With the goal of improving chemical detection methods for buried improvised explosive devices (IED’s), the intention of this study is to show that functionalized nano-particles improve the sensing properties of a polymer applied to gas sensors. The approach was reinforcing the polymer, Nafion, with acid-functionalized carbon nanotubes (CNT’s). Ammonia was chosen as the analyte for its similarity to IED byproducts without the dangers of toxicity or explosion. Two sensor platforms were investigated: Quartz crystal microbalances (QCM’s) and microcantilevers (MC’s). Preliminary evaluation of treated QCM’s, via frequency analyzer, showed improvements in sensitivity and fast reversal of adsorption; and suggested increased stability. Tests with coated MC’s also supported the findings of QCM tests. Amplitude response of MC’s was on average 4 times greater when the Nafion coating contained CNT’s. Quantitative QCM testing with gas-flow meters showed that with CNT inclusion: the average number of moles adsorbed increased by 35% (>1.2 times frequency response); sensitivity improved by 0.63 Hz/ppt on average; although the detection threshold decreased marginally; but reusability was much better after extended exposures to concentrated ammonia. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2013.

Recent advances in materials engineering have given rise to a new class of materials known as active materials. These materials when used appropriately can aid in development of smart structural systems. Smart structural systems are adaptive in nature and can be utilized in applications that are subject to time varying loads such as aircraft wings, structures exposed to earthquakes, electrical interconnections, biomedical applications, and many more. Materials such as piezoelectric crystals, electrorheological fluids, and shape memory alloys (SMAs) constitute some of the active materials that have the innate ability to response to a load by either changing phase (e.g., liquid to solid), and recovering deformation. Active materials when combined with conventional materials (passive materials) such as polymers, stainless steel, and aluminum, can result in the development of smart structural systems (SSS). This Dissertation focuses on characterization of SMAs and structures that incorporate SMAs. This characterization is based on a hybrid analytical, computational, and experimental solutions (ACES) methodology. SMAs have a unique ability to recover extensive amounts of deformation (up to 8% strain). NiTiNOL (NOL: Naval Ordinance Lab) is the most commonly used commercially available SMA and is used in this Dissertation. NiTiNOL undergoes a solid-solid phase transformation from a low temperature phase (Martensite) to a high temperature phase (Austenite). This phase transformation is complete at a critical temperature known as the transformation temperature (TT). The low temperature phase is softer than the high temperature phase (Martensite is four times softer than Austenite). In this Dissertation, use of NiTiNOL in representative engineering applications is investigated. Today, the NiTiNOL is either in ribbon form (rectangular in cross-section) or thin sheets. In this Dissertation, NiTiNOL is embedded in parent materials, and the effect of incorporating the SMA on the dynamic behavior of the composite are studied. In addition, dynamics of thin sheet SMA is also investigated. The characterization is conducted using state-of-the- art (SOTA) ACES methodology. The ACES methodology facilitates obtaining an optimal solution that may otherwise be difficult, or even impossible, to obtain using only either an analytical, or a computational, or an experimental solution alone. For analytical solutions energy based methods are used. For computational solutions finite element method (FEM) are used. For experimental solutions time-average optoelectronic holography (OEH) and stroboscopic interferometry (SI) are used. The major contributions of this Dissertation are: 1. Temperature dependent material properties (e.g., modulus of elasticity) of NiTiNOL based on OEH measurements. 2. Thermomechanical response of representative composite materials that incorporate NiTiNOL“fibers". The Dissertation focuses on thermomechanical characterization of NiTiNOL and representative structures based on NiTiNOL; this type of an evaluation is essential in gainfully employing these materials in engineering designs.

No description available.

