Sustainability through replacement of non-renewable fibers with renewable fibers is an ecological need. Impact of transportation costs from South-east Asia on the life cycle analysis of the composite is detrimental. Kenaf is an easily grown crop in America. Farm based processing involves placing the harvested crop in rivers and ponds, where retting of the fibers from the plant (separation into fibers) can take 2 weeks or more. The objective of this thesis is to analyze industrially viable processes for generating fibers and examine their synergistic impact on mechanical performance, surface topography and chemistry for functional composites. Comparison has been made with commercial and conventional retting process, including alkali retting, enzymatic retting, retting in river and pond water (retting occurs by natural microbial population) with controlled microbial retting. The resulting kenaf fibers were characterized by dynamic mechanical analysis (DMA), Raman spectroscopy (FT-Raman), Fourier transform infrared spectroscopy (FT-IR), polarized optical microscopy (POM), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM) optical fluorescence microscopy, atomic force microscopy (AFM) and carbohydrate analysis. DMA results showed that pectinase and microbe treated fibers have superior viscoelastic properties compared to alkali retting. XPS, Raman, FT-IR and biochemical analysis indicated that the controlled microbial and pectinase retting was …

Mechanics of bone is widely studied and researched, mainly for the study of fracture. This has been done mostly on a macro scale. In this work hierarchical nature of bone has been explored to investigate bone mechanics in more detail. Flexural test were done to classify the bones according to their strength and deflection. Raman spectroscopy analysis was done to map the mineralization, collagen crosslinking changes across the thickness of the bone. Nanoindentation was done to map indentation hardness and indentation modulus across femoral cortex of the bone. The results indicate that the composition of the bone changes across the thickness of the femoral cortex. The hypothesis is confirmed as increase in mineralization, carbonate to phosphate ratio and collagen crosslinking shows the effect as increased indentation hardness and modulus and decreased deflection.

Novel net shaping technique Laser Engineered Net shaping™ (LENS) laser based manufacturing solution (Sandia Corp., Albuquerque, NM); Laser can be used to deposit orthopedic implant alloys. Ti-35Nb-7Zr-5Ta (TNZT) alloy system was deposited using LENS. The corrosion resistance being an important prerequisite was tested electrochemically and was found that the LENS deposited TNZT was better than conventionally used Ti-6Al-4V in 0.1N HCl and a simulated body solution. A detailed analysis of the corrosion product exhibited the presence of complex oxides which are responsible for the excellent corrosion resistance. In addition, the in vitro tests done on LENS deposited TNZT showed that they have excellent biocompatibility. In order to improve the wear resistance of the TNZT system boride reinforcements were carried out in the matrix using LENS processing. The tribological response of the metal matrix composites was studied under different conditions and compared with Ti-6Al-4V. Usage of Si3N4 balls as a counterpart in the wear studies showed that there is boride pullout resulting in third body abrasive wear with higher coefficient of friction (COF). Using 440C stainless steel balls drastically improved the COF of as deposited TNZT+2B and seemed to eliminate the effect of “three body abrasive wear,” and also exhibited superior …

While amorphous phases have been reported in immiscible alloy systems, there is still some controversy regarding the reason for the stabilization of these unusual amorphous phases. Direct evidence of nanoscale phase separation within the amorphous phase forming in immiscible Cu-Nb alloy thin films using 3D atom probe tomography has been presented. This evidence clearly indicates that the nanoscale phase separation is responsible for the stabilization of the amorphous phase in such immiscible systems since it substantially reduces the free energy of the undercooled liquid (or amorphous) phase, below that of the competing supersaturated crystalline phases. The devitrification of the immiscible Cu-Nb thin film of composition Cu-45% Nb has been studied in detail with the discussion on the mechanism of phase transformation. The initial phase separation in the amorphous condition seems to play a vital role in the crystallization of the thin film. Detailed analysis has been done using X-ray diffraction, transmission electron microscopy and 3D atom probe tomography.

