Interactions between organic polymers and cement hydration products

Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

Non-linear temperature response of Bragg gratings in doped and un-doped holey polymer optical fibre

We present measurements on the non-linear temperature response of fibre Bragg gratings recorded in pure and trans-4-stilbenemethanol-doped polymethyl methacrylate (PMMA) holey fibres.

Editorial

This time of year we look back at the year that has passed and make plans for the next year. I like to reflect on things that I have learnt and people that I have met, especially those who facilitated that learning. In 2009 I went to various conferences, The BCLA conference in Manchester, The Romanian Optical Society meeting in Brasov, Transylvania (where the university is actually on Vlad Tepes Street), The European Council for Optometry and Optics (ECOO) in Brno, Czech Republic, The American Academy of Optometry (AAO) in Orlando USA, The International Association of Contact Lens Educators (IACLE) meeting in Tianjin China and finally The Vereinigung Deutscher Contactlinsen-Spezialisten (VDCO) meeting in Jena. All were interesting places and thoroughly all were enjoyable conferences with their own highlights but I wanted to focus on Jena and one person I met there and his inspirational search for knowledge and the contributions he made in the field of contact lenses. Jena itself is a fascinating place and should be on the ‘must visit’ list of anyone involved in eye care. It is the birth place of Carl Zeiss of course and where he started his company. It is also the birth place of Ernst Abbe (physicist and optometrist and expert lens maker), and Otto Schott (chemist and technologist who made high quality glass. There are many road signs bearing witness to these famous pioneers. The optical museum is worth spending a few hours looking around too. I was invited to speak at the VDCO at the kind invitation from colleagues at the Jena School of Optometry, Professor Wolfgang Sickenberger and Professor Sebastian Marx. At this meeting I met 87-year-old Willi KAUE who was being awarded the Adolf Wilhelm Müller-Welt prize by the VDCO for contribution to contact lenses over his 60-year career. At the age of 15 Willi Kaue took up an apprenticeship to become an Optician in Germany in 1937. At this time he first heard about the scleral glass lenses made by the Carl Zeiss Company in Jena. This started his lifelong fascination which was to become his passion but not yet his career. During the war he was enlisted into military service but immediately after was back to his former career. In 1950 Willi corrected his own 3.5 dioptres of myopia with a plastic scleral lens. His fascination strengthened as for the first time he himself could experience a wider field of view than his spectacles gave him, less aberrations and less retinal minification. He also appreciated the fact that contact lenses did not cause pressure on the nose or ears and did not slide down his nose plus remained optically centred with his eye movements. He decided that form now on he would make fitting contact lenses his career. He travelled to London to learn more about contact lenses and how to fit them but initially did not find many willing teachers and to start with became largely self-taught. He wanted to know how to make scleral lenses. So far he only knew that pulverized polymethyl methacrylate (PMMA) was pressed and moulded. In 1951 he met Berlin optician Otto Marzock. He made his only scleral lenses from using military PMMA windshields. His process involved lathe cutting the lenses and resulted in lenses that were thinner than moulded ones. Willi developed a manufacturing method, using a rotary diamond drill, starting form the outer edge and towards the centre at a constant cut speed. This enabled him to make more reproducible lenses and in less time. His enthusiasm in the field was clear from the travels he made in the pursuit of advancement - travelling around Europe, South America, North America and Asia. In 1963 he visited George Nissel in Hemel Hempstead, England. Constantly thriving towards innovations Willi came across the new Naturalens from the USA made from HEMA at a congress in Marseille in 1969. Amongst his contributions to the field, was his own technique of fitting ocular prosthetics, using an alginate impression of the orbit. I was fortunate enough to have dinner with Willi Kaue and learnt more about his fascinating career through the patient interpreting skills of Hilmar Bussacker (the 2008 winner of the same award and the 2007 winner of the European Federation of the Contact Lens and IOL Industries Award). I look forward to 2010 with eager anticipation as to what I may learn and who I might meet!!! Copyright © 2009 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.

