The development and identification of new biomaterials that can replace specific tissues and organs is desirable. In the presented PhD thesis polymer microarrays were applied for the screening of polyacrylates and polyurethanes and evaluation for material discovery for applications in the life sciences. In the first part of the thesis, the largest polymer microarray ever made with more than 7000 features was fabricated and subsequently used for the screening of polyacrylates that can control the fate of human embryonic stem cells. As stem cells have unique properties that offer the potential of replacing damaged or diseased tissue in future, the identification of cultivation substrates that can replace current biological and animal derived products was desirable. The water contact angle, roughness and cell doubling time of the cells on the identified polymers was determined and the stem cells characterised after 5 passages and compared to the currently most widely used animal derived substrate MatrigelTM. In the second part of the thesis, the development of a new polymer gradient microarray is presented. Initial studies involved the optimisation of printing parameters for the generation of linear polymer gradient lines and confirmed by XPS analysis. Cellular binding studies with the suspension cell line K562 and the adherent cell line HeLa were carried out and compared to previous binding studies to confirm the success of the concept. In further studies, the polymer gradients were functionalised with small molecules and proteins, allowing the generation of a protein gradient microarray with Semaphorin 3F. In binding studies with neuron cells it could be shown that the binding of the cells was concentration-dependent. The identification of polyacrylates for the effective and rapid activation and aggregation of platelets is described in the third part of the presented thesis. Here, polymer microarrays were applied for the binding of platelets in human blood samples. The amount of bound platelets as well as their activation state was compared to the natural agonist collagen by employing fluorescence intensity studies and scanning electron microscopy. In shear studies, the activation of the platelets by the polymers was evaluated under physiological conditions. The mechanism by which the polymer triggered the activation was further explored by protein binding studies. It was shown that the initial adsorption of fibrinogen and von Willebrand factor on the polymers lead to the adherence and aggregation of platelets. In the final part of the presented thesis, polymer microarrays were used to identify polymers that can sort and collect the precursor cells of platelets (megakaryocytes). For this purpose, the cell lines K562 and MEG-01 were used as cellular models. The identified polymers and the effect on the immobilised cells was further investigated by scanning electron microscopy, flow cytometry and miRNA studies. The adsorbed proteins on the different polymers were found to influence the cellular morphology on the different substrates.

No description available.

Thesis (Ph.D.)--Brown University, 2008. / Vita. Advisor : Edith Mathiowitz. Includes bibliographical references (leaves 70-71).

Surface micromachining using deposited polysilicon films is a technology that is widely used for the fabrication of micro-electromechanical structures. One of the biggest yield and reliability problems in the fabrication of such structures is "stiction" or adhesion to the substrate. This may occur during the drying step that is required after wet processing and/or during use of a device. Deposition of self-assembled monolayer coatings is one of the most successful approaches to chemical modification of silicon surfaces to reduce stiction. This approach involves making the surfaces of pre-oxidized polysilicon highly hydrophobic. As a result, microstructures come out of the final water rinse extremely dry without being broken or adhered to the substrate. Available technology requires that these coatings are applied from organic media . However, increasing pressure on semiconductor companies to reduce the generation of organic wastes has sparked interest in the feasibility of applying these coatings from aqueous media. The objective of this research was to develop the chemistry and techniques for the application of hydrophobic coatings on polysilicon from aqueous media. The results obtained from three commercially available water dispersible silanes and cationic alkoxysilanes are discussed. Key experimental variables that were investigated are concentration of reactive silane, type of oxidation pretreatment of polysilicon, pH and temperature of the silane dispersion and curing temperature of the coating. The stability of the dispersions was characterized by viscosity measurements. The formation and quality of the films were studied using atomic force microscopy (AFM), ellipsometry, dynamic contact angle measurements and electrochemical impedance spectroscopy (EIS). The coatings showed contact angles greater than 100°. It was found using AFM that the structure of these films is a continuous film with some particulates attributed to bulk polymerization of the precursor molecule in water. EIS results indicated that the coatings had low porosity as well as high charge transfer resistance across the silicon/HF interface. Ellipsometric analysis showed that thickness of these coatings is roughly a (statistical) monolayer. The stability improvement of the dispersions by the addition of quaternary ammonium cationic surfactants is also discussed.