Many industries including the medical, aerospace, and automobile industries have increasingly adopted the use of shape memory alloys (SMAs) for a plethora of applications due to their unique thermomechanical properties. From the commercially available SMAs in the market, binary NiTi SMAs have shown the most desirable properties. However, SMA properties can be significantly affected by the fabrication process. One of the most familiar applications of NiTi SMAs is in the design of actuating devices where the shape memory effect properties are highly advantageous. Spring NiTi SMA actuators are among the most commonly used and are generally made by torsion loading a straight wire. Consequently, stress concentrations are formed causing a reduction in recovery force. Other methods for producing springs and other NiTi SMA components is the fast emerging manufacturing method of additive manufacturing (AM). AM often uses metal powders to produce the near-net shape components. A major challenge for SMAs, in particular, is their well-known composition sensitivity. Therefore, it is critical to control composition in NiTi SMAs. In this thesis, a novel method for processing NiTi SMAs for pre-alloyed NiTi SMA powders and springs is presented. A low pressure and low temperature hydriding-pulverization-dehydriding method is used for preparing the pre-alloyed …

Polymeric coatings are being used in a growing number of applications, contributing to protection against weather conditions and localized corrosion, reducing the friction and erosion wear on the substrate. In this study, various polypropylene (PP) coatings were applied onto steel substrates by compression molding. Chemical modification of PP has been performed to increase its adhesion to metallic surfaces by grafting of maleic anhydride (MAH) onto PP in the presence of dicumyl peroxide (DCP). Influence of different concentrations of MAH and DCP on the properties of resulting materials have been examined. The coated steel samples are characterized by scanning electron microscopy (SEM), shear adhesion testing, FTIR and tribometry. The coatings with 3 wt. % MAH have shown the maximum adhesion strength due to maximum amount of grafting. The wear rates increased with increasing the amount of MAH due to simultaneous increase in un-reacted MAH.

Methylsilsesquioxane (MSQ) and organosilicate glass (OSG) are the materials under this study because they exhibit the dielectric constant values necessary for future IC technology requirements. Obtaining a low-k dielectric value is critical for the IC industry in order to cope time delay and cross talking issues. These materials exhibit attractive dielectric value, but there are problems replacing conventional SiO2, because of their chemical, mechanical and electrical instability after plasma processing. Several techniques have been suggested to mitigate process damage but supercritical silylation offers a rapid single repair step solution to this problem. Different ash and etch damaged samples were employed in this study to optimize an effective method to repair the low-k dielectric material and seal the surface pores via supercritical fluid processing with various trialkylchlorosilanes. Fourier transform infrared spectroscopy (FTIR), contact angle, capacitance- voltage measurements, and x-ray photoemission spectroscopy, dynamic secondary ion mass spectroscopy (DSIMS), characterized the films. The hydrophobicity and dielectric constant after exposure to elevated temperatures and ambient conditions were monitored and shown to be stable. The samples were treated with a series of silylating agents of the form R3-Si-Cl where R is an alkyl groups (e.g. ethyl, propyl, isopropyl). Reactivity with the surface hydroxyls was inversely …

One of the final steps in fabricating microelectromechanical devices often involves a liquid etch release process. Capillary forces during the liquid evaporation stage after the wet etch process can pull two surfaces together resulting in adhesion of suspended microstructures to the supporting substrate. This release related adhesion can greatly reduce yields. In this report, a wet etch release method that uses polystyrene microspheres in the final rinse liquid is investigated. The polystyrene microspheres act as physical barriers between the substrate and suspended microstructures during the final liquid evaporation phase. A plasma ashing process is utilized to completely remove the polystyrene microspheres from the microstructure surfaces. Using this process, release yields > 90% were achieved. It is found that the surface roughness of gold surfaces increases while that of the silicon is reduced due to a thin oxide that grows on the silicon surface during the plasma process.

