Cure time is often the bottleneck of composite manufacturing processes, therefore it is important to understand the cure of today's thermosetting adhesives. This research attempts to characterize the cure rate of two commercial phenol-formaldehyde adhesives. Two methods are used, parallel-plate rheometry and dielectric spectroscopy. Viscosity data from a parallel-plate rheometer may be used to track the advance of polymerization as a function of temperature. This data can then be used to optimize press conditions and reduce production times and costs. The research will further examine resin cure through dielectric analysis; such a technique could monitor resin cure directly and in real-time press situations. Hot-pressing processes could conceivably no longer require a set press schedule; instead they would be individually set based on dielectric data for every press batch. Such a system may lead to a more efficient and uniform product because press times could be based on individual press cycles instead of entire product lines. A more likely scenario, however, is the use of in situ adhesive cure monitoring for troubleshooting or press schedule development. This research characterized the cure of two phenol-formaldehyde resins using parallel-plate rheometry, fringe-field dielectric analysis, and parallel-plate dielectric analysis. The general shape of the storage modulus vs. time curve and the gel and vitrification points in a temperature ramp were found. Both dielectric analysis techniques were able to characterize trends in the resin cure and detect points such as vitrification. The two techniques were also found to be comparable when the cure profiles of similar conditions were examined. / Master of Science

The design and synthesis of new finely tunable porous materials has spurred interest in developing novel uses in a variety of systems. Zeolites, inorganic materials with high thermal and mechanical stability, in particular, have been widely examined for use in applications such as catalysis, ion exchange and separation. A relatively new class of inorganic-organic hybrid materials known as metal-organic frameworks (MOFs) has recently surfaced, and many have exhibited their efficiency in potential applications such as ion exchange and drug delivery. A more recent development is the design and synthesis of a subclass of MOFs based on zeolite topologies (i.e. ZMOFs), which often exhibit traits of both zeolites and MOFs. Bio-compatible hydrogels already play an important role in drug delivery systems, but are often limited by stability issues. Thus, the addition of ZMOFs to hydrogel formulations is expected to enhance the hydrogel mechanical properties, and the ZMOF-hydrogel composites should present improved, symbiotic drug storage and release for delivery applications. Herein we present the novel composites of a hydrogel with a zeolite-like metal-organic framework, rho-ZMOF, using 2-hydroxyethyl methacrylate (HEMA), 2,3-dihydroxypropyl methacrylate (DHPMA), N-vinyl-2-pyrolidinone (VP) and ethylene glycol dimethacrylate (EGDMA), and the corresponding drug release. An ultraviolet (UV) polymerization method is employed to synthesize the hydrogels, VP 0, VP 15, VP 30, VP 45 and the ZMOF-VP 30 composite, by varying the VP content (mol%). The rho-ZMOF, VP 30, and ZMOF-VP 30 composite are all tested for the controlled release of procainamide (protonated, PH), an anti-arrhythmic drug, in phosphate buffer solution (PBS) using UV spectroscopy. Blister agents are chemical compounds that induce severe skin, eye, mucosal pain and irritation. The research focuses on sequestering a blister agent analog, thioanisole in hydrogels. HEMA polymers and copolymers of HEMA with 2,3-dihydroxyproyl methacrylate (DHPMA) and vinyl pyrrolidone (VP) were synthesized with crosslinkers of various dimensions. These were: ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DiEGDMA), triethylene glycol dimethacrylate (TriEGDMA), tetraethylene glycol dimethacrylate (TetEGDMA) and neopentyl glycol dimethacrylate (NPEGDMA). Equilibrium swelling was characterized gravimetrically and pore size was estimated via scanning electron microscopy (SEM). Glass transition temperatures were measured by differential scanning calorimetry (DSC). The absorption of thioanisole in methanol was characterized with via ultra-violet (UV) spectroscopy. Poly(2-hydroxyethyl methacrylate) (PHEMA) composites constructed from a paddle-wheel, a secondary building unit (SBU) for metal organic frameworks, Cu2(p-OH benzoate)4(DMSO)2*2DMSO (CPW) were also investigated for a broad analysis of dielectric spectra. The dielectric spectrum of poly(2-hydroxyethyl methacrylate) and its copolymer with Poly(2,3-dihydroxy propyl methacrylate) (PDHPMA) are already reported in the literature. This study delineates the effects on the dielectric behavior as a result of CPW addition. The dielectric permittivity and the loss factor were measured using a dielectric analyzer in the frequency range of 1 Hz to 100 k Hz and between the temperature range of -140 and 250°C. The electric modulus formalism was used to reveal the viscoelastic and conductivity relaxations