PERFORMANCE EVALUATION OF LLDPE/CaCO3 MODIFIERS WITH AND WITHOUT TITANATE COUPLING AGENT ON ASPHALT BINDER AND MIXTURE

The complexity and challenge created by asphalt material motivates researchers and engineers to investigate the behavior of this material to develop a better understanding, and improve the performance of asphalt pavement. Over decades, a wide range of modification at macro, meso, micro and nano scales have been conducted to improve the performance of asphalt pavement. This study was initiated to utilize the newly developed asphalt modifier pellets. These pellets consisted of different combinations of calcium carbonate (CaCO3), linear low-density polyethylene (LLDPE) and titanate coupling agent (CA) to improve the asphalt binder as well as pavement performance across a wide range of temperature and loading pace. These materials were used due to their unique characteristics and promising findings from various industries, especially as modifiers in pavement material. The challenge is to make sure the CaCO3 disperses very well in the mixture. The rheological properties of neat asphalt binder PG58-28 and modified asphalt binder (PG58-28/LLDPE, PG58-28/CaCO3, PG58-28/CaCO3/LLDPE, and PG58-28/CaCO3/LLDPE/CA), were determined using rotational viscometer (RV) test, dynamic shear rheometer (DSR) test and bending beam rheometer test. In the DSR test, the specimens were evaluated using frequency sweep and multiple shear creep recovery (MSCR). The asphalt mixtures (aggregate/PG58-28, aggregate/ PG58-28/LLDPE, aggregate/PG58-28/CaCO3, aggregate/PG58-28/LLDPE/CaCO3 and aggregate/PG58-28/LLDPE/CaCO3/CA) were evaluated using the four point beam fatigue test, the dynamic modulus (E*) test, and tensile strength test (to determines tensile strength ratio, TSR). The RV test results show that all modified asphalt binders have a higher viscosity compared to the neat asphalt binder (PG58-28). Based on the Jnr results (using MSCR test), all the modified asphalt binders have a better resistance to rutting compared to the neat asphalt binder. A higher modifier contents have resulted in a better recovery percentage of asphalt binder (higher resistance to rutting), except the specimens prepared using PECC’s modified asphalt binder (PG58-28/CaCO3/LLDPE). The BBR test results show that all the modified asphalt binders have shown comparable performance in term of resistance to low temperature cracking, except the specimen prepared using the LLDPE modifier. Overall, 5 wt% LLDPE modified asphalt binder was found to be the best asphalt binder in terms of resistance to rutting. Meanwhile, 3 wt% PECC-1CA’s modified asphalt binder can be considered as the best (in terms of resistance to thermal cracking) with the lowest mean critical cracking temperature. The appearance of CaCO3 was found useful merely in improving the resistance to fatigue cracking of asphalt mixture. However, application of LLDPE has undermined the fatigue life of asphalt mixtures. Adding LLDPE and coupling agent throughout this study does not sufficiently help in terms of elastic behavior which essential to enhance the resistance to fatigue cracking. In contrast, application of LLDPE has increased the indirect tensile strength values and TSR of asphalt mixtures, indicates a better resistance to moisture damage. The usage of the coupling agent does not change the behavior of the asphalt mixture, which could be due to imbalance effects resulted by combination of LLDPE and CaCO3 in asphalt binder. Further investigations without incorporating CaCO3 should be conducted further. To investigate the feasibility of using LLDPE and coupling agent as modifiers in asphalt pavements, more research should be conducted on different percentages of LLDPE (less than 3 wt%), and at the higher and w wider range of coupling agent content, from 3 wt% to 7 wt% based on the polymer mass.

