The time dependence of the physical properties of ethylene/1-octene (EO)-copolymers after primary crystallization is investigated by calorimetry, density, and creep measurements. The temporal evolution of the multiple melting of EO-copolymers is monitored by differential scanning calorimetry. The low temperature endotherm displays an evolution similar to that observed for the enthalpy recovery in glasses after physical aging. Using this analogy, a calorimetry-aging rate is defined, which quantifies the change in the low endotherm temperature with time. Similarly a density-aging rate is defined from the evolution of density with time. A non-classical creep behavior is observed for short aging times, consistent with crystallization-induced shrinkage. The change in crystallinity during aging leads to a change in the shape of the relaxation spectrum. Hence, analysis of creep data cannot be carried out using Struik's superposition method. For both short and long aging times, the creep rate exhibits a dependence on copolymer composition similar to those associated with the calorimetry- and the density-aging rates, suggesting a common origin for the evolution of the low endotherm, the creep behavior and the bulk density. The calorimetry, density, and creep data are reexamined based on the following assumptions: First, a single population of small crystals is formed during crystallization at low temperature; Second, these small crystals increase in stability under isothermal conditions, easily melt and recrystallize during heating and serve as efficient thermo-reversible cross-links to increase the conformational constraints in the residual amorphous fraction. These assumptions appear to be consistent with all observations made to date. / Master of Science

For the first time, triblock copolymers of novel styrenic-based macromolecules were investigated in detail and examined for structure-morphology-performance relationships. We were able to design novel imidazolium- and phosphonium-containing styrenic macromolecules using controlled radical polymerization and conventional free radical polymerization strategies, for a variety of potential applications including electromechanical devices, ionic liquids, adhesives, and lithium-ion batteries. Block copolymers have a unique architecture providing physical crosslinking to behave as thermoplastic elastomers. We preferred ABA triblock copolymers as compared to random and diblock copolymers for improved mechanical performance. ABA triblock copolymers synthesized using nitroxide-mediated polymerization (NMP) of polystyrene external blocks and a charged imidazolium-containing central block, exhibited sufficient modulus and ionic conductivity for electromechanical transducers. We successfully reported the actuation behavior of triblock copolymers in the presence of added ionic liquid for the first time. We proposed that diluting the ion concentration of the ion-rich phase with neutral polymer comonomers that reduces Tg, increases ion dissociation, and potentially maximizes ionic conductivity. Tendency of ethylene-oxide units to coordinate cations, forming stable crown ether-like, multi-nuclear coordination complexes, promotes solvation and dissociation of ionic aggregates. In situ Fourier transform infrared spectroscopy (FTIR) was used to monitor the thermal polymerization in various acrylate and methacrylate monomers. It was found that acrylates have lower activation energy than methacrylates. The copolymerizations of poly(ethylene glycol)methyl ether acrylate (EG9MEA) and imidazole-containing monomer (VBIm) resulted in controlled polymerization kinetics with narrow molecular weight distributions. The control behavior of the copolymerizations is likely attributed to the observed decrease in calculated apparent rate constants for the copolymerizations with addition of VBIm as comonomer. Reversible addition fragmentation transfer (RAFT) successfully synthesized well-defined A-BC-A triblock copolymers containing a synergy of pendant ether and imidazolium sites. We demonstrated that electromechanical transducers derived from these triblock copolymer membranes with added ionic liquid showed superior actuation performance compared to a benchmark Nafion® membrane, suggesting potential for ionic polymer device applications. This was attributed to optimum modulus, improved ionic conductivity, and microphase-separated morphology of triblock copolymers. Conventional free radical polymerization and anion metathesis of 4-(diphenylphosphino)styrene (DPPS) successfully generated high molecular weight triaryl phosphine-containing copolymers. These macromolecules have no -CH2 group at the benzylic position increasing the thermal stability of the DPPS-containing polymers. Counterion exchange to fluorinated, bulkier anions broadened the library of polyelectrolytes, led to improved thermal stabilities, lower glass transition temperatures, and tunable wetting behavior. We also reported the synthesis of salt-responsive copolymers using conventional free radical polymerization. Adhesive performance measurements such as peel tests and probe tack enforced the application of these polymers as pressure sensitive adhesives. We also demonstrated the synthesis and subsequent neutralization of novel, well-defined A-BC-A triblock copolymers containing a soft central 'BC' block consisting of Sty-Tf2N and DEGMEMA with polystyrene external blocks. Sty-Tf2N monomer enables an important delocalization of the negative charge. Li+ has weak interactions with this anionic structure, consequently enabling a high dissociation level. Li+ ions are associated to the polymer chain to produce high transport numbers. Furthermore, incorporating DEGMEMA lowers the Tg of the charged block copolymers, thereby increasing the segmental mobility and thus ionic conductivity. Finally, the structure-property-morphology study of these triblock copolymers will be helpful for their use in potential applications such as ion-containing membranes, lithium-ion batteries. / Ph. D.