present in the polymers. Significant changes were observed as CPW concentration increased from 0.1 to 0.5 wt%. It was determined through DSC that the glass transition temperature increased with the filler concentration. The secondary dielectric relaxations were also affected as it was recorded that the activation energy for the γ, Β, and conductivity relaxation increased with CPW content. AC and DC conductivity are also evaluated. The ionic conductivity data revealed that the CPW impedes the ion mobility when compared to the neat PHEMA. Organic azides have become a very vital class of chemical compounds in synthetic organic chemistry and in many more fields due to their applications. Azido compounds are considered high-energetic compounds and are studied very little due to their explosive nature. There is an urge to evaluate the thermal stability of this wide variety of compounds which have tremendous applications in synthetic as well as organic chemistry. Here in we report the thermal stability of some organic azides such as sulfonyl, phosphoryl and carbonyl azides using differential scanning calorimetry (DSC) as an evaluating tool. Initial temperature of decomposition (Ti) and temperature of maximum decomposition (Tmax) are recorded. The area under exotherm peak during decomposition is used to determine the energy of decomposition (Ed) and is compared to threshold value for hazardous/explosive compounds. The effect of substituent groups at different positions, nature of the substituent groups (electron donating or electron withdrawing) and the steric hindrance on the thermal stability of these azides is studied in detail to verify the explosive nature of these compounds.

With the emergence of Matrix Assisted Laser Desorption/Ionization-Time-of-flight as a tool for diagnosis of diseases via proteomics, there is an increasing need for greater sensitivity. Analysis of peptides by MALDI-TOF-MS is affected by sample formulation and spotting onto a MALDI target. This dissertation investigates a novel MALDI sample preparation technique, Induction Based Fluidics (IBF), for depositing precise volumes (pL to nL) of samples onto the target. We have seen that while using IBF, the induced electric field accompanying deposition enhances matrix crystallization yielding smaller crystals with more homogeneity, as compared to conventional manual micropipette (MP) depositions. An investigation of the signal-to-noise (S/N) for IBF deposition of tryptic digested Bovine Serum Albumin (BSA) showed a significant improvement in the signal-to-noise ratio for 0.5 and 0.25 pmol/µL BSA sample compared to equivalent MP depositions. The S/N enhancement for IBF and MP depositions of BSA were studied using à-cyano-4-hydroycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) matrices, and CHCA showed better results than DHB . The exciting results obtained by IBF prompted us to probe sample morphology more fully and to relate morphology to the detections level and hopefully, to increase the utility of MALDI-TOF-MS for detection of a larger range of peptides. Morphology results were correlated to sensitivity limits using both dispensing techniques. Because of dissimilar rates of evaporation, different or uneven deposition thickness, or crystal lattice morphology, discontinuous crystallization patterns were observed for MP depositions. However, IBF deposited samples occupied less planar area with uniform distribution of crystals, thereby reducing sample crystal heterogeneity and laborious hunt for a "sweet" or "hot" spot to produce high quality spectra. The application of IBF was extended to the tryptic digested BSA protein using peptide mass fingerprinting. IBF deposition resulted in a larger number of detectable peptides as well as higher sequence coverage as compared to equivalent MP depositions. In last few decades, advanced research and potential applications in the field of microelectronics have spurred interest in the development of reticulated doped polymer films. Bis (ethylenedioxy) tetrathiafulvalene (BEDO-TTF)/Polycarbonate (PC) films were synthesized and characterized for use in hand-held real time explosives sensors, capable of detecting nitro-based compounds (nitroaromatics, nitoamines and nitroesters), which are the main components of Improvised Explosive Devices or IEDs. Reticulated doped polymer films were prepared by exposing solid solutions of BEDO-TTF in PC to iodine to form conductive charge transfer complexes. The resulting films exhibited room temperature conductivities ranging from 6.33-90.4*10-5 S cm-1. The colored iodine complexes in the film were reduced by cyclic voltammetry yielding conductive, colorless, transparent films. Dielectric analysis (DEA) was used to probe relaxations in neat PC and BEDO-TTF/PC showed that BEDO-TTF plasticized the PC and decreased the glass transition temperature. Two secondary relaxations appeared in PC films, whereas the transitions merged in the doped film. DEA also revealed conductivity relaxations above 180°C, which were characterized by the electric modulus formalism and showed that BEDO-TTF increased the alternating current, (AC) conductivity in PC.

