The purpose of this thesis was to develop microscale fracture toughness tests to be performed in situ based off previously used macroscale fracture toughness tests. The thesis also was to use these tests to perform in situ analysis and imaging of reinforced adhesives during crack propagation. Two different fracture toughness tests were developed for this thesis through developing fixtures and sample geometry. A microscale double cantilever beam (DCB) test was developed for mode I fracture (opening mode). A microscale end notch flexure (ENF) test was developed for mode II fracture (sliding mode). Three different types of materials were used as a reinforcing agent and tested using the micro-DCB and micro-ENF tests. Magnetoelectric nanoparticles (MENs) doped adhesive showed a 12% increase in mode II toughness and 33% increase in total fracture energy for micro-DCB. Similarly, the graphene foam (GrF) doped adhesive showed an approximate 34% increase in mode II toughness and a 71% increase in total fracture energy for mode I. In situ imaging provided real time imaging of crack propagation for all three reinforcing agents that allowed for a novel analysis of the crack propagation and general fracture.

NOx (NO, NO2) is one of the most harmful air-pollutants from exhaust, resulting in series of environmental problems as well as severe healthy issues for human beings. Selective catalytic reduction (SCR) system is a common approach to eliminate NOx onboard by using ammonia as a reductant. However, ammonia storage unit has been one of the restriction factors for the NOx conversion efficiency because of insufficient ammonia dosing rate and the corrosive and hazardous nature of ammonia. Thus, a reliable ammonia storage and delivery system is of high scientific and commercial desire. In this thesis, novel composites were fabricated and studied based on MgCl2 and SrCl2, two commercial alkaline earth metal halides (AEMH) for ammonia storage. In order to reduce the melting issue and enhance the kinetics of the ammonia sorption, carbon materials, graphite (Gt) and graphene nanoplatelets aggregates (GNA) were added to MgCl2 at 1 wt.%, 10 wt.% and 20 wt.%. With ball milling and hydraulic pressing, the aforementioned carbon-MgCl2 composites were structured into pellets for various characterization. With real-time recording in the tube furnace at 1073 K, we observed that with 20% carbon additives, the pelletized composites maintained their structure with 95% mass retention, while the pure MgCl2 completely melted and disintegrated. According to the SEM images, carbon materials separated MgCl2 so that the molten MgCl2 cannot form large droplet to spread out. Furthermore, the 20 wt.% GNA-80 wt.% MgCl2 (GNA20) composites demonstrated enhanced kinetics in both absorption and desorption of ammonia, which is 83% faster in ammonia absorption and 73% faster in desorption in the first two minutes compared to the pure MgCl2. The BET surface area and mercury intrusion porosimetry results explains the kinetic elevation by the GNA by introducing extra reaction surface and nanopores as the diffusion path for ammonia. The enhancement of both structural stabilityand kinetics make the GNA20 composite a robust ammonia carrier. During the chemical absorption process, SrCl2 uptakes 8 ammonia molecules resulting in 4 times volume expansion. This dramatic expansion and shrinkage during the absorption and desorption will destroy the structure and disintegrate the SrCl2 into powder, which could bring the dust explosion risk for many applications. Based on the carbon-salts composites, a novel porous SrCl2 structure is designed and fabricated with graphene oxide as skeleton by freeze casting process. Porous SrCl2 structure is feasible for various geometries with different molds at a wide SrCl2 load from 0 wt.% to 96 wt.%. The ammonia capacity of the porous SrCl2 is linear proportional to the SrCl2 load. During the ammonia absorption and desorption cycles, the graphene oxide skeleton could self-adjust along with the volume swing to within its flexibility. This porous SrCl2 demonstrates excellent tolerance of volume swing and enhanced kinetics as a promising ammonia storage material. Our approach and results may cast light on the obstacles of structuring self-expansion and shrinkage materials as well as on enhancing the gas sorption properties.

