another molecule with suitablecharacteristics. The influence of plasma treatment in hydrogen, argon andoxygen on the silicone elastomer was characterized by X-rayphotoelectron spectroscopy (XPS). To quantify the effect ofplasma treatment, the method of ternary XPS diagrams wasdeveloped. It was found that undesired silica-like layers wereformed under severe treatment conditions. Argon plasma at lowpower and short treatment time was the most suitable parametersetting. Subsequent hydrosilylation grafting ofallyltetrafluoroethylether, aminopropylvinylether andN-vinylformamide showed that it was possible to functionalizethe surface via a covalent link to the surface. The primaryamino groups introduced onto the surface were accessible forfurther coupling reactions. Heparin surfaces were obtained by acoupling reaction with the introduced amino groups. Keywords:Silicone elastomers, PDMS, XPS, ESCA, surfacemodification, plasma

Glass is a common material in each person’s life, e.g. drinking vessels, windows, displays, insulation and optical fibres. By modifying the glass surface it is possible to change the performance of the entire glass object, generally known as Surface Engineering. Ion exchange is a convenient technique to modify the glass surface composition and its properties, e.g. optical, mechanical, electrical and chemical properties, without ruining the surface finish of the glass.   This thesis reports the findings of two different research tasks; characterisation of the single-side ion exchange process and the novel properties induced. The characterisation of the ion exchange process was mainly performed by utilising a novel analytical equipment: the Surface Ablation Cell (SAC), allowing continuous removal of the flat glass surface by controlled isotropic dissolution. SAC-AAS has provided concentration vs. depth profiles of float glass ion exchanged with K+, Cu+, Rb+ and Cs+. In addition, SEM-EDX has provided concentration vs. depth profiles of Ag+ ion exchanged samples and validation of a copper concentration vs. depth profile. From the concentration vs. depth profiles, the effective diffusion coefficients and activation energies of the ion exchange processes have been calculated. Depending on the treatment time and treatment temperature, penetration depths in the range of 5-10 μm (Rb+, Cs+), 20-30 μm (K+, Cu+) and 80-100 μm (Ag+) can be readily obtained. The effective diffusion coefficients followed the order Ag+&gt;K+&gt;Cu+&gt;Rb+&gt;Cs+. This is in accordance with the ionic radii for the alkali ions (K+&lt;Rb+&lt;Cs+) but reverse for the noble metal ions (Cu+&lt;Ag+).   The glass properties modified by single-side ion exchange have mainly been characterised by UV-VIS spectroscopy and flexural strength measurements. Cu+ and Ag+ ion exchange give rise to surface colouration, Cu+ copper-ruby and Ag+ yellow/amber. The surface-ruby colouration was found to depend on the residual tin ions in the tin-side of the float glass. The flexural strength was studied using the coaxial double ring-test method which also was suitable for holed specimens. The flexural strength of K+ ion exchanged float glass samples was found to substantially increase compared to untreated.

Quantum dots are inorganic nanocrystals of semiconductor metals that have unique light emitting properties. Due to their tunable and narrow emission profile, broad absorption spectra, resistance to photobleaching and high level of brightness they have emerged as inorganic fluorophores and numerous applicabilities for in vitro, in situ as well as in vivo studies are present. The chemical nature of the quantum dot surface needs to be altered in order to make the inorganic nanoparticles applicable to biological systems. Water soluble and biocompatible particles that limit unspecific binding to proteins can be obtained through functionalization of the surface coating with appropriate molecules.   In this pilot study, two surface modification strategies were performed upon two commercially available quantum dots in order to attach the zwitterionic molecules L-cysteine and thiolated sulfobetaine methacrylate, both shown to create non-fouling and biocompatible surfaces.   A biphasic exchange method was successfully used to perform ligand exchange of Qdot® ITK™ Organic Quantum Dots (QD-Organic) in order to exchange the structurally unknown, native lipophilic coating to one consisting of the amino acid L-cysteine (QD-Cysteine). The quantum dots transferred from the organic to the aqueous phase after the natively hydrophobic coating was changed to the hydrophilic L-cysteine. A characteristic mass fragment of protonated trioctylphosphine oxide (TOPO) was found for QD-Organic, using TOF-SIMS, suggesting TOPO is a part of the native coating. Further, the mentioned mass fragment was no longer present after the exchange. The C (1s) XPS-spectrum showed a new peak for carboxylic carbon, characteristic for L-cysteine, and expected changes in elemental composition were consistent with measured changes for all relevant elements. Large amounts of buffer remained after purification, suggesting the purification protocol needs further evaluation. Traces of the native coating were found in the C (1s) XPS-spectrum for QD-Cysteine, indicating not all ligands were exchange.      Additionally, a strategy for surface functionalization of Qdot® 655 ITK™ amino (PEG) quantum dots (QD-PEG-NH2) with L-cysteine and thiolated sulfobetaine methacrylate was outlined and performed, using Michael addition and the heterobifunctional linker 3-Maleimidobenzoic acid N-hydroxysuccinimide ester. Unfortunately, no indications of successful attachment of the linker to the quantum dot have been found, neither by TOF-SIMS nor XPS, and thus functionalization with L-cysteine and tSBMA was not achieved. In theory, the proposed coupling chemistry used during the pilot study is promising, but further experiments are needed to obtain a successful and optimized protocol for the functionalization.

A framework to compartmentalize microfluidic surfaces was developed. Substrates are separated from surface modifying agents with an intermediate binding layer (IBL). The IBL is comprised of two compounds which bind together using a non-covalent interaction; a host compound is immobilized on the substrate, and a guest compound is conjugated to the surface modifying agent. The primary benefit of the IBL architecture is adaptability: substrates and surface compounds become modular components with standard connectors. Beta-Cyclodextrin (BCD) and adamantane (AD) were selected as the model immobilized host and conjugated guest, respectively. A quartz crystal microbalance (QCM) was assembled and developed to study the BCD/AD complexation interaction. Kinetic, thermodynamic, and Langmuir isotherm data were reported for AD-derivatives binding with immobilized BCD. QCM was also used to investigate neutravidin (NA) binding onto AD-PEG and AD-PEG-biotin coatings immobilized to t-BCD surfaces. QCM was an effective platform to validate the use of BCD/AD as the IBL interaction prior to microfluidic implementation. The BCD/AD IBL was successfully demonstrated in a microfluidic environment. Microfluidic devices were fabricated using the soft-lithographic technique. Adapted surface modifications were visualized using fluorescein isothiocyanate (FITC) probes within the microfluidic device and detected using confocal laser scanning microscopy (CLSM). Surface modifications were applied to demonstrate the fundamental functions of surface passivation, specific binding, and visualization using the IBL architecture. Consistent with QCM data, AD-PEG passivated the surface and AD-PEG-biotin specifically bound NA to the BCD surface. Thus, an adaptable surface modification architecture for microfluidic applications was developed and demonstrated.