Polystyrene (PS) nanocomposite foams were prepared using supercritical fluid (SCF) CO2 as a solvent and blowing agent. PS was first in-situ polymerized with a range of concentrations of montmorillonite layered silicate (MLS). The polymerized samples were then compression molded into 1 to 2mm thick laminates. The laminates were foamed in a batch supercritical CO2 process at various temperatures and pressures from 60°-85°C and 7.6-12MPa. The resulting foams were analyzed by scanning electron microscopy to determine effect of MLS on cellular morphology. Differential scanning calorimetry was used to determine the impact of nanocomposite microstructure on glass transition of the foamed polymer. X-ray diffraction spectra suggested that the PS/MLS composite had an intercalated structure at both the 1% and 3% mixtures, and that the intercalation may be enhanced by the foaming process.

Single wall carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were dispersed in mineral oil and epoxy resin. The magnetorheological properties of these dispersions were studied using a parallel plate rheometer. Strain sweeps, frequency sweeps, magneto sweeps and steady shear tests were conducted in various magnetic fields. G', G", h* and ty increased with increasing magnetic field, which was partially attributed to the increasing degree of the alignment of nanotubes in a stronger magnetic field. The SWNT/mo dispersions exhibited more pronounced magnetic field dependence than SWNT/ep and MWNT/mo counterparts due to their much lower viscosity. The alignment of SWNTs in mineral oil increased with rising nanotube concentration up to 2.5vol% but were significantly restricted at 6.41vol% due to nanotube flocculation.

The thesis studied quantized conductance in nanocontacts formed between two thin gold wires with one of the wires coated by alkainthiol self assembly monolayers (SAM), by using the cross-wire junction. Using the Lorenz force as the driving force, we can bring the two wires in contact in a controlled manner. We observed conductance with steps of 2e2 / h. The conductance plateaus last several seconds. The stability of the junction is attributed to the fact that the coating of SAM improves the stability and capability of the formed contact.

This study deals with crystal orientation effect along with the effects of microstructure on the pile-ups which affect the nanoindentation measurements. Two metal classes, face centered cubic (FCC) and body centered cubic (BCC, are dealt with in the present study. The objective of this study was to find out the degree of inaccuracy induced in nanoindentation measurements by the inherent pile-ups and sink-ins. Also, it was the intention to find out how the formation of pile-ups is dependant upon the crystal structure and orientation of the plane of indentation. Nanoindentation, Nanovision, scanning electron microscopy, electron dispersive spectroscopy and electron backscattered diffraction techniques were used to determine the sample composition and crystal orientation. Surface topographical features like indentation pile-ups and sink-ins were measured and the effect of crystal orientation on them was studied. The results show that pile-up formation is not a random phenomenon, but is quite characteristic of the material. It depends on the type of stress imposed by a specific indenter, the depth of penetration, the microstructure and orientation of the plane of indentation. Pile-ups are formed along specific directions on a plane and this formation as well as the pile-up height and the contact radii with the indenter …

The effect of incorporation two clays; layered double hydroxides (LDH) and montmorillonite layered silicates (MLS) in linear low density polyethylene (PE) matrix was investigated. MLS and LDH were added of 5, 15, 30 and 60 weight percent in the PE and compounded using a Brabender. Ground pellets were subsequently compression molded. Dispersion of the clays was analyzed using optical microscopy, SEM and XRD. Both the layered clays were immiscible with the PE matrix and agglomerates formed with increased clay concentration. The thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Both clays served as nucleation enhancers increasing recrystallization temperatures in the composites. Flame retarding properties were determined by using the flammability HVUL-94 system. LDH indicated better flame retarding properties than MLS for PE. The char structure was analyzed by environmental scanning electron microscopy. Mechanical properties were studied by tensile testing and Vickers microhardness testing apparatus.