A new microrheology set-up is described, which allows us to quantitatively measure the transient rheological properties and microstructure of a variety of solvent-responsive complex fluids. The device was constructed by integrating particle tracking microrheology and microfluidics and offers unique experimental capabilities for performing solvent-response measurements on soft fragile materials without applying external shear forces. Transient analysis methods to quantitatively obtain rheological properties were also constructed, and guidelines for the trade-off between statistical validity and temporal resolution were developed to accurately capture physical transitions. With the new device and methodology, we successfully quantified the transient rheological and microstructural responses during gel formation and break-up, and viscosity changes of solvent-responsive complex fluids. The analysis method was expanded for heterogeneous samples, incorporating methods to quantify the microrheology of samples with broad distributions of individual particle dynamics. Transient microrheology measurements of fragile, heterogeneous, self-assembled block copolypeptide hydrogels revealed that solvent exchange via convective mixing and dialysis can lead to significantly different gel properties and that commonly applied sample preparation protocols for the characterization of soft biomaterials could lead to erroneous conclusions about microstructural dynamics. Systematic investigations by varying key parameters, like molecular structure, gel concentration, salt concentration, and tracer particle size for microrheology, revealed that subtle variations in molecular architecture can cause major structural and microrheological changes in response dynamics. Moreover, the results showed that the method can be applied for studying gel formation and breakup kinetics. The research in this thesis facilitates the design of solvent-responsive soft materials with appropriate microstructural dynamics for in vivo applications like tissue engineering and drug delivery, and can also be applied to study the effect of solvents on self-assembly mechanisms in other responsive soft materials, such as polymer solutions and colloidal dispersions.

This work showcases the utility of switchable materials. Included are a switchable room-temperature ionic liquid, a switchable solvent, a switchable heterogeneous catalyst system, and a switchable gel. First, the switchable ionic liquid 2-butyl-1,1,3,3-tetramethylguanidium methylcarbonate is fully investigated. Its use in a complete chemical process (including reaction, separation, reformation, and recycle) is demonstrated with several reactions. Furthermore, its potential use for bitumen separation and purification and SO2 capture/isolation are discussed, and preliminary data is presented. Next, piperylene sulfone (PS), a switchable solvent, is synthesized and fully characterized. Anionic nucleophilic substitution reactions were performed in PS, the products were isolated in high yields, and then the PS was reformed for reuse. Then, we designed an immobilized fluorous microphase system that uses F-MonoPhos to induce high enantioselectivities as a switchable heterogeneous catalyst system. Finally, stable reversible polyethyleimine-CO2 gels have been synthesized with 1-octanol. Our findings indicate that PEI-1200/octanol/CO2 gels have potential as a possible drug carrier matrix for transdermal delivery applications.

Strain engineering is used as a means of manufacturing micro- and nano- scale particles with the ability to reversibly alter their geometry from three dimensional tubes to two dimensional flat layers. These particles are formed from a bi-layer of two dissimilar materials, one of which is the elastomeric material polydimethylsiloxane (PDMS), deposited under stress on a sacrificial substrate. Upon the release of the bi-layer structure from the substrate, interfacial residual stress is released resulting in the formation of tubes or coils. These particles possess the ability to dramatically alter their geometry and, consequently, change some properties that are reversible and can be triggered by a stimulus. This work focuses on the material selection and manufacturing of the bi-layer structures used to create the responsive particles and methods for characterizing and controlling the responsive nature of the particles. Furthermore, the potential of using these particles for a capture/release application is explored, and a systematic approach to scale up the manufacturing process for such particles is provided. This includes addressing many of the problems associated with fabricating ultra-thin layers, tuning the size of the particles, understanding how the stress accumulated at the interface of a bi-layer structure can be used as a tool for triggering a response as well as developing methods (i.e. experiments and applications) that allow the demonstration of this response.