This work combines many characterization techniques in an effort to enhance understanding of molecular motions of polymers and. how they are influenced by' structure. The primary characterization method was dielectric spectroscopy which utilizes an AC electric field as the stress field. A variety of new, well controlled polymeric systems were studied. The first series included a number of radial starblock copolymers, styrene/isoprene, t-butyl- styrene/isoprene, and t-butyl-styrene/butadiene. These ABA copolymers consisted of hard and soft blocks, with the soft block comprising 75% by weight. The effect of microstructure of the soft block, casting solvent, hydrogenation, and chemical composition of the hard block were some of the variables studied. The amount of phase separation and the molecular motions occurring will be influenced by these parameters. Hydrogenation of the soft block increased the phase separation. Another system investigated included some stereospecific poly(alkyl methacrylates) which were synthesized anionically. In this series the alkyl group was systematically changed in order to study the effects of the bulkiness of the substituent and the tacticity on the a and ß transitions. The ß transition associated with side chain rotations was only observed in the case of the methyl and ethyl substituents. The Havriliak-Negami data analysis was used to evaluate the breadth and the skewness of the distribution of relaxation times. Finally, some high temperature thermoplastic polymers were evaluated with dielectric spectroscopy. The effect of the backbone composition, moisture, and fillers on the β transition was looked at. These studies showed that moisture and fillers play an important role on the magnitude and temperature of the observed β transition. / Ph. D.

In this project, the sensitivity of the phase behaviour of AB diblock copolymers to the addition a single C-monomer is investigated using self-consistent mean-field theory. The reference diblock copolymers are composed of the minority A block with N_A = 12 monomers and the majority B block with N_B monomers. The blocks are mutually repulsive and their interaction is characterised by χ_{ij} and acts over range σ_{ij}, where i and j represent the monomer species. When a C-monomer is added to the junction of the diblock copolymers, we observe a notable shift of the phase boundaries to the larger NB and smaller χ_{AB}. The shift to larger NB is due to an increased polymer stretching. When the C-monomers is nearly-neutral, the shift does not strongly depend on the interaction strength. Similarly, the shift is not visibly affected by changing σ_{AC} and σ_{BC}. However, when the the strength of the interaction is selective such that χ_{AC} = χ_{AB} + α and χ_{BC} = χ_{AB} − α, the shift size decreases with increasing α. Conversely, when the selective C-monomer is added to the majority end, the phase boundaries are shifted to the smaller N_B, with the smallest α giving the largest shift. The shifts can be generically understood to be cause by the interplay between the changes in the interfacial tension and polymer stretching due to the C-monomer. These results demonstrate sensitivity of phase behaviour of AB diblock copolymers to the addition of a C-monomer and may provide a useful link between experiment and theory. / Thesis / Master of Science (MSc)

