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Title: Research into order parameters and graphene dispersions in liquid crystal systems using Raman spectroscopy
Author: Zhang, Zhaopeng
ISNI:       0000 0004 5356 4619
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2015
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Polarized Raman Spectroscopy (PRS) is one of the experimental methods which can be employed to deduce orientational order parameters, e.g. 〈P_200 〉, 〈P_400 〉, in liquid crystals from the experimental depolarization ratio graph via fitting. However, it has long been known that the order parameters deduced from the different vibrational modes are found to be different within the same sample. As a result, only certain vibrational modes can be reliably selected for analysis, limiting the application of PRS. The possible explanations are discussed in this thesis. The first explanation is given by considering a dipole tilt β_0 which is defined as the tilt angle of the dipole vibrational direction and the molecular long axis. A second explanation comes from assuming different vibrational symmetries, i.e. cylindrical or elliptic cylindrical. Molecular biaxial order parameters are introduced in both explanations. A systematic check via calculation shows that a common set of order parameters (including molecular biaxial order parameters) can be obtained with different depolarization ratio graphs when the explanations are considered. Both depolarization ratio graphs can also agree well with that obtained from phenyl and cyano stretching modes experimentally. A supplementary discussion shows that by using the first explanation, 〈P_400 〉 which, in previous fitting, shown an excessive value by using cyano stretching mode is reduced (15% reduced at β_0=15°, 〈P_402 〉=0.0536). PRS is also employed to analyse the order parameters in a bent-core system using a molecular model with the bend angle Ω and tilt angle B_0. The effects of each of the uniaxial and phase biaxial order parameters are considered. With a total Raman tensor generated by the sum of Raman tensor from each arm, reasonable uniaxial order parameters fitting values can be obtained from PRS without considering biaxial order parameters. These results agree well with those deduced from the refractive index measurements, which shows a new approach to the investigation of bent-core systems. However, it is also shown that introducing phase biaxial order parameters can’t provide robust fitting, leading inaccurate fitting values in the end. Several different liquid crystals (5CB, E7, HAT-6 and SSY) have been examined on seeking graphene/graphene oxide dispersions in liquid crystal systems. Unfortunately, no stable dispersion was obtained by applying simple experimental techniques. However, a highlight comes from the test of a lyotropic liquid crystal formed by a discotic molecule in NMP suggesting a possible dispersion medium for graphene. Meanwhile, by using Raman spectroscopy, the interaction between liquid crystal molecules and graphene can be obtained from the peak shift of vibrational modes. The experimental results suggest a stronger interaction in E7 compared to 5CB. No shift in ZLI-1695 indicates the different effects from the rigid core. Further, the discotic liquid crystal (HAT-6) shows a strong interaction with graphene. These facts lead to a conclusion that the interaction still exists in the graphene/liquid crystal dispersion providing a guide on controlling and optimizing the dispersion quality for the future research.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Liquid Crystal ; Raman Spectroscopy ; Order Parameter ; Graphene