This work focused on laser powder bed fusion (LPBF) of H13 tool steel to examine microstructure and melt pool morphology. Experiments were conducted with varying laser power (P) in the range of 90-180 W and scan speed (v) in the range of 500-1000 mm/s. layer thickness (l) and hatch spacing (h) were kept constant. Volumetric energy density (γ) was calculated using the above process parameters. In order to find a relation between the recorded density and top surface roughness with changing process parameters, set of equations were derived using the non-dimensional analysis. For any chosen values of laser power, scan speed, hatch spacing and layer thickness, these equations help to predict top surface roughness and density of LPBF processed H13 tool steel. To confirm the universal relation for these equations, data of In718 and SS316L processed in LPBF was input which gave a R-square of >94% for top surface roughness and >99% for density. A closed box approach, response surface model, was also used to predict the density and surface roughness which allows only in the parametric range. Material microstructures were examined to identify the melting modes such as keyhole, transition and conduction modes. X-ray diffraction data revealed that there …

In recent years, advancements in additive manufacturing (AM) technologies have paved the way for 3D-printed flexible hybrid electronics (FHE) and created opportunities for extending these gains to RF applications. However, printed metal interconnects and devices are typically characterized by high porosity and chemical impurities that significantly limit their electrical conductivity and RF performance compared to bulk equivalents. Using direct ink writing (DIW), two silver inks, a nanoflake suspension and a nanoparticle-reactive ink, were investigated to understand the relationship between free interfacial energy, sintering behavior, DC conductivity, and RF loss. The printed silver samples were characterized using scanning electron microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy to monitor microstructural evolution, grain size and orientation, and chemical purity as a function of heat treatment temperature. Three heat treatments were applied to each ink: the manufacturer's recommendation, 225°C for 30 minutes, and 350°C for 30 minutes. Four-wire structures and coplanar waveguides were printed to compare the DC and RF performance up to 18 GHz, respectively. The results show that ink formulations that facilitate larger grains, high density, and good chemical purity have superior RF performance. A low resistivity of 1.4 times bulk Ag, average of 0.8% greater RF loss factor than evaporated Ag, …

Switchable adhesives using stimuli-responsive systems have many applications, including transfer printing, climbing robots, and gripping in pick and place processes. Among these adhesives, electroadhesive surface can spontaneously adjust their adhesion in response to an external electric field. However, electroadhesives usually need high voltage (e.g. kV) and the adhesion disappears upon turning off the signal. These limitations make them complicated and costly. In this research, we demonstrated a gold-coated silica microsphere (GCSM) with highly switchable and memorable adhesion triggered by a relatively small voltage (<30 V). In the experiment, a silica microsphere with a diameter of 15 μm was glued to a tipless atomic force microscope (AFM) cantilever. The nanoscale thick gold coating was sprayed on the surface of the microsphere by a sputter coater. AFM was used to explore the tunable adhesion with an external voltage at different relative humidity (RH). The results revealed that when applying a positive electrical bias at high RH, the adhesive force increased dramatically while it decreased to almost zero after applying a negative potential. Even if the bias was turned off, the adhesive force state could still be kept and erased on demand by simply applying a negative voltage. The adhesive force can be …

Recent progress in layered transition metal dichalcogenides (TMDs) has led to various promising electronic and optoelectronic applications. However, the structure of materials plays a critical role in electronic and optoelectronic devices, and determines performance. Electronic and optoelectronic devices typically consist of multiple layers that form electrical homojunctions or heterojunctions. Therefore, in a device it can be expected that a WS2 layer may serve as the substrate for a subsequent layer in a multilayer device stack and determine how the layer grows. In transistor structures, roughness at the channel/gate dielectric interface introduces field variations and charge scattering. Therefore, understanding the relations between processing, surface morphology and properties is important. In this project, the effects of pulsed laser deposition (PLD) processing conditions on the surface morphology of few layered WS2 films were studied. WS2 films were synthesized under processing conditions that represent the extremes of surface supersaturation and kinetic energy transfer from the flux to the growing films, and evolution of the surface morphology was studied. The specific conditions were 1Hz/50mJ, 10Hz/50mJ, 1Hz/300mJ, and 10Hz/300mJ respectively. Combining AFM, XRD and Raman analyses, it was determined that deposition at 10Hz/300mJ, provided the best structural properties and surface morphology. Growth appeared to be 3D-cluster, …

