No description available.

Polymer brushes provide the responsive smart surfaces which can be used for fabrication of various devices. In this thesis work, adhesion, friction, and wear of polystyrene (PS) - poly(2-vinyl pyridine) (P2VP) and polystyrene - poly(acrylic acid) (PAA) binary brushes and corresponding monobrushes were investigated in dried state under controlled environment. Spin-coated films were also investigated for comparison. The aim was to explore possibilities to control/tune adhesion, friction, and wear between inorganic or polymeric surfaces by use of polymer brushes. Atomic force microscopy (AFM) with sharp silicon nitride tip and colloidal probes was employed to investigate the nanoscale adhesion and friction forces between different inorganic and polymeric surfaces. Adhesion and friction on the polymer brushes were comparable to that on the spin-coated films. Adhesion and friction force values were correlated, and were in accordance with the wettability of the brush surfaces for most of the samples. Switching in the adhesion and friction forces was observed for the PS+P2VP and PS+PAA binary brushes on treatment with selective solvents. Maximum switching in adhesion force and friction coefficient was by a factor of 2.7 and 5.4, respectively. Furthermore, switching of friction for mixed brush surface was observed during macroscale friction measurements using nanoindenter. Friction coefficients at macroscale were higher than those at the nanoscale. Moreover, adhesion and friction forces between the surfaces were significantly influenced by the humidity, grafting density of polymer brushes, chemical composition of top of the binary brush surface, and tip scan velocity. Nanowear studies were carried out with AFM using sharp silicon nitride tip while macrowear studies were carried out using nanoindenter. Nanowear on the surfaces was affected by molecular entanglements, adhesion and friction forces as well as shape and status of the tip. It was observed that the typical wear mode for PS brushes (treated with toluene) was ripple formation. In case of P2VP brushes (treated with ethanol) and PAA brushes (treated with pH 10 water), wear occurred via removal of the polymeric material. Wear mechanism observed for the monobrushes was similar to that observed for the spin-coated thick films of the same polymeric material. However, extent of the wear on the brush surfaces significantly differed from that on the spin-coated films. In case of PS+P2VP and PS+PAA binary brush samples, change in the wear mode was observed on treatment with the different selective solvents. On treatment with toluene (PS on the top), both of these binary brushes showed the wear by formation of the ripples. On the other hand, when these binary brushes were treated with selective solvent for P2VP or PAA, wear occurred mainly via removal of the polymeric material. The amount of wear increased with the number of scans for all the polymer brush samples. Moreover, wear on the polymer brush surfaces was also increased on increase in the applied load and decrease in the scan speed. Wear behavior on macroscale was averaged due to contact between surfaces at large number of asperities. Our results show that adhesion, friction, and wear of polymer surfaces can be controlled/tuned by the use of binary polymer brushes.

No description available.

A systematic study of the surface-initiated polymerisation kinetics of a relatively new type of atom transfer radical polymerisation (ATRP), activators regenerated by electron transfer (ARGET) ATRP, is first demonstrated in this report. Poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(methyl methacrylate) (PMMA) were successfully grown from silicon surfaces at room temperature by surface-initiated ARGET ATRP using a "3rd generation" cationic macroinitiator. The polymer films were analysed by ellipsometry, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). With the initial experiment showing that water accelerated conventional ATRP but made it less controlled, the effect of solvent on ARGET ATRP was also evaluated. The living character of ARGET ATRP was demonstrated by successfully reinitiating PHEMA-grafted silicon wafers to grow a second block of PHEMA. Initiator density was shown to have a great effect on the growth rate of PHEMA film thickness on silicon surfaces by comparing the ARGET ATRP growth of PHEMA films using two different initiators, "1st generation" and "3rd generation" cationic macroinitiators, which have different ratios of initiating groups to positive charge. Another type of initiator for ATRP systems, an amide silane, was then investigated as an alternative to polyelectrolyte macroinitiators to avoid degrafting. The effects of solvent, 2, 2′ bipyridyl (bpy) ligand concentration and different types of reducing agent on the growth of PHEMA film from amide-initiator coated silicon wafers by ARGET ATRP were then explored at room temperature. However, it was found that the swings in the uncontrolled laboratory ambient temperature caused inter-sample and inter-experiment variability and so could make the evaluations inaccurate or even wrong. An investigation of temperature on ARGET ATRP showed a dramatic effect on the polymerisation rate. The higher the temperature, the faster the polymerisation proceeded. Therefore, the effects of solvent, ratio of bpy to Cu and reducing agent on the ARGET ATRP growth of PHEMA brushes from amide initiator-coated silicon wafers were re-evaluated at a constant temperature, 30 °C. The development of a polydopamine-based initiator, which was designed to be able to be immobilised on a wide range of surfaces, is then presented in this report. Polydopamine was first shown to be able to deposit on various types of material surfaces by oxidative polymerisation in aqueous solution. Bromoester initiating groups for ATRP systems were incorporated into polydopamine coatings by reacting a fraction of the dopamine monomer with 2-bromoisobutyryl bromide (BIBB) before polymerisation. The modified polydopamine initiator film grew at a comparable rate to unmodified polydopamine, with a 45 nm being grown in 24 hours. Successful incorporation of initiator groups was confirmed by XPS and FTIR, and by the growth of PMMA and PHEMA polymer brushes by ARGET ATRP from the polydopamine initiator coatings. A PMMA brush with a thickness of 239 nm was grown in 72 hours, indicating that the grafting density is sufficiently high to be in the brush regime. This initiator was demonstrated to be able to deposit on a range of substrates, such as metals (steel) and polymers (polystyrene), and successfully initiate polymer growth, demonstrating its broad applicability. The assessment of ARGET ATRP as a simple and effective tool for interfacial shear strength improvement in cellulose-based fibre reinforced thermoplastic composites is finally presented. It was demonstrated by control experiments that grafting polystyrene on glass fibre surfaces via ARGET ATRP greatly improved the interfacial adhesion between glass fibres and a high-impact polystyrene (HIPS) matrix, although a specific value of interfacial strength was not obtained due to failure of the modified glass fibre composite samples in areas other than the interface. It was then demonstrated that PMMA was successfully grown from the surfaces of polydopamine initiator coated cotton fibre and BIBB-modified cotton fibre by ARGET ATRP. Polydopamine initiator was shown to be a better initiator for cotton fibre than BIBB, possibly since the adsorbed water on cotton fibres can react with BIBB. The improvement of interfacial adhesion between cotton fibres and a PMMA matrix by grafting PMMA on the cotton surface was assessed by peel testing of cotton fibres pressed into PMMA sheets. There is a clear trend in the relationship between the peeling force and growth time of PMMA on the cotton fibre by ARGET ATRP, although the inter-sample reproducibility is not good.