Nanoscale materials enable unique opportunities at the interface between physical and life sciences. The interface between nanoelectronic devices and biological systems makes possible communication between these two diverse systems at the length scale relevant to biological functions. The development of a bottom-up paradigm allows the nanoelectronic units to be synthesized and patterned on unconventional substrates. In this thesis, I will focus on the development of three-dimensional (3D) nanoelectronics, which mimics the structure of porous biomaterials to explore new methods for seamless integration of electronics with other materials, with a special focus on biological tissue. / Chemistry and Chemical Biology

This dissertation presents enabling technologies to fabricate thermo-responsive polymer composite based Lab-on-a-Chip (LOC) devices. LOC devices, also known as micro-total-analytical systems (microTAS) or microfluidic devices can amalgamate miniaturized laboratory functions on a single chip. This significant size reduction decreases the amount of required fluid volumes down to nano or pico-liters. The main commercial application of LOC devices is the biomedical fields. However, these devices are anticipated to make a technological revolution similar to the way miniaturization changed computers. In fact, medical and chemical analyses are predicted to shift from room-sized laboratories to hand-held portable devices. This dissertation is divided into three technologies. First, a series of terpolymer systems were synthesized and characterized to fabricate crosslinked coatings for phototunable swelling and create chemically patterned regions in order to conjugate cationic markers, proteins, or nanoparticles to the terpolymer coating. Second, antifouling surfaces were fabricated using magnetic thermo-responsive hydrogel structures via soft lithography. The structures were remote control activated with the use of AC magnetic fields. Finally, in order for LOC devices to fulfill its promise of bringing a laboratory to a hand-held device, they will have to be integrated with CMOS technology. Packaging will play a crucial role in this process. The last section will focus on the importance of coefficient of thermal expansion (CTE) mismatch in multi-chip modules. For the first technology, multi-functionalized terpolymer systems have been developed comprising of three units: N-isopropylacrylamide (NIPAAm), a stimuli responsive monomer that swells and collapses in response to temperature; methacryloxybenzophenone (MaBP), a photo-crosslinkable monomer that is activated at λ = 365 nm; and phenacyl methacrylate (PHEm), a photolabile protected functional group that generates localized free carboxyl groups in response to deprotection at λ = 254 nm. The multifunctional terpolymers can be spin-casted to form thin films of well-defined thickness, photo-crosslinked by a long UV wavelength light (λ = 365 nm) to form distinct structural patterns, and subsequently photo-chemically modified by a short UV wavelength light (λ = 254 nm). The photocleavage reaction by UV irradiation allows the production of free carboxylic groups that can be used to conjugate cationic markers, proteins, or nanoparticles to the terpolymer coating. Furthermore, the free carboxyl groups can be used to locally tune the swelling characteristics and transition temperature of the coatings. For the second technology, when Fe3O4 magnetic nanoparticles are integrated into PNIPAAm based composite systems, their resultant hyperthermia behavior becomes an ideal mechanism for remote controlled actuation. In this work, nano Fe3O4 octopods were seeded in fabricated PNIPAAm hydrogel micro-actuators. When the magnetic hydrogel structures were exposed to a magnetic field strength of 63 kA/m at a frequency of 300 kHz, the hydrogel micro-beams underwent a buckling effect when the field was absent and an unbuckling effect when the field was present. The hydrogel micro-beams were fabricated at an approximate distance from one another developing micromanipulating surfaces that were remote control activated. The response time, heating efficiency, and magnetic behavior were thoroughly studied. Lastly, micron sized polystyrene beads were exposed to the antifouling surfaces and movement of the beads was observed as the magnetic hydrogel micro-beams underwent their physical changes. For the third technology, a major reason of device failure in multi-chip module assemblies is a CTE mismatch between the underfill encapsulant material and the integrated circuit chip. Some of the failure mechanisms of microelectronic packaging due to CTE mismatch include fractures, delamination, or cracks through the device. In this section, the CTE of a commercially available underfill material is greatly reduced by loading the polymer resin material with hollow glass beads, to realize an overall effective CTE of 6.6 ppm/°C. Furthermore, the newly developed composite material exhibited outstanding thermomechanical stability at high temperatures beyond 150°C by holding a 3X lower CTE and a higher glass transition temperature.

