Development of polypropylene – waste tyre crumbs based tpe's with the aid of vistamaxxtm as a compatibiliser
- Authors: Masele, Siyamtanda
- Date: 2019
- Subjects: Polymers , Polymerization Crumb rubber Rubber
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/42589 , vital:36670
- Description: Polypropylene (PP) is a semi crystalline thermoplastic polymer and one of the most commonly used polyolefins. It is well known for its poor impact resistance; hence, for industries such as the automotive and packaging, reinforced PP is widely used. In general plastic waste disposal is a global crisis raising environmental and human health concerns, with PP being the highest consumed polymer globally; hence a push in the reuse and recycling of PP. Recycled polypropylene has limited uses for industrial applications due to its highly reduced properties owing to the recycling process which inhabits cutting of chains lengths, broadened molecular weight distributions and compromised crystallinity. Several studies have investigated the use of reinforcing fillers and modifiers in order to improve properties of PP. Inorganic materials and minerals such as CaCO3, Mica, Talc and glass fibre are used as fillers to improve mechanical properties (tensile and hardness), but still lacks in improving the impact resistance. Thermoplastic elastomers (TPE) are typically used where elastomer and thermoplastics fail as individual components. This is because they have the benefit of thermoplastic properties at hypo ambient condition and elastomer properties such as good impact and elongation at sub-zero conditions. The study took a route of using PP and waste tyre crumb rubber (CR) material to prepare potentially low-cost waste based TPE’s, which would then inherit both properties of PP and the rubber component. VistamaxxTM 6202 (EPR), a commercial name for ethylene-propylene monomer (EPR), was used as a compatibiliser to improve interaction between PP and CR and to contribute towards the overall improvement of various properties such as mechanical properties. VistamaxxTM has a low glass transition temperature (Tg, = -30 ºC), which is important for low temperature applications such as cold storage; it also has a very high elongation and as a result contributed significantly to the overall properties when used in TPE blends. The study highlighted differences between two TPE compounding formulation pathways; namely master-batch (MB) and design of experiments (DoE). The MB formulations were blends that were prepared by a conventional way of compounding; where a pre-mixed CR/EPR blend, in the ratio of 80(CR):20(EPR), was used to form a master-batch. Results showed that there are some similarities between TPEs prepared in different ways, which suggests that the ultimate properties such as thermal stability are in fact more PP matrix based. Thermal analyses results revealed that when high amount of CR was added to the TPE blends, there was a substantial amount of residue mainly due to inherent carbon black. The degree of crystallinity of the blends decreased with increased amounts of CR irrespective of whether it was the MB or DoE blends. The MB TPE blends demonstrated that hardness is not linked to the amount of the MB nor the crystallinity of blends. Meanwhile, tensile elongation and tensile stress were affected by crystallinity. On the other hand, the impact strength findings showed that the amount of MB in TPE blends reached a threshold at 30%. The DoE based TPE blends demonstrated that the optimum mechanical properties are observed when components of the blends are incorporated individually during compounding. This was observed for impact strength, tensile stress as well as elongation at break. The results showed that the incorporation of EPR should be at least 20% for good impact and elongation properties; however, for tensile and hardness, the PP matrix must be high. The study also showed that, for better mechanical properties it was more suitable to use the blends formulated with DoE, because the master-batch approach limited the improving of the mechanical properties by an addition of up to 30% of both the CR and EPR. The storage modulus as well as the tan delta for both MB and DoE decreased when the elastomeric phases were added on both methods, whereas tan delta Tg values decreased as more of the elastomeric phase was added. Evidence from morphology studies showed that the majority of TPE blends suffer from inadequate distribution and adhesion between PP and elastomer; resulting in poor mechanical properties. Furthermore, a threshold of matrix invasion is observed from 30% and above of CR in the blend, where lack of in capsulated lamps of CR were observed hindering the stress induced crystallization and relaxation of the PP phase. The latter was observed irrespective of the type of blend, which strongly suggests and highlights the limits of blending PP with elastomers. Study demonstrated the ability of VistamaxxTM to be utilized as a binding material for PP and CR and displaying the challenges that might arise when used as a master-batch with crumb rubber.
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- Date Issued: 2019
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.
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- Date Issued: 2019