New electrochemical storage and conversion materials hold promise as important additions to the world's energy supply, and the growing ability to control both sequestration and transfer of charge and matter via functionally responsive materials promises to transform the field. Already, new understanding of the role played by nano-scale morphology of materials in transport function has contributed to considerable material improvements, with functional polymers possessing specific chemistry and morphology playing a key role in the future of electrochemical material applications. However, many challenges to optimizing properties still exist due to incomplete descriptions of transport. In this work, fluorescence spectroscopy and single molecule spectroscopy experimental techniques and analysis are developed and employed to reveal details of the mechanisms underpinning ion transport in structurally ordered polyelectrolyte polymer-brush membranes. The studies reveal the existence and nature of heterogeneous transport mechanisms in these polymer films, and provide a description of the dynamic association of molecular ions with the brush. It is also shown that it is possible to tune charged ion transport characteristics in the thin films by controlling the solvent pH, with an effective switching of ion transport rates in these brushes past a threshold pH value. Additionally, Monte Carlo models designed to model molecular scale interactions that give rise to experimental observables are developed to provide additional insight into the physical nature of transport processes in these materials. These models provide additional support for the conclusions of the experimental work.

A non-crosslinking approach that covalently bonds nitroxide polymer brushes onto the ITO substrates via surface-initiated atom transfer radical polymerization (ATRP) was develpoed. Since the indium tin oxide (ITO)-silane covalent bonding providesvery strong chemical bonds to adsorb the nitroxide polymer brushes on ITO, it prevents polymers from dissolving into electrolyte solvent and thus improves its electrochemical properties. Moreover, micro-contact printing technology was used to pattern nitroxide polymer brushes on an ITO surface for the potential application in microbatteries. The morphology of electrodes was observed by atomic force microscopy.The electrochemical properties of the cathode were also studies.

Nitroxide polymer brushes grafted on silica nanoparticles as binder-free cathode for organic radical battery have been investigated. Scanning electron microscopy, transmission electron microscopy, infrared spectroscopy and electron spin resonance confirm that the nitroxide polymer brushes are successfully grafted onto silica nanoparticles via surface-initiated atom transfer radical polymerization. The thermogravimetric analysis results indicate that the onset decomposition temperature of these nitroxide polymer brushes is found to be ca. 201 ◦C. The grafting density of the nitroxide polymer brushes grafted on silica nanoparticles is 0.74¡V1.01 chains nm−2. The results of the electrochemical quartz crystal microbalance indicate that the non-crosslinking nitroxide polymer brushes prevent the polymer from dissolving into organic electrolytes. Furthermore, the electrochemical results show that the discharge capacity of the polymer brushes is 84.9¡V111.1 mAh g−1 at 10 C and the cells with the nitroxide polymer brush electrodes have a very good cycle-life performance of 96.3% retention after 300 cycles.

Exploitation of well defined responsive polymer brushes for direct and controlled immobilization of metal/semiconductor nanoparticles on macroscopic surfaces has been demonstrated. The employed approach offers the possibility of the organization of a variety of inorganic nanoparticles by irreversible bonding and homogenous distribution on an underlying substrate. The immobilization process has been realized by chemical grafting of a variety of polymer brushes on a suitable substrate followed by the attachment of pre-/in-situ formed nanoparticles exploiting the chemical/physical interactions between surface functionalities of nanoparticles and polymer chain segments. A number of polymer brushes including poly (acrylic acid), polystyrene, poly (2-vinyl pyridine) and poly (N-isopropyl acrylamide) brushes have been prepared on silicon substrate by the “grafting to” approach. A variety of inorganic nanoparticles such as quantum dots (CdTe) noble metals (gold and silver) and magnetic (Fe3O4) were immobilized on macroscopic surfaces to impart them photo luminescent, catalytic or magnetic properties. In addition, responsiveness of grafted polymer brushes in terms of variation in thickness (due to changes in chain conformation) as a function of external stimuli such as solvent and pH allowed to use the resulting polymer brush-nanoparticles nanoassemblies in the fabrication of nanosensors. The design of fabricated nanosensors is based on the modulation in the interparticle distance of immobilized nanoparticles due to swelling/deswelling of underlined polymer brushes in response to some external trigger.

Polymer brushes can be used to tailor the physical and chemical properties of materials on demand to meet potential applications. Therefore, fabrication of polymer brushes with well-defined structure and functional groups enables the engineering of new materials with diverse functions. In addition, two-dimensional (2D) materials have their unique physical/chemical properties and potential applications in (opt)electronics, catalysis, energy storage, sensing, and other related fields. However, the dispersibility, chemical stability, charge transport behavior, mechanical properties of the 2D materials hinder their further applications. Therefore, combining polymer brushes and 2D materials may bring in new properties which are not available by either of them alone. This thesis focuses on brushing up 2D materials (from inorganic to organic) with universal photografting techniques. (1) The first chapter introduces the outline and research content of the thesis. (2) The second chapter describes the background of 2D materials and polymer brushes. In particular, this chapter analyzes mechanisms, drawbacks and benefits of different polymerization methods, and also summarizes the general approaches to grow polymer brushes on 2D material surfaces, coupling with potential applications of polymer functionalized 2D materials. (3) The third chapter shows the motivation and aim of this thesis. (4) The fourth chapter discusses the results of the functionalization of hexagonal boron nitride (hBN), MoS2, graphitic-carbon nitride (gCN), alkyl-polydopamine (alkyl-PDA), and conjugated 2D polymers (2DPs) with polymer brushes by the same self-initiated photografting and photopolymerization (SIPGP) method and their related applications in detail, respectively. First, the direct photopolymerization of vinyl monomers results in the formation of thick and homogeneous polymer brushes covalently bounded to hBN. The brush layer mechanically and chemically stabilizes the material and allows facile handling as well as long-term use in water splitting hydrogen evolution reactions. Second, the chapter demonstrates the MoS2 can be directly modified with polymer brushes by SIPGP. After modifying MoS2 with polymer brushes, the dispersibility of polymer brushes-modified MoS2 was obviously improved. Third, the polymer brushes functionalized gCN significantly improves the dispersibility. Application of polymer brush functionalized gCN as excellent recyclable substrates for an outstanding SERS as well as photocatalytic degradation of dyes is demonstrated. Fourth, to directly obtain the 2D materials with functional groups, the chapter proposes a facile method to prepare amphiphilic polymeric Janus nanosheets with hydrophilic PDA and hydrophobic alkyl chains at both sides. Benefiting from the Janus property of the alkyl-PDA nanosheets, the nanosheets can be grafted polymer brushes through photografting and be conjugated Fe3O4 nanoparticles selectively onto the PDA side. Finally, the chapter shows that various polymer brushes can be directly grafted onto 2DPs and freestanding system is also obtained. Moreover, it is found that the morphology of freestanding system quickly and reversibly responds to solvent quality by shrinking/stretching. (5) The fifth chapter addresses the general conclusion and future prospective of the whole work. (6) The sixth chapter describes the experiment part of the whole thesis.

Title: Bioactive interfaces between synthetic surfaces and biological fluids Author: Andrés de los Santos Pereira Institute: Institute of Macromolecular Chemistry, Czech Academy of Sciences Supervisor of the doctoral thesis: RNDr. Eduard Brynda, CSc., Institute of Macromolecular Chemistry, Czech Academy of Sciences Abstract: The application in medicine of label-free affinity biosensors, advanced implants, and blood-contacting devices requires that their surfaces resist non-specific protein adsorption (fouling) and associated complications in blood-derived fluids while displaying immobilized bioreceptors that provide specific biofunctionality. The aim of this thesis was to explore the strategies for the preparation of these antifouling bioactive surfaces. Various types of recently developed antifouling polymer brushes were synthesized and evaluated in terms of their ability to prevent fouling from blood plasma (obtained from various commercial sources and individual donors) as well as thrombus formation when contacted with whole blood. Moreover, single-cell force spectroscopy was utilized to characterize the bacterial adhesion force and energy on these polymer brushes, which were significantly reduced in comparison to various reference substrates. The immobilization of bioreceptors was tackled by means of a...