The work contained within this document discusses the polymerization and subsequent characterization of Polypyrrole based electrodes for lithium batteries. Polypyrrole and Polypyrrole/polyethyloxy copolymers were compared and contrasted in an attempt to show the superior kinetics of the copolymer electrode. It was found that the diffusion of dopant ions across the electrode and electrolyte interface was increased by on order of magnitude in the copolymer sample. It was also found that the reversibility of the Polypyrrole electrode was greater than that of the copolymer electrode. While the diffusion coefficient of the copolymer electrode was altered to be comparable to that of the transition metal oxide cathodes in production today, the capacity of the copolymer material is still too low to be considered as an alternative cathode material in the lithium battery industry.

Composites are known for their unique blend of modulus, strength, and toughness. This study focuses on two types of composites; organic-inorganic hybrids and the mineralization of highly swollen polymer gels. Both of these composite systems mimic the biological process of composite formation, known as biomineralization. Biomineralization allows for the control of the precipitating phase through an interaction with the organic matrix. This allows higher volume fractions of inorganic material than can be achieved by many traditional processing techniques. Solid freeform fabrication is a processing method that builds materials by the sequential addition of thin layers. As long as the material can easily be converted from a liquid to a solid, it should be amenable for this processing technique. Freeform fabrication has three distinctions from traditional processing techniques that may enable the formation of composite materials with improved mechanical properties. These are the sequential addition of layers, which allows a layer by layer influence of chemistry, the ability to form complex geometries, and finally, extrusion freeform fabrication has been shown to align fibers due to the extrusion of the slurry through a needle. Cracking and shrinkage still play a major role in forming solid parts. The use of an open mesh structure in combination with proper materials selection allowed the formation of highly loaded composite materials without cracking. The modulus values of these materials ranged from 0.1 GPa to 6.0 GPa. The mechanical properties of these materials were modeled.

PS-based nonionic, but polar, diblock copolymers (polystyrene-b-polymethacrylates, polystyrene-b-polyacrylates, polystyrene-b-poly(dimethyl siloxane)) have been systematically studied using the Langmuir film balance (LFB) technique, transmission electron microscopy (TEM), and atomic force microscopy (AFM). It has been found that these nonionic copolymers can form 2D surface micelles as has been found for ionic diblocks such as polystyrene-b-poly(vinyl pyridinium iodide) diblocks. This suggests that formation of surface micelles is a general phenomenon among AB diblock copolymers. Both structural parameters (aggregation number, aggregate size distribution, corona length and thickness, morphologies, boundaries etc.) and the response to conditions (temperature of the subphase, surface tension of the subphase, hysteresis, compression rates, etc.) have been explored for the monolayers formed from these materials. Many of these diblocks exhibit plateaus or inflections in their isotherms. Experimental data allow for the calculation of the thermodynamic parameters $ rm ( Delta S sb{t}$ and $ rm Delta H sb{t})$ associated with the transitions. Differences between the $ rm Delta S sb{t}$ and $ rm Delta H sb{t}$ values observed with the nonionic diblocks in question and the ionic diblocks studied before suggests that the nonionic diblocks monolayers have unique properties. Different mechanisms of the transitions(s) are proposed for samples which have one transition plateau or inflection and samples which have multiple transitions or inflections. A scaling theory-based calculation of the corona length and $ pi$-A isotherm are reasonably consistent with experimental data and thus provides a useful tool in these studies. Selected properties (i.e. subphase surface tension, waiting time etc.) for several ionic diblocks were also studied. Finally, the minimum chain lengths for circular micelles were calculated using a scaling theory methodology.