Yes / 2D materials such as graphene, LAPONITE® clays or molybdenum disulfide nanosheets are of extremely high interest to the materials community as a result of their high surface area and controllable surface properties. While several methods to access 2D inorganic materials are known, the investigation of 2D organic nanomaterials is less well developed on account of the lack of ready synthetic accessibility. Crystallization-driven self-assembly (CDSA) has become a powerful method to access a wide range of complex but precisely-defined nanostructures. The preparation of 2D structures, however, particularly those aimed towards biomedical applications, is limited, with few offering biocompatible and biodegradable characteristics as well as control over self-assembly in two dimensions. Herein, in contrast to conventional self-assembly rules, we show that the solubility of polylactide (PLLA)-based amphiphiles in alcohols results in unprecedented shape selectivity based on unimer solubility. We use log Poct analysis to drive solvent selection for the formation of large uniform 2D diamond-shaped platelets, up to several microns in size, using long, soluble coronal blocks. By contrast, less soluble PLLA-containing block copolymers yield cylindrical micelles and mixed morphologies. The methods developed in this work provide a simple and consistently reproducible protocol for the preparation of well-defined 2D organic nanomaterials, whose size and morphology are expected to facilitate potential applications in drug delivery, tissue engineering and in nanocomposites. / University of Warwick, Materials GRP, EPSRC, The Royal Society, ERC

Yes / Developing medical devices that resist bacterial attachment and subsequent biofilm formation is highly desirable. In this paper, we report the optimization of the molecular structure and thus material properties of a range of (meth)acrylate copolymers which contain monomers reported to deliver bacterial resistance to surfaces. This optimization allows such monomers to be employed within novel coatings to reduce bacterial attachment to silicone urinary catheters. We show that the flexibility of copolymers can be tuned to match that of the silicone catheter substrate, by copolymerizing these polymers with a lower Tg monomer such that it passes the flexing fatigue tests as coatings upon catheters, that the homopolymers failed. Furthermore, the Tg values of the copolymers are shown to be readily estimated by the Fox equation. The bacterial resistance performance of these copolymers were typically found to be better than the neat silicone or a commercial silver containing hydrogel surface, when the monomer feed contained only 25 v% of the “hit” monomer. The method of initiation (either photo or thermal) was shown not to affect the bacterial resistance of the copolymers. Optimized synthesis conditions to ensure that the correct copolymer composition and to prevent the onset of gelation are detailed. / Impact Accelerators Account at the University of Nottingham; Camstent Ltd; The Wellcome Trust (ref 085245 and 103882)

Yes / In this work we report a facile method to prepare a fluorescence active self-healable hydrogel via incorporation of fluorescence responsive ionic block copolymers (BCPs). Ionic block copolymers were prepared via a combined effect of ring opening polymerization (ROP) of ε-caprolactone and xanthate mediated reversible addition–fragmentation chain transfer (RAFT) polymerization. Here polycaprolactone (PCL) was modified with xanthate to prepare a PCL based macro-RAFT agent and then it was utilized to prepare block copolymers with cationic poly(2-(methacryloyloxy)ethyltrimethyl ammonium chloride) (PCL-b-PMTAC) and anionic poly(sodium 4-vinylbenzenesulfonate) (PCL-b-PSS). During the block formation, the cationic segments were randomly copolymerized with a trace amount of fluorescein O-acrylate (FA) (acceptor) whereas the anionic segments were randomly copolymerized with a trace amount of 9-anthryl methylmethacrylate (AMMA) (donor) to make both the segments fluorescent. The block copolymers form micelles in a DMF : water mixture (1 : 4 volume ratio). The ionic interaction of two BCPs was monitored via Förster resonance energy transfer (FRET) and zeta potential measurements. The oppositely charged BCPs were incorporated into a polyacrylamide (PAAm) based hydrogel that demonstrated self-healing behavior and is also highly fluorescent. / IIT Kharagpur and MRC (MR/N501888/2)

Three block copolymer systems where one block was that of an engineering thermoplastic were examined. The first was that of polysulfone-polyarylester block copolymers where glassy-crystalline block copolymers were synthesized and characterized. The morphology of the block copolymers could be controlled by varying the chemical microstructure of the polyester segment. Solvent resistance was shown to improve as the level of crystallinity was increased. Segmented block copolymers of an amorphous polyarylester and polydimethylsiloxane were also investigated. Both the random-block and perfectly alternating synthetic routes were used and it was found that the perfectly alternating technique produced a more regular morphology; than the random-block technique. A study was also carried out on the incorporation of small amounts of polysulfone-polydimethylsiloxane block copolymers blended into homopolysulfone. Improved fracture toughness was observed without a significant loss of stiffness. The morphology of block copolymer particles dispersed in the polysulfone matrix was directly observed through transmission electron microscopy. / Ph. D.