ABSRACT: This research focuses on two hydrophilic polymers that form hydrogels when they sorb water: Poly(2-hydroxyethyl methacrylate) (PHEMA) and Poly(2,3-dihydroxypropyl methacrylate) (PDHPMA). Present work in the field obviated the need to properly characterize the thermal and dielectric properties of these materials.The dielectric permittivity, e', and the loss factor, e", of dry poly(2-hydroxyethyl methacrylate) and poly(2,3-dihydroxypropyl methacrylate) were measured using a dielectric analyzer in the frequency range of 0.1Hz to 100 kHz and between the temperature range of -150 °C to 275°C. The dielectric response of the sub-Tg gamma transition of PHEMA has been widely studied before but little to no DEA data above 50°C is present in the literature. This study is the first to present the full range dielectric spectrum of PHEMA, PDHPMA and their random copolymers up to and above the glass transition region. The electric modulus formalism and several mathematical proofs were used to reveal the gamma, beta, alpha and conductivity relaxations. Dielectric analysis gives insight into the network structure of the polymer; it has been shown through thermal analyses that as the DHPMA content increased in HEMA-DHPMA copolymers the polymer matrix increased in available free volume and facilitated the movement of ions in its matrix. This is of significance as we then investigated the feasibility of using PHEMA, PDHPMA and their random copolymers as materials for a biocompatible coating for an implantable glucose sensor. The biocompatibility of hydrogels can be attributed to the low interfacial tension with biological fluids, high gas permeability, high diffusion of low molecular weight compounds, and reduced mechanical and frictional irritation to surrounding tissue. Once the biocompatibility of the hydrogels was established, the task to coat the polyurethane (PU)/epoxy coated metal glucose sensor was addressed. Plasma polymerization was found to be the most feasible technique for the application of the biocompatible hydrogel as a coating on the implantable glucose sensor. It has also been shown that thermal analysis techniques provide a mode of investigation that can be used to investigate the interfacial interactions of a novel hydroxylated, self-assembled nanoparticle with two functionally different polymers, poly(2-dihydroxyethyl methacrylate) and poly(methyl methacrylate).

The interpretation and modelling of the dielectric response of thermosetting materials during cure was the main focus of this study. The equivalence of complex permittivity and complex impedance in terms of information content was outlined in a series of case studies covering the separate effects of dipolar movements and charge migration as well as the combined effect of the two polarisation mechanisms. Equivalent electrical circuits were used in order to model the evolution of the complex impedance during cure. A numerical method that can model consecutive spectra throughout the cure was developed. The method is based on Genetic Algorithms and requires only input from the modelling of the initial spectra. Complex impedance spectra were collected during the cure of a commercial epoxy resin formulation under isothermal and dynamic heating conditions. The spectra were analysed and modelled. The modelling was successful over the whole frequency range of the measurements (1 Hz – 1 MHz). The analysis of the estimated model parameters showed that charge migration dominates the dielectric response in a wide frequency range. In addition, the modelling algorithm also distinguished between the effects of electrode polarisation and dipolar movements in the signal. A new equivalent circuit was used in order to map the frequency regions where the each one of the three phenomena that together comprise the dielectric signal can be monitored most effectively. A chemical cure kinetics model was developed for the studied system. A correlation between the maximum point of the imaginary impedance spectrum and the reaction conversion was established. A mathematical model, based on a simple linear dependence of the dielectric signal on conversion and temperature, was built. The model predictions agreed well with the experimental data. The aim of simplifying the interpretation of the dielectric signals led to the development of a new experimental technique. Temperature Modulated Dielectric Analysis employs temperature modulations superimposed on an underlying thermal profile in order to separate the influence on the signal of the temperature alone from that of the cure reaction. The early study carried out here shows that such measurements are feasible and reveals important issues for its further development.

The design, fabrication, and characterization of polymer-carbon nanotube (CNT) composites have generated a significant amount of attention in the fields of materials science and polymer chemistry. The challenge in fabricating composites that exploit the unique properties of the CNT and the ideal processing ability and low cost of the polymer is in achieving a uniform dispersion of the filler in the polymer matrix. This body of work focuses on (1) techniques employed to disperse CNTs into a polymer matrix and (2) the effects of CNTs on the mechanical and electrical properties of the polymer. Poly (methyl methacrylate) (PMMA), an amorphous polymer, and poly (4-methyl-1-pentene) (P4M1P), a semi crystalline polymer, were chosen as the matrices. Non-functionalized single-walled carbon nanotubes and soot (unpurified carbon nanotubes) were chosen as the filler material. In the first study, single-walled carbon nanotubes (SWNTs) were sonicated in methyl methacrylate monomer and initiated via thermal energy, UV light, and gamma radiation. Composite films with increased dielectric constants and unique optical transparency were produced. Samples were characterized using differential scanning calorimetry, dielectric analysis, and dynamic mechanical analysis. Refractive Indices were obtained and correlated to the dielectric constant using Maxwells relationship. PMMA/soot composites were fabricated in the second study. Dispersion was accomplished by way of sonication and melt compounding. The PMMA/soot composites were exposed to gamma radiation, with a 137Cs gamma source, in order to investigate how the filler affects the polymers ability to resist radiation. Samples were characterized by differential scanning calorimetry, dielectric analysis, and dynamic mechanical.

