Nonlinear optical responses of targeted phthalocyanines when conjugated with nanomaterials or fabricated into polymer thin films
- Authors: Nwaji, Njemuwa Njoku
- Date: 2019
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Thin films , Polymers , Nonlinear optics , Nonlinear optical spectroscopy , Nanostructured materials , Raman effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/71625 , vital:29926
- Description: A number of zinc, gallium and indium metallophthalocyanines (MPcs) with diverse substituents have been synthesized and characterized using various characterization tools such as proton nuclear magnetic resonance (1HNMR), matrix assisted laser desorption time of flight (MALDI-TOF) mass spectrometry, Fourier-transformed infra-red (FT-IR), Ultraviolet-visible (Uv-vis) spectrophotometry, magnetic circular dichroism and CHNS elemental analysis. The time dependent density functional theory was employed to probe the origin of spectroscopic information in these complexes. Complexes with gallium and indium as central metal showed higher triplet quantum yield compared to the zinc derivatives. Some of the MPcs were covalently linked to nanomaterials such as CdTe, CdTeSe, CdTeSe/ZnO, graphene quantum dots (GQDs) as well as metallic gold (AuNPs) and silver (AgNPs) nanoparticles. Others were either surface assembled onto AuNPs and AgNPs or embedded into polystyrene as polymer source. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). The thickness of the thin films was determined by utilization of the knife edge attachment of the A Bruker D8 Discover X-ray diffraction. The optical limiting properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. The investigated MPcs complexes generally showed good optical limiting properties. The nonlinear optical response of the MPcs were improved in the presence of nanomaterials such as the semiconductor quantum dots (SQDs), graphene quantum dots (GQDs) as well as metallic AuNPs and AgNPs with MPc-QDs showing the best optical limiting behavior. The optical limiting properties of the MPcs were greatly enhanced in the presence of polymer thin films.
- Full Text:
- Date Issued: 2019
- Authors: Nwaji, Njemuwa Njoku
- Date: 2019
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Thin films , Polymers , Nonlinear optics , Nonlinear optical spectroscopy , Nanostructured materials , Raman effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/71625 , vital:29926
- Description: A number of zinc, gallium and indium metallophthalocyanines (MPcs) with diverse substituents have been synthesized and characterized using various characterization tools such as proton nuclear magnetic resonance (1HNMR), matrix assisted laser desorption time of flight (MALDI-TOF) mass spectrometry, Fourier-transformed infra-red (FT-IR), Ultraviolet-visible (Uv-vis) spectrophotometry, magnetic circular dichroism and CHNS elemental analysis. The time dependent density functional theory was employed to probe the origin of spectroscopic information in these complexes. Complexes with gallium and indium as central metal showed higher triplet quantum yield compared to the zinc derivatives. Some of the MPcs were covalently linked to nanomaterials such as CdTe, CdTeSe, CdTeSe/ZnO, graphene quantum dots (GQDs) as well as metallic gold (AuNPs) and silver (AgNPs) nanoparticles. Others were either surface assembled onto AuNPs and AgNPs or embedded into polystyrene as polymer source. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). The thickness of the thin films was determined by utilization of the knife edge attachment of the A Bruker D8 Discover X-ray diffraction. The optical limiting properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. The investigated MPcs complexes generally showed good optical limiting properties. The nonlinear optical response of the MPcs were improved in the presence of nanomaterials such as the semiconductor quantum dots (SQDs), graphene quantum dots (GQDs) as well as metallic AuNPs and AgNPs with MPc-QDs showing the best optical limiting behavior. The optical limiting properties of the MPcs were greatly enhanced in the presence of polymer thin films.