Shape memory alloys (SMAs) operating as solid-state actuators pose economic and environmental benefits to the aerospace industry due to their lightweight, compact design, which provides potential for reducing fuel emissions and overall operating cost in aeronautical equipment. Despite wide applicability, the implementation of SMA technology into aerospace-related actuator applications is hindered by harsh environmental conditions, which necessitate extremely high or low transformation temperatures. The versatility of the NiTi-based SMA system shows potential for meeting these demanding material constraints, since transformation temperatures in NiTi can be significantly raised or lowered with ternary alloying elements and/or Ni:Ti ratio adjustments. In this thesis, the expansive transformation capabilities of the NiTi-based SMA system are demonstrated with a low and high-temperature NiTi-based SMA; each encompassing different stages of the SMA development process. First, exploratory work on the NiTiSn SMA system is presented. The viability of NiTiSn alloys as low-temperature SMAs (LTSMAs) was investigated over the course of five alloy heats. The site preference of Sn in near-equiatomic NiTi was examined along with the effects of solution annealing, Ni:Ti ratio adjustments, and precipitation strengthening on the thermomechanical properties of NiTiSn LTSMAs. Second, the thermomechanical processability of NiTiHf high-temperature SMA (HTSMA) wires is presented. The evolution of …

An in-depth study of Al2W3O12 negative thermal expansion (NTE) ceramic was performed, focused on synthesis, phase mappings, and the underlying mechanisms shown to be responsible for NTE. Review of the literature has shown inconsistencies in reported values of the dilatometry measured coefficients of thermal expansion, and the temperature for the known monoclinic to orthorhombic phase transition. Two synthesis techniques are introduced: an ionic-liquid non-hydrolytic sol-gel synthesis route; and a low temperature solid state reaction synthesis for Al2W3O12. X-ray diffraction, Raman spectroscopy, and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) were used to verify the techniques. Two differential scanning calorimetry (DSC) experiments (high and low temperature) were performed on the material showing the transition between -5 and -20 °C and no other phase changes until a reported degradation above 1100 °C. Extensive dilatometry on the material led to the discovery of elastic transitions occurring in the polycrystalline sample capable of explaining the inconsistencies in reported dilatometry results. This is further developed into a proposed model defining the regions between these transitions. Each region has a different thermal expansion as well as a direct effect on the reaction of the material upon cooling. This proposed model may allow more consistent reporting of …

The method of optical emission spectroscopy has been used with Fe-Ni and other complex alloys to investigate in-situ compositional control for additive manufacturing. Although additive manufacturing of metallic alloys is an emerging technology, compositional control will be a challenge that needs to be addressed for a multitude of industries going forward for next-gen applications. This current scope of work includes analysis of ionized species generated from laser and metal powder interaction that is inherent to the laser engineered net shaping (LENS) process of additive manufacturing. By quantifying the amount of a given element's presence in the electromagnetic (EM) spectrum, this amount can be compared to the actual amount present in the sample via post-processing and elemental dispersive x-ray (EDX) data analysis. For this work a commercially available linear silicon CCD camera captured metallic ion peaks found within the ultraviolet (UV) region to avoid background contamination from blackbody radiation. Although the additive manufacturing environment can prove difficult to measure in-situ due to time dependent phenomena, extreme temperatures, and defect generation, OEM was able to capture multiple data points over a time series that showed a positive correlation between an element's peak intensity and the amount of that element found in the …