Matrix Assisted Laser Desorption Ionization–Time of Flight (MALDI-TOF) mass spectroscopy is used in the characterization of synthetic polymers. MALDI allows for determination of: modal, most probable peak (M P), molecular number average (MN), molecular weight average (MW), polydispersity (PD), and polymer spread (PSP). We evaluate a new sample preparation method using Induction Based Fluidics (IBF) to kinetically launch and direct nanoliter volumes to a target without contact. IBF offers signal improvement via field enhanced crystallization. This is the first study to discuss filed enhanced crystallization in MALDI sample preparation. IBF can increase signal/noise (S/N) and signal intensity for polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(ethylene glycol) (PEG) across a mass range of 2,500 to 92,000 Da showing more accurate PSP. Increases in S/N range up to: 279% for PS, 140% for PMMA, and 660% for PEG. Signal intensities increased up to: 438% for PS, 115% for PMMA, and 166% for PEG. Cross-polarization microscopy indicates dramatic morphology differences between IBF and micropipette. Finally, we speculate as to why IBF nanoliter depositions afford higher S/N values in experiments conducted in different instrumental configurations even without optimization. Next we sought to investigate whether nanoliter volumes of concentrated polar liquids and organic monomers launched to targets using IBF can be verified through the real time charge measurements. We show that using a nanoliter IBF dispensing device and nanocoulomb meter, charge measurements made on nanoliter drops in real time are correlated with the droplets surface area following Gauss’s Law. We infer the "induction only" formation of the double layer showing the ability to determine nanoliter volumes, nearly instantaneously, in real time. Implications are presented from these IBF measurement observations on improving/monitoring MALDI quantitation and its quality control. Polymer-dye interactions were further investigated using PMMA composites made from a polar metalloporphyrin [5-(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)-10,20-diphenylporphyrinato]zinc(II) (Zn(II)Bpin-DPP) in select weight %s (wt%s). Fluorescence spectroscopy has revealed that the porphyrin was well dispersed within the composite. Differential Scanning Calorimetry (DSC) showed that porphyrin acted as an antiplasticizer raising the glass transition (Tg) from 105 °C to 123 °C. Dielectric Analysis (DEA) was performed in the frequency range of 0.3 Hz to 100 kHz between -150 to 270 ⁰C. Permittivity (ε’), loss factor (ε’’) and dielectric response of beta (β), alpha beta (αβ), and conductivity relaxations were studied. Previous DEA data was limited to 190 ⁰C. This study brings analysis to 270 ⁰C which is start point for the first part of PMMA degradation. Thus forwarding DEA can be used to evaluate PMMA degradation. The electric modulus formalism is used to reveal the β and conductivity relaxations. The apparent activation energies (Ea) for the molecular relaxations are presented. AC (ζAC) and DC (ζDC) conductivity are also evaluated. Tan delta (δ), dissipation factor, evaluated between 1 Hz to 100 kHz was shown to increase with porphyrin loading although locally affected by free volume restriction. Havriliak-Negami (H-N) equation was fit using the complex electric modulus (M*) modified form and was performed on the conductivity region 160 to 190 ⁰C and degradation region 190 to 270 °C. Relaxations above the Tg were proven to be conductivity relaxations using four proofs. This is the first study to investigate PMMA degradation DEA with the complex electric modulus, M*, revealing a unique occurrence of increasing central relaxation times (s-1) and reducing electric loss modulus (M") frequency maxima (Hz) after the degradation temperature of 220 ⁰C was reached supporting current literature of the first of a two part degradation process that proceeds via end chain scission.

No description available.

