The impetus for this study was the noise generated by an automotive stabilizer bar, rotating in an elastomeric bushing. The focus of the research is to determine the conditions under which noise or stick-slip occurs. Elastomers tested include natural rubber with 0,5,10, 20, and 50 phr (parts per hundred rubber) carbon black, butyl, polydimethyl siloxane, and fluorocarbon. The hard counterfaces include chromium oxide, aluminum, epoxy paint, and glass. Various combinations of these materials were tested in an elastomeric hemisphere-on-flat configuration. Three regimes of sliding have thus far been identified: 1. Steady state sliding where the sliding friction is constant; 2. A high frequency self-excited oscillation of the test structure superimposed on the mean value of friction; 3. Stick-slip, where the elastomeric specimen goes through alternating periods of no relative and relative motion to the counterface. Friction maps which showed the regimes of stick-slip and steady state sliding as a function of load and velocity were experimentally determined. Stick-slip, the dominant mode of unsteady sliding did not occur below a critical velocity. The effects of surface energy, surface roughness and temperature on the critical velocity for stick-slip were also investigated. Stick-slip motion of materials has been attributed to a difference in static and kinetic coefficients of friction (typically for metallic systems) or a negative slope of the friction velocity curve. It has also been related to a maximum of tan delta or the loss modulus. Test results show that it is possible to