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Title: A new rheological polymer based on boron siloxane cross-linked by isocyanate groups
Author: Shmelin, George
Awarding Body: University of Hertfordshire
Current Institution: University of Hertfordshire
Date of Award: 2012
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The research described in this thesis originated from an idea to develop new body protection for the sport of fencing. The ultimate goal is to develop body armour which would be flexible, wearable, washable, light and breathable, offer protection from injuries and cover the entire body of a sportsman. A new material which exhibits shear thickening behaviour has been specially developed for this purpose in the process of this investigation. The material was designed and synthesised as a soft polymeric system which is flexible, chemically stable and able to increase the value of its modulus of elasticity upon impact at a high strain rate, while remaining in its soft gel-like elastomeric state when low strain rate deformation is applied. The polymeric system that has been developed is based on interpenetrating polymeric networks (IPN) of immiscible polyurethane/urea-ester/ether and poly(boron)n(dimethylsiloxane)m (where on average m ≈ 16 n). In addition, as the polydimethylsilane (PDMS) based polymeric system strongly tends to phase separation, the siloxane polymeric network was chemically cross-linked to the polyurethane polymeric network through polyurethane chemical cross-link-bridges. In order to introduce polyurethane cross-links to a siloxane-based polymeric network, some of the attached methyl groups in the PDMS polymeric backbone were substituted by ε-pentanol groups. The resulting polymeric system combines properties of an alternating copolymer with IPN. The actual substitution of the methyl groups of PDMS into alternating ε-pentanol groups was performed by Grignard reaction of trifunctional chlorosilane monomers, magnesium and 1,5-dibromopentane. Chemical analytical techniques like FT-IR, 13C NMR and 1H NMR spectroscopy were used to reveal the chemical structure of the synthesised polymeric network. The mechanical and dynamical properties of the obtained polymeric system were analysed by dynamic mechanical analysis (DMA). This part of the investigation indicated that the novel polymeric system exhibited shear thickening behaviour, but only at a narrow diapason of deformations (i.e., deformations between 2 to 3 % of the length of the sample). At this limited diapason of deformation an effective increase of the modulus of elasticity from 6 MPa (at lower frequencies, i.e., up to ≤6 Hz of the applied oscillating stress) to 65 MPa (at frequencies between 12.5 to 25 Hz) was obtained. However, no increase in the modulus of elasticity was recorded at deformations below 1.5 % or above 3.5 % of length of the sample at the same frequencies (0 to 25Hz) of the applied oscillating stress.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Polymer ; rheology ; silicone ; siloxane ; hetero-siloxane ; polyurethane ; polyurea-urethane ; polyurethane-siloxane co-polymer ; polymeric synthesis ; DMA polymer analysis ; FT-IR and HNMR/CNMR spectroscopy polymer analysis ; IPN ; scarcely cross-linked IPN ; one side Grignard reaction of short a?-di halo olefins