The Variable Temperature Size Exclusion Chromatography (VTSEC) was used to study the dilute solution properties of various homo- and block copolymers as well as polymer blends, focus being primarily on the configuration-dependent properties such as average chain dimensions and hydrodynamic behavior of polymers. The study constituted of three parts. In the first part, the dilute solution properties of a series of poly(alkyl methacrylates) with varying side alkyl(ester) group were investigated as to the effect of the size of the side group on the average chain dimensions at various temperatures. The VTSEC results were found to reveal that the effect of the side group depends on the extent of chain flexibility imparted by the side group. In the second part, VTSEC was employed to investigate the applicability and validity of the various models for block copolymers in solution. For this purpose, several series of samples (all anionically synthesized) with various composition and molecular weight were used: i) poly(alkyl methacrylates), their diblock copolymers and blends and ii) diblock and triblock copolymers of poly(styrene/substituted styrene) and poly(butadiene/isoprene). VTSEC results showed that the applicability of each model to a block copolymer in solution depends on the compatibility among the components, the composition of the samples, the solvating power of the solvent used and the operating temperature. Micellization in the hydrocarbon diblock copolymer solutions was found to occur in selective solvent, its extent depending on the solubility parameter difference between the components, molecular weight, composition and solvent power. In the third part, poly(methyl methacrylate) samples with varying tacticities were studied as to the effect of stereochemical configuration on their dilute solution behavior and found to indicate that both syndiotactic and isotactic stereosequences are required for stereoassociation. Two new VTSEC data reduction procedures were devised in order to correct for the temperature drifts due to instrumentation in the first and to neutralize the effect of molecular weight in the second. In the second, termed as the Molecular Weight-Elution Volume Superposition Procedure, the effect of molecular weight alone was enutralized leaving only the effect of the intrinsic character (such as the size of the side group) of the sample in the elution behavior. Numerical computations, using the Matxrix Generation method based on the Rotational Isomeric State approximation, were carried out for stereoregular chains in order to evaluate their chain dimensions at various temperatures. / Ph. D.

The accuracy and utility of using Inverse Gas Chromatography (IGC) to characterize the microphase structure of block copolymers, and the strength of the thermodynamic interactions between the components of polymer blends and the unlike segments of block copolymers was examined. There were three parts to the study. First, the Scott ternary solution model, which is used for the study of thermodynamic interactions in polymer blends, was extended to low molecular weight mixtures. From vapor-liquid equilibrium data in the literature, the Gibbs free energy of mixing of binary mixtures (G_M ) calculated with the model were compared to experimental values. Mixtures containing ketones, aromatics hydrocarbons, chlorinated hydrocarbons, alcohols and water were studied. With the exception of mixtures containing water and low molecular weight alcohols, a fair to good correlation between theoretical and experimental values was observed. Second, the Gibbs free energy of mixing of nitrocellulose, polyvinyl chloride and poly(vinylidene fluoride) containing blends were measured with the Scott model from IGC data. For the nitrocellulose containing blend, the calculated Gibbs free energy of mixing values were large in magnitude (-2.0 to -5.0 calories/gram) and in fair agreement with the experimental heats of mixing determined from microcalorimetry measurements. For the remaining blends, the IGC data could not be distinguished from the results normally obtained for immiscible blends. The calculated G_M values were small in magnitude relative to the experimental error of the quantities. Concerning the block copolymers, the relative incompatibility of the constituent blocks of perfectly alternating block copolymers of polydimethylsiloxane and bis-A-polycarbonate and styrene-isoprene-styrene triblock copolymers was reflected in the measured G_M values. Overall, it was concluded that IGC is a good method for characterizing thermodynamic interaction between blend and copolymer constituents, but a severe limitation of the method is that the interactions are often too weak to measure accurately. Finally, the microphase structure of the above copolymers were studied by IGC from the retention behavior of hydrocarbon probes below the upper glass transition temperature of the copolymers. The degree of microphase separation, the size of the hard phases and the continuity of the soft phases in the copolymers characterized, and the results obtained were consistent with small angle x-ray, electron microscopy and differential scanning calorimetry data on the same materials. / Doctor of Philosophy