Piezoelectricity in two-dimensional (2D) transition metal dichalcogenides (TMDs) has attracted significant attention due to their unique crystal structure and the lack of inversion centers when the bulk TMDs thin down to monolayer. Although the piezoelectricity effect in atomic-thickness TMDs has been demonstrated, they are not scalable. Herein, we demonstrate a piezoelectric effect from large-scale, sputtered MoS2 and WS2 using a robust defect-engineering based on the thermal-solvent annealing and solvent immersion process. This yields a higher piezoelectric output over 20 times after annealing or solvent immersion. Indeed, the piezoelectric responses are strengthened with the increases of defect density. Moreover, the MoS2 or WS2 piezoelectric device array shows an exceptional piezoelectric sensitivity with a high-level uniformity and excellent environmental stability under ambient conditions. A detailed study of the sulfur vacancy-dependent property and its resultant asymmetric structure-induced piezoelectricity is reported. The proposed approach is scalable and can produce advanced materials for flexible piezoelectric devices to be used in emerging bioinspired robotics and biomedical applications.

Chiral nematic liquid crystals or cholesteric liquid crystals (CLC) can be obtained by adding a chiral dopant into a nematic liquid crystal. Liquid crystal molecules spontaneously rotate along a long axis to form helical structures in CLC system. Both pitch size and orientation of the helical structure is determined by the boundary conditions and can be further tuned by external stimuli. Particularly, the uniform lying helical structure of CLC has attracted intensive attention due to its beam steering and diffraction abilities. Up to now, studies have worked on controlling the in-plane orientation of lying helix through surface rubbing and external stimuli. However, it remains challenging to achieve steady and uniform lying helical structure due to its higher energy, comparing with other helical configurations. Here, by varying the surface anchoring, uniform lying helical structure with long-range order is achieved as thermodynamically stable state without external support. Poly (6-(4-methoxy-azobenzene-4'-oxy) hexyl methacrylate) (PMMAZO), a liquid crystalline polymer, is deposited onto the silicon substrate to fine-tune the surface anchoring. By changing the grafting density of PMMAZO, both pitch size and orientation of lying helical structure are precisely controlled. As the grafting density increases, the enhanced titled deformation of helical structure suppresses the pitch size …

The aim of this study was to understand the processing – structure – property relationships in spark plasma sintered (SPS) boron carbide (B4C) and B4C-titanium diboride (TiB2) ceramic composites. SPS allowed for consolidation of both B4C and B4C-TiB2 composites without sintering additives, residual phases, e.g., graphite, and excessive grain growth due to long sintering times. A selection of composite compositions in 20% TiB2 feedstock powder increments from 0% to 100%, was sintered at 1900°C for 25 minutes hold time. A homogeneous B4C-TiB2 composite microstructure was determined with excellent distribution of TiB2 phase, while achieving ~99.5% theoretical density. An optimum B4C-23 vol.% TiB2 composite composition with low density of ~3.0 g/cm3 was determined that exhibited ~30-35% increase in hardness, fracture toughness, and flexural bend strength compared to commercial armor-grade B4C. This is a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B4C matrix in compression and TiB2 phase in tension, and c) TiB2 phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB2 serves as a strengthening and toughening agent, and SPS shows promise for the manufacture of hybrid ceramic …

Poly(vinyl chloride)(PVC) wire and cable insulation has poor thermal stability, causing the plasticizer to separate from the PVC chain and produce an oily residue, lowering the tensile elongation at break and thus increasing brittleness. We have added 4 wt.% of three different types of cross-linking agents and antioxidants, as well as mixtures of both, to improve the thermal stability of the plasticizer and tensile properties of PVC after thermal exposure. We performed tensile tests, tribological tests, profilometry, scanning electron microscopy(SEM) and water absorption determination before and after thermal exposure at 136 ℃ for 1 week. After adding the agents, elongation at break increased by 10 to 20 % while the wear rate and water absorption were lower than for the control sample. Less voids are seen in the SEM images after adding these two kinds of agents. The thermal resistance of the PVC cable insulation is best enhanced by combinations of cross-linking agents and antioxidants.