Synthesis and evaluation of nanoparticle-polymer composites

This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

Non-linear temperature response of Bragg gratings in doped and un-doped holey polymer optical fibre

We present measurements on the non-linear temperature response of fibre Bragg gratings recorded in pure and trans-4-stilbenemethanol-doped polymethyl methacrylate (PMMA) holey fibres.

Fabrication of Dense Non-Circular Nanomagnetic Device Arrays Using Self-Limiting Low-Energy Glow-Discharge Processing

We describe a low-energy glow-discharge process using reactive ion etching system that enables non-circular device patterns, such as squares or hexagons, to be formed from a precursor array of uniform circular openings in polymethyl methacrylate, PMMA, defined by electron beam lithography. This technique is of a particular interest for bit-patterned magnetic recording medium fabrication, where close packed square magnetic bits may improve its recording performance. The process and results of generating close packed square patterns by self-limiting low-energy glow-discharge are investigated. Dense magnetic arrays formed by electrochemical deposition of nickel over self-limiting formed molds are demonstrated.

The optical properties of metamaterials

This thesis studies the parametric investigation, polarisation dependence and characterization of fishnet structure at near infrared wavelengths. Detailed simulations are performed to understand the behaviour of the structure at near infrared and optical wavelengths. Simulations are performed to obtain negative refractive index of the fishnet structure formed from nanoimprint lithography (NIL) by taking into account the effect of substrate and polymethyl methacrylate (PMMA) beneath it. Two different structures have been designed and fabricated of varying dimensions using NIL and their resonant wavelength measured in the near infrared at 1.45 µm and 1.88 µm. Simulations suggest that a negative refractive index real part with the magnitude -0.24 is found at 1.53 µm and this decrease to a maximum magnitude of -0.57 at 1.9 µm. The PMMA and suppressed pillars are here responsible for the increasing material losses and limiting the value of negative refractive index. An analytical approach has been suggested to characterise fishnet structures at oblique incidence. The expressions for an absorbing medium are rewritten for an alternative definition of refractive index. The expressions are initially validated for a dielectric slab and a metal film. These results provide the possibility that this proposal may yield a general algorithm for obtaining the complex reflection and transmission coefficients for artificial structures. FDTD simulations have been extensively used in this thesis to understand the optical metamaterials and their characterization.

Methacrylate-functionalized oligomers based on lactide, E-caprolactone and trimethylene carbonate for application in stereo-lithography

Photo-curable biodegradable macromers were prepared by ring opening polymerization of D,L-lactide (DLLA), (similar to)-caprolactone (CL) and 1,3-trimethylene carbonate (TMC) in the presence of glycerol or sorbitol as initiator and stannous octoate as catalyst, and subsequent methacrylation of the terminal hydroxyl groups. These methacrylated macromers, ranging in molecular weight from approximately 700 to 6000 g/mol, were cross-linked using ultraviolet (UV) light to form biodegradable networks. Homogeneous networks with high gel contents were prepared. One of the resins based on PTMC was used to prepare three-dimensional structures by stereo-lithography using a commercially available apparatus.

Methacrylate-functionalized oligomers based on lactide, ε- caprolactone and trimethylene carbonate for application in stereo-lithography

Photo-curable biodegradable macromers were prepared by ring opening polymerization of D,L-lactide (DLLA), ε-caprolactone (CL) and 1,3-trimethylene carbonate (TMC) in the presence of glycerol or sorbitol as initiator and stannous octoate as catalyst, and subsequent methacrylation of the terminal hydroxyl groups. These methacrylated macromers, ranging in molecular weight from approximately 700 to 6000 g/mol, were cross-linked using ultraviolet (UV) light to form biodegradable networks. Homogeneous networks with high gel contents were prepared. One of the resins based on PTMC was used to prepare three-dimensional structures by stereo-lithography using a commercially available apparatus.