NICKEL-COBALT SOLID SOLUTION AND ITS APPLICATIONS AS CATALYSTS FOR CARBON DIOXIDE REFORMING OF METHANE

Global warming issue becomes more significant to human beings and other organisms on the earth. Among many greenhouse gases, carbon dioxide (CO2) has the largest contribution to global warming. To find an effective way to utilize the greenhouse gas is urgent. It is the best way to convert CO2 to useful compounds. CO2 reforming of methane is an attractive process to convert CO2 and methane into synthesis gas (CO/H2), which can be used as a feedstock for gasoline, methanol, and other hydrocarbons. Nickel and cobalt were found to have good activity for CO2 reforming. However, they have a poor stability due to carbon deposition. This research developed efficient Ni-Co solid solution catalysts with excellent activities and high stability for CO2 reforming of methane. First, the structure of binary oxide solid solution of nickel and cobalt was investigated. It was found that while the calcination of Ni(NO3)2 and Co(NO3)2 mixture with 1:1 molar ratio at a high temperature above 800 oC generated NiO-CoO solid solution, only Ni3O4-Co3O4 solid solution was observed after the calcination at a low temperature of 500 oC. Furthermore, if the calcination was carried out at a medium temperature arranged from 600 to 700 oC, both NiO-CoO and Ni3O4-Co3O4 solid solutions can be formed. This occurred because Co3O4 can induce the formation of Ni3O4, whereas NiO can stabilize CoO. In addition, the lattice parameter of Ni3O4, which was predicted by using Vegard’s Law, is 8.2054 Å. As a very important part of this dissertation, Ni-Co solid solution was evaluated as catalysts for CO2 reforming of methane. It was revealed that nickel-cobalt solid solution showed excellent catalytic performance and high stability for CO2 reforming of methane. However, the stability of Ni-Co solid solution catalysts is strongly dependent on their composition and preparation condition. The optimum composition is 50%Ni-50%Co. Furthermore, the structure of Ni-Co catalysts was characterized by XRD, Vvis, TPR, TPD, BET, AES, TEM, XANES and EXAFS. The relationship between the structure and the catalytic performance was established: (1) The reduced NiO-CoO solid solution possesses better catalytic performance and stability than the reduced Ni3O4-Co3O4 solid solution. (2) Ni is richer on surface in Ni-Co catalysts. And (3) the reduction of Ni-Co-O solid solution generated two types of particles, small and large particles. The small ones are dispersed on large ones as catalytic component.

COMBUSTION INITIATION BY ELECTRICAL-DISCHARGE-INDUCED PLASMA IN LEAN AND DILUTE METHANE-AIR MIXTURE: EXPERIMENTAL AND MODELING INVESTIGATION

This dissertation represents experimental and numerical investigations of combustion initiation trigged by electrical-discharge-induced plasma within lean and dilute methane air mixture. This research topic is of interest due to its potential to further promote the understanding and prediction of spark ignition quality in high efficiency gasoline engines, which operate with lean and dilute fuel-air mixture. It is specified in this dissertation that the plasma to flame transition is the key process during the spark ignition event, yet it is also the most complicated and least understood procedure. Therefore the investigation is focused on the overlapped periods when plasma and flame both exists in the system. Experimental study is divided into two parts. Experiments in Part I focuses on the flame kernel resulting from the electrical discharge. A number of external factors are found to affect the growth of the flame kernel, resulting in complex correlations between discharge and flame kernel. Heat loss from the flame kernel to code ambient is found to be a dominant factor that quenches the flame kernel. Another experimental focus is on the plasma channel. Electrical discharges into gases induce intense and highly transient plasma. Detailed observation of the size and contents of the discharge-induced plasma channel is performed. Given the complex correlation and the multi-discipline physical/chemical processes involved in the plasma-flame transition, the modeling principle is taken to reproduce detailed transitions numerically with minimum analytical assumptions. Detailed measurement obtained from experimental work facilitates the more accurate description of initial reaction conditions. The novel and unique spark source considering both energy and species deposition is defined in a justified manner, which is the key feature of this Ignition by Plasma (IBP) model. The results of numerical simulation are intuitive and the potential of numerical simulation to better resolve the complex spark ignition mechanism is presented. Meanwhile, imperfections of the IBP model and numerical simulation have been specified and will address future attentions.