In general, the basic concept of an intelligent material is defined as the multifunctional material that has a sensor, a processor and an actuator function in the material that allows it to maintain optimum conditions in response to environmental changes. Despite the fact that these materials have demonstrated varying degrees of success in shape and position control, active and passive control of vibration and acoustic transmission of materials subjected to dynamic loads, impact damage and creep resistance in structures and have been applied in industries from aerospace to biomechanics to civil engineering structures, very little literature is available on the subject. Thus, the objective of this dissertation is to add to the fundamental understanding of the behaviour of these special materials by investigating the possibility of a magnetostrictive SMA hybrid metalmatrix composite beam with piezoelectric actuator, to enhance the materials load attenuation and energy absorption characteristics under low velocity impact loading. The methodology employed in this investigation is driven by two primary factors. The first is the unique approach that the author puts forward to attempt to simplify the characterisation of damage in not just metal matrix composites, but in materials in general. The second factor is the lack of available literature on smart material energy absorption as well as a lack of precise theory for short fibre composites. The methodology includes an extensive literature review, the development of an analytical model, based on the new damage modulus approach, verification of the model using experimental results presented by Agag et. aI., adjustment of the model to include smart material effects and finally numerical simulation using the MATLAB® software to predict the effect of smart materials on the energy absorption capacity of the material under impact. The results show that the damage modulus (ED) is a material characteristic and can be derived from the stress strain diagram. Further, it takes into account degradation of the material through the plastic region, up to the point just before ultimate failure. Thus, ED lends itself to the simplification of many damage models in terms of a reducing sustainable load and energy absorption capacity. Only the energy consumed through material rupture remains to be characterised. The results also show that smart fibres diminish the capacity of the beam to sustain a load, but increase the displacement to failure. Thus, for a compatible substrate material, this increased displacement translates to a significant enhancement of energy absorption characteristics. The effect of prestrain on energy absorption is also considered and there appears to be a definite turning point where the dissertation thus achieves its objective in investigating the ability of smart materials to enhance the energy absorption characteristics of regular fibre reinforced metal-matrix composite materials subject to low velocity impact loading. Of equal importance to the achievement of this objective is the introduction in the dissertation of the unique damage modulus that goes to the foundation of material characterisation for mechanical engineering design and has profound implications in damage theory and future design methodologies. Significant learning has taken place in the execution of this PhD endeavour and this dissertation will no doubt contribute to other investigations in the field of smart materials. / Thesis (Ph.D.)-University of Natal,Durban,2003.

Shape memory materials have been known for many years to possess the unique ability of memorising their shape at some temperature. If these materials are pre-strained into the plastic range, they tend to recover their original un-strained shapes via phase transformation when subjected to heat stimulation. In recent years, this shape memory effect (SME) or strain recovery capability has been explored in aerospace structures for actuating the real-time movement of structural components. Among all the shape memory materials, the nickel-titanium based shape memory alloy (SMA) has by far received the most attention because of its high recovery capabilities. Since SMAs are usually drawn into the form of wires, they are particularly suitable for being integrated into fibre-reinforced composite structures. These integrated composite structures with SMA wires are thus called smart adaptive structures. To achieve the SME, these wires are normally embedded in the host composite structures. In returning to their unstrained shape upon heat application, they tend to exert internal stresses on the host composite structures in which they are embedded. This action could result in a controlled change in shape of the structural components. Although there has been a significant amount of research dedicated to characterising and modelling the SME of SMA wires, little experimental work had been done to offer an in-depth understanding of the mechanical behaviour of these smart adaptive polymeric composite structures. This project examined the deflection and shape change of carbon/epoxy and glass/epoxy cantilever beams through heating and cooling of internal nitinol SMA wires/strips. The heat damage mechanism and cyclic behaviour are major factors in the operation of such a system and need to be clearly understood in order to develop and gain confidence for the possible implementation of future smart actuating systems. Therefore, the objectives of the proposed research were to investigate (i) effect of embedding SMA, wires on mechanical properties of host composite, (ii) assessment of single-cycle and multiple-cycle actuation performance of smart beams, and (iii) thermal effects of excessive heat on the surrounding composite matrix.