- Full Text:
- Date Issued: 2019
Ultra-high precision machining of contact lens polymers
- Authors: Olufayo, Oluwole Ayodeji
- Date: 2015
- Subjects: Contact lenses , Polymers
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/3001 , vital:20385
- Description: Contact lens manufacture requires a high level of accuracy and surface integrity in the range of a few nanometres. Amidst numerous optical manufacturing techniques, single-point diamond turning is widely employed in the making of contact lenses due to its capability of producing optical surfaces of complex shapes and nanometric accuracy. For process optimisation, it is ideal to assess the effects of various conditions and also establish their relationships with the surface finish. Presently, there is little information available on the performance of single point diamond turning when machining contact lens polymers. Therefore, the research work undertaken herewith is aimed at testing known facts in contact lens diamond turning and investigating the performance of ultra-high precision manufacturing of contact lens polymers. Experimental tests were conducted on Roflufocon E, which is a commercially available contact lens polymer and on Precitech Nanoform Ultra-grind 250 precision machining. Tests were performed at varying cutting feeds, speed and depth of cut. Initial experimental tests investigated the influence of process factors affecting surface finish in the UHPM of lenses. The acquired data were statistically analysed using Response Surface Method (RSM) to create a model of the process. Subsequently, a model which uses Runge-Kutta’s fourth order non-linear finite series scheme was developed and adapted to deduce the force occurring at the tool tip. These forces were also statistically analysed and modelled to also predict the effects process factors have on cutting force. Further experimental tests were aimed at establishing the presence of the triboelectric wear phenomena occurring during polymer machining and identifying the most influential process factors. Results indicate that feed rate is a significant factor in the generation of high optical surface quality. In addition, the depth of cut was identified as a significant factor in the generation of low surface roughness in lenses. The influence some of these process factors had was notably linked to triboelectric effects. This tribological effect was generated from the continuous rubbing action of magnetised chips on the cutting tool. This further stresses the presence of high static charging during cutting. Moderately humid cutting conditions presented an adequate means for static charge control and displayed improved surface finishes. In all experimental tests, the feed rate was identified as the most significant factor within the range of cutting parameters employed. Hence, the results validated the fact that feed rate had a high influence in polymer machining. The work also established the relationship on how surface roughness of an optical lens responded to monitoring signals and parameters such as force, feed, speed and depth of cut during machining and it generated models for prediction of surface finishes and appropriate selection of parameters. Furthermore, the study provides a molecular simulation analysis for validating observed conditions occurring at the nanometric scale in polymer machining. This is novel in molecular polymer modelling. The outcome of this research has contributed significantly to the body of knowledge and has provided basic information in the area of precision manufacturing of optical components of high surface integrity such as contact lenses. The application of the research findings presented here cuts across various fields such as medicine, semi-conductors, aerospace, defence, telecom, lasers, instrumentation and life sciences.
- Full Text:
- Date Issued: 2015
- Authors: Olufayo, Oluwole Ayodeji
- Date: 2015
- Subjects: Contact lenses , Polymers
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/3001 , vital:20385
- Description: Contact lens manufacture requires a high level of accuracy and surface integrity in the range of a few nanometres. Amidst numerous optical manufacturing techniques, single-point diamond turning is widely employed in the making of contact lenses due to its capability of producing optical surfaces of complex shapes and nanometric accuracy. For process optimisation, it is ideal to assess the effects of various conditions and also establish their relationships with the surface finish. Presently, there is little information available on the performance of single point diamond turning when machining contact lens polymers. Therefore, the research work undertaken herewith is aimed at testing known facts in contact lens diamond turning and investigating the performance of ultra-high precision manufacturing of contact lens polymers. Experimental tests were conducted on Roflufocon E, which is a commercially available contact lens polymer and on Precitech Nanoform Ultra-grind 250 precision machining. Tests were performed at varying cutting feeds, speed and depth of cut. Initial experimental tests investigated the influence of process factors affecting surface finish in the UHPM of lenses. The acquired data were statistically analysed using Response Surface Method (RSM) to create a model of the process. Subsequently, a model which uses Runge-Kutta’s fourth order non-linear finite series scheme was developed and adapted to deduce the force occurring at the tool tip. These forces were also statistically analysed and modelled to also predict the effects process factors have on cutting force. Further experimental tests were aimed at establishing the presence of the triboelectric wear phenomena occurring during polymer machining and identifying the most influential process factors. Results indicate that feed rate is a significant factor in the generation of high optical surface quality. In addition, the depth of cut was identified as a significant factor in the generation of low surface roughness in lenses. The influence some of these process factors had was notably linked to triboelectric effects. This tribological effect was generated from the continuous rubbing action of magnetised chips on the cutting tool. This further stresses the presence of high static charging during cutting. Moderately humid cutting conditions presented an adequate means for static charge control and displayed improved surface finishes. In all experimental tests, the feed rate was identified as the most significant factor within the range of cutting parameters employed. Hence, the results validated the fact that feed rate had a high influence in polymer machining. The work also established the relationship on how surface roughness of an optical lens responded to monitoring signals and parameters such as force, feed, speed and depth of cut during machining and it generated models for prediction of surface finishes and appropriate selection of parameters. Furthermore, the study provides a molecular simulation analysis for validating observed conditions occurring at the nanometric scale in polymer machining. This is novel in molecular polymer modelling. The outcome of this research has contributed significantly to the body of knowledge and has provided basic information in the area of precision manufacturing of optical components of high surface integrity such as contact lenses. The application of the research findings presented here cuts across various fields such as medicine, semi-conductors, aerospace, defence, telecom, lasers, instrumentation and life sciences.
- Full Text:
- Date Issued: 2015
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