Carbon nanotubes (CNT) and graphene have been one of the noticeable research areas in science and technology. In recent years, the assembly of these carbon nanostructures is one of the most interesting topic to the scientific world due to its variety of applications from nano to macroscale. These bulk nanostructures to be applicable in shock absorbers, batteries, sensors, photodetectors, actuators, solar cells, fuel cells etc. The present work is motivated to study the detailed compressive behavior of three dimensional cellular assemblies of CNT and graphene. The CNT foams are synthesized by chemical vapor deposition method. It is interesting to study the compressive behavior of CNT foam in the presence external magnetic field applied perpendicular to CNT axis. The peak stress and energy absorption capability of CNT foam enhances by four and nearly two times in the presence of magnetic field as compared to the absence of the magnetic field. In the absence of magnetic field the deformation of CNT foam is obtained elastic, plateau and densification regions. Further CNT foam is loaded with iron oxide nanoparticles of diameter is ~ 40nm on the surface and detailed study of the compressive behavior of the foam by varying iron nanoparticles concentration. The peak stress and energy absorption capability of CNT foam initially decreases with increasing the intensity of the magnetic field, further increases the intensity of the magnetic field the maximum stress and energy absorption capability increases which is due to magnetic CNT and particles align in the direction of the magnetic field. CNT surfaces were further modified by fluid of different viscosities. The mechanical behavior of CNT foam filled with fluids of varying viscosities like 100%, 95% and 90% glycerol and silicone oil are 612, 237, 109 and 279 mPa-s respectively. The mechanical behavior of CNT foam depends on both the intensity of magnetic field and fluid viscosity. The non linear relation between peak stress of CNT and magnetic field intensity is σp(B, η) = σ0 ± α(B-B0) where σ0 is the peak stress at B = B0 , η is the fluid viscosity, parameter α depends on properties of the MR fluid and B0 is an optimum magnetic field for which peak stress is maximum or minimum depending on the fluid viscosity. Graphene is assembled into a three dimensional structure called graphene foam. The graphene foam is infiltrated with polymer and study the detailed compressive behavior of graphene foam and graphene foam/PDMS at different strains of 20, 40, 60 and 70%. The maximum stress and energy absorption capability of graphene foam/PDMS is six times higher than the graphene foam. Also the graphene foam/PDMS is highly stable and reversible for 100 cycles at strains of 30 and 50%. The mechanical behavior of CNT, graphene foam, CNT/PDMS and graphene foam/PDMS is compared. Among all the foams, graphene foam/PDMS has shown the highest elastic modulus as compared to other foams. This behavior can be attributed to the wrinkles formation during the growth of graphene and a coupling between PDMS and interfacial interactions of graphene foam. Therefore it suggests potential applications for dampers, cushions and electronic packaging. Furthermore, the interaction between nanoparticles and polymer in a novel architecture composed of PDMS and iron oxide nanoparticles is studied. The load bearing capacity of uniform composites enhanced by addition of nanoparticles, reaching to a maximum to 1.5 times of the PDMS upon addition of 5wt.% of nanoparticles, and then gradually decreased to 1/6th of PDMS upon addition of 20wt.% of nanoparticles. On the other hand, the load bearing capacity of architectured composites at high strains (≥40%) monotonically increased with addition of nanoparticles in the pillars.

Three-dimensional graphene foam (3D GrF) is an interconnected, porous structure of graphene sheets with excellent mechanical, electrical and thermal properties, making it a candidate reinforcement for polymer matrices. GrF’s 3D structure eliminates nanoparticle agglomeration and provides seamless pathways for electron travel. The objective of this work is to fabricate low density GrF reinforced epoxy composites with superior mechanical and electrical properties and study the underlying deformation mechanisms. Dip coating and mold casting fabrication methods are employed in order to tailor the microstructure and properties. The composite’s microstructure revealed good interfacial interaction. By adding mere 0.63 wt.% GrF, flexural strength was improved by 56%. The addition of 2 wt.% GrF showed a surge in glass transition temperature (56oC), improvement in damping behavior (150%), and electrical conductivity 11 orders of magnitude higher than pure epoxy. Dip coated and mold casted composites showed a gauge factor of ~2.4 indicating electromechanically robust composite materials.