The strain amplitude dependency , i.e. the Fletcher-Gent effect and Payne effect, and the strain rate dependency of rubber with reinforcing fillers is modelled using a modified boundary surface model and implemented uniaxially. In this thesis, a split of strain instead of stress is utilized, and the storage and loss modulus are captured over two decades of both strain amplitudes and frequencies. In addition, experimental results from bimodal excitation are replicated well, even though material parameters were obtained solely from harmonic excitation. These results are encouraging since the superposition principle is not valid for filled rubber, and real-life operational conditions in general contain several harmonics. This means that formulating constitutive equations in the frequency domain is a cumbersome task, and therefore the derived model is implemented in the time domain. Filled rubber is used irreplaceable in several engineering solutions, such as tires, bushings, vibrations isolators, seals and tread belts, to name just a few. In certain applications, it is sufficient to model the elastic properties of a component during finite strains. However, Hooke’s law is inadequate for this task. Instead, hyperelastic material models are used. Finally, the thesis presents a methodology for obtaining the required material parameters utilizing experiments in pure shear, uniaxial tension and the inflation of a rubber membrane. It is argued that the unloading curve rather than the loading curve is more suitable for obtaining these parameters, even at very low strain rates. / <p>QC 20140917</p>

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DC resistance and AC conductance and capacitance have been measured under various conditions in an effort to electrically characterize and make electrical-mechanical correlations for 15 carbon black filled rubber samples. Resistance, conductance and capacitance have been monitored as functions of uniaxial compressive stress, time, temperature, and mechanical and thermal history. Capacitance and conductance have also been monitored as functions of frequency under various degrees of compressive loading and before and after specific heat treatments. A direct relationship has been found between sample • conductance and capacitance under any thermal and/or mechanical condition. This is in agreement with previous theories of conduction network formation and percolation. Various conduction mechanisms have been enumerated and an equivalent circuit of a network of lumped R-C "microelements'' has been qualitatively described. Stress, relaxation, frequency, and temperature dependences of the macroscopic parameters measured ( conductivity and capacitance) are discussed in terms of this model. / M.S.

The mixing of additives into a plastic is an extremely important step in the plastics industry, necessary for the manufacture of almost every conceivable product. Therefore the costs in developing new products can prove very expensive as the testing is usually carried out using full scale machines, usually using twin screw extruders because they are able to provide good dispersive and distributive mixing. This is particularly important when compounding difficult to disperse additives and nano-additives. What is required is a machine that can replicate the mixing abilities of a twin-screw extruder but on a laboratory scale. There have been attempts by industry to develop smaller machines, such as the Thermo Scientific HAAKE Minilab II Micro Compounder which processes on the scale of 7 cm3 of material volume. This can be too small for some needs and therefore a machine is required to produce material on the 10g to 100g scale. To this end a laboratory mixer of novel design was devised and its mixing performance was assessed using conductive carbon black and compared against the Thermo Scientific HAAKE Minilab II Micro Compounder, a 19 mm co-rotating twin-screw extruder and a 40 mm co-rotating twin-screw extruder. Carbon black was used because mixing performance can be assessed by measuring the minimum carbon loading necessary to induce electrical conductivity. It was found that the minimixer was able to induce electrical conductivity at loading of 5.75% but the comparison with the other machines proved difficult as the achievement of the threshold at which semi-conductivity occurred appeared independent of shear rate and mixing duration. / EPSRC / The following files are not available online: Americhem raw data; Carbon Black raw data; Videos.

The interactions which occur between both polar and non-polar fluid phases and surfaces of various carbon materials: Activated Carbon (AC), non-porous Carbon Black (CB) and Multiwall Carbon Nanotubes (MWCNTs)with different surface chemistry have been studied. These are currently of great interest as they govern the interfacial behaviour of carbons in a wide range of applications; separation adn composite technologies being two prime examples. Consequently, techniques for chemical modification of carbon surfaces ar also of interest. Surface oxygen functional groups have been introduced, or modified, using the following oxidation techniques: liquid-phase oxidation (both AC and CB), Fenton and Birch reduction treatment (MWCNTs) and in a more controlled manner using gas-phase ozone treatment (CB). The chemistry of all the resulting carbon surfaces were characterised using X-ray Photoelectron Spectroscopy (XPS), which gives a quick and direct quantitative measure of the external surface composition. This technique, which has not yet been extensively employed in detailed adsorption studies, is a promising alternative to Temperature Programmed Desorption (TPD) and Boehm titration method in the determination of oxygen and other surface groups. Physical effects of the various surface modifications have been studied using a variety of techniques appropriate for the material in question. Scanning Electron Microscopy (SEM) images show some deteriorating effects of the liquid-phase oxidations on the structure of both activated carbon and carbon black materials. Conversely, surface areas from nitrogen adsorption at 77oK, coupled witj immersion calorimetry data for toluene, show thet the physical structure of the carbon blacks is not modified by ozone treatment. This has allowed a detailed study of the effects of surface oxygen level (i.e. polarity) on vapour adsorption. Regarding the MWCNT materials, detailed High-Resolution Electron Microscopy (HRTEM) photographs show that the multi-wall structure of the nanotubes in not significantly disrupted during the introduction of active functional groups by the Fenton or Birch treatment and therefore keeping intact their mechanical properties which augurs well for their use as reinforcement in composite structures whilst also improving their dispersion properties in polar fluids. A systematic shift to higher adsorption values, due to the increasing specific interactions between the alcohol -OH groups and the surface oxygen groups, is observed in all the isotherms of alcohols from the CB series as the total surface oxygen concentration ([O]T) increases. Moreover, this effect was observed to be most significant for methanol confirming that the mechanism of adsorption is dominated by hydrogen bonding and therefore dependant on the surface concentration of oxygen sites; whereas it becomes less marked in the case of ethanol and isopropanol respectively due to the increasing non-specific, dispersion, interactions of the alkyl chain with the non-polar carbon surface. Overall correlations were observed between the surface oxygen concentration [O]T, the resulting enthalpy of immersion -^Hi values and the characteristic energy E of the Dubinin-Radushkevich-Kaganer (DRK) equation obtained for toluene and these alcohols and the influence of the carbon surface chemistry on the character of the adsorption isotherms is also discussed. This behaviour is also observed and much more pronounced in the case of water adsorption on other oxidised carbon materials (AC, CB and MWCNT) due to the higher polarity of water molecules. The water adsorption data were analysed using in particular the Dubinin-Serpinsky (DS) equation and also some of its recent variations such as Barton and D'Arcy & Watt equations. The DS2 and various Barton equations were found to fit best the AC and CB materials modified by liquid-phase oxidations and also for the CB 03 series with increasing level of oxidation while both D'Arcy & Watt equations gave the best fittings for the MWCNTs materials. It was also shown that the resulting parameters ao (for the DS equation) describing the surface concentration of primary polar adsorption sites and as the limiting water adsorption value were both linked to the surface oxygen level [O]T. Regarding interfacial bonding, the oxidised CB and MWCNT materials are expected to show an improved physicochemical wetting of their surfaces by various resin compunds