Polymer composites containing nanosized fillers have generated explosive interest since the early 1980's. Many recent studies have been conducted incorporating nano-fillers into polymer matrices to design and synthesize materials with tunable mechanical, thermal, and optical properties. Conventional filled polymers, where the reinforcement is on the order of microns, have been replaced by composites with discrete nanosized fillers. Gradually, theories that predicted that composite properties are independent of particle size in the micron range were challenged by nanocomposites. Rather, nanocomposite properties are greatly influenced by the surface area of the. All of this is complicated by the fact that nanoparticles are inclined to aggregate or migrate to interfaces. Much effort has been devoted to optimize dispersion of nanofillers in the polymer matrices, as polymer-nanoparticle interactions and adhesion greatly influence performance of the material. A well- dispersed composite system with various noncovalent interactions such as those that arise from hydrogen bonding, electrostatic attractions and π-π interactions between the filler and the matrix, can transfer stress and the interface will stop the development of cracks and impede stress concentrations. Overall, large reinforcement increases are noted at low nanoparticle loadings. Additionally, functional properties such as thermal, electrical conductivity and porosity can be tailored for specific applications. The design of high performance composites requires optimizing dispersion, nanoparticle-polymer noncovalent interactions and the chemistry of the materials. Therefore polymer composites with different types of nanofillers were investigated to prove various noncovalent interaction and to improve the mechanical, thermal and electrical properties in this study. Poly (methyl methacrylate) (PMMA) with BaTiO3 and Bi2O3 composites were fabricated by two different methods; sonication of fillers in PMMA and in situ polymerization. Samples were irradiated in air via a JL Shepherd Mark I cesium-137 source. The dose rate was 985 rads/min and the total dose was 2.0 Mrad. The polymer sonication (PSON) method has a greater effect than in situ polymerization on sample uniformity. With the PSON method there was a slight improvement in rad hardness in the barium titanate composites. This is the case with and without MWNTs and coupling agents. The storage modulus and loss modulus were measured via Dynamic Mechanical Analyzer (DMA) under the tension film mode using a heating rate of 5 °C min-1 from -150 °C to 200 °C and a scanning frequency range of 1-100 Hz. Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. An aliphatic isocyanate, polyether, polyol thermoplastic polyurethane, Tecoflex® SG-85A, was solution processed with the varying amounts of silica nanowire. A new grade polyurethane, Tecoflex®, was synthesized from the aliphatic 4,4-methylene dicyclohexyl diisocyanate (H12MDI) with polytetramethylene ether glycol. Despite Tecoflex®'s longevity and wide use, this polymer's dielectric behavior has not been widely studied. Therefore, the dielectric response of neat PU, Tecoflex®, and PU composites with silica nanowire from -150 to 150 °C is presented. The mechanism of nanowire growing with diameters ranging from 50 to 500 nm has been established to follow the vapour liquid solid (VLS) model via the PtSi phase acting as the catalyst. Our previous thermal stability study of PU nanowire composites have yielded increased heat stability to 330 °C. In comparison, neat PU only maintains thermal stability in temperatures that range to 250 °C. The onset of decomposition temperature was measured by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. A series of PMMA-dodecyloxy NB and PHEMA-dodecyloxy NB composites were synthesized in situ and characterized. The dodecyl groups significantly alter the solubility of the nanoballs, imparting hydrophobicity to the surface of the nanoball. A comparison study was made between the PMMA-NB and PHEMA-NB nanocomposites. Structure property relations are discussed in terms of interactions between the polymer matrices and nanoball surfaces and interiors. These OC12 NB and the hydroxyl NB polymer composites are the first studies to date that probe relaxations and conductivity in discrete polyhedral metal-organic polymer composites. A novel ultra-flexible polycarbonate-polyurethane (PCPU) was synthesized with methylene bis(4-cyclohexylisocyanate), 1,4 butanediol as a chain extender and a polycarbonate polyol containing 1,6-hexanediol and 3-methyl-1,5-pentanediol. Through the techniques of water coagulation, the synthesis of self-healing PCPU with various concentrations of SWNT (Single-Walled Nanotubes) is possible. The resulting features of this synthesized rubber-like substance are to be evaluated to determine glass transition temperature. This novel type of polyurethane material targets growing markets for biocompatible polymers. Also, a secondary goal of this project is to obtain information useful to determining whether PCPU-carbon nanotube composites would be good candidates for use as a gel electrolyte in polymer batteries. All nanocomposites were characterized by differential scanning calorimetry (DSC) to determine glass transition temperatures. The dielectric permittivity (ε’) and loss factor (ε”) were also measured via Dielectric Analysis (DEA) in the frequency range 1Hz to 100 kHz and between the proper temperatures in all polymer composite. The electric modulus formalism was used to reveal structural relaxations including conductivity relaxation. The activation energies for the relaxations are presented.