Poly(acrylonitrile-co-butadiene) or nitrile-butadiene rubber (NBR) is frequently used as an O-ring material in the oil extraction industry due to its excellent chemical properties and resistance to oil. However, degradation of NBR gaskets is known to occur during the well completion and oil extraction process where packers are exposed to completion fluids such as ZnBr2 brine. Under these conditions NBR exhibits accelerated chemical degradation resulting in embrittlement and cracking. Samples of NBR, poly(acrylonitrile) (PAN) and poly(butadiene) (PB) have been exposed to ZnBr2 based completion fluid, and analyzed by ATR and diffuse reflectance IR. Analysis shows the ZnBr2 based completion fluid promotes hydrolysis of the nitrile group to form amides and carboxylic groups. Analysis also shows that carbon-carbon double bonds in NBR are unaffected after short exposure to zinc bromide based completion fluid, but are quickly hydrolyzed in acidic bromide mixtures. Although fluoropolymers have excellent chemical resistance, their strength is less than nitrile rubber and replacing the usual gasket materials with fluoroelastomers is expensive. However, a fluoropolymer surface on a nitrile elastomer can provide the needed chemical resistance while retaining their strength. In this study, we have shown that this can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O-rings have been fluorinated by exposure to F2 and F2/HF mixtures at various temperatures. Fluorination with F 2 produces the desired fluoropolymer layer; however, fluorination by F2/HF mixtures gave a smoother fluorinated layer at lower temperatures and shorter times. Fluorinated samples were exposed to ZnBr2 drilling fluid and solvents. Elemental analysis shows that the fluorinated layer eliminates ZnBr2 diffusion into the NBR polymeric matrix. It was also found that surface fluorination significantly retards the loss of mechanical properties such as elasticity, tensile strength, toughness and compression set of nitrile rubber when exposed to zinc bromide fluid. This surface fluorination can be applied to extend the useful life of O-rings and packers in the field during oil extraction. The extended life can save millions of dollars by limiting the downtime of the well.

The development of composites of single-walled carbon nanotubes (SWNTs) with thermoplastics requires methods for good dispersion and achieving good interaction between SWNTs and the matrix. This thesis presents a new method to achieve good dispersion by a preliminary treatment called incipient wetting. The SWNTs dispersed in a solvent are mixed with polymer particles and deposited over them as the solvent is evaporated to give an initial dispersion. Factors that make this more effective are: good wetting of the polymer by the solvent, swelling of the polymer, high surface area of the polymer. Swelling enhances the initial dispersion with some initial mixing. A high surface area is achieved using polymer powder. High shear mixing alone does not achieve the same uniform and repeatable level of dispersion that the combination with incipient wetting allows. The incipient wetting method was studied and applied to different polymers. The possibility of recovering SWNTs from thermoplastics by dissolving or burning away the matrix is an extension of this study. A new comprehensive approach to control the interface of thermoplastics with SWNTs is studied. This is based on achieving direct chemical bonding between polymer molecules and functional groups on oxidized open ends, sidewalls, or both, in the SWNTs. Different concepts and approaches to these "fully integrated nanotube composites" are discussed. The concepts have been applied to epoxies elsewhere and are tested here with nylon-6,6 as a model system. Nylon was synthesized by interfacial polymerization in the presence of SWNTs resulting in excellent dispersion in the composite without further processing. The essential requirement for good dispersion is that the SWNTs are well dispersed in the solvent. Interfacial polymerization opens the way to many types of polymer-SWNT composites. Tests of full integration of SWNTs with open ended nanotubes showed promising results and hints of integration but were limited by dispersion in the solvent. Fluorinated SWNTs were dispersed effectively with dichlorobenzene, another solvent may be better. There is no conclusive evidence of integration with F-SWNTs but they may react with the polymer chain with thermal post-processing.

Single-walled carbon nanotubes are high strength materials with nano-sized dimensions, which make them attractive as reinforcing materials for polymer matrices. Their nano-sized dimensions however make them difficult to manipulate for macroscopic applications. This thesis focuses on manufacturing and studying nanotube continuous fibers as a means of manipulating these stronger reinforcing materials in thermoplastic polymer matrices to increase the mechanical properties of the composite generated. The thermoplastic polymers used in this thesis are polypropylene and nylon 6,6. This thesis demonstrates the effects of alignment, new chemical functionalizations and increasing weight percentages of the single-walled carbon nanotubes in the nanotube continuous fiber systems. The functionalizations studies include the use of fluorinated single-walled nanotubes, and an attempt to use benzoyl peroxide to initiate covalent bonding of single-walled nanotubes to the polymer in the processing stage of the polypropylene composite systems. (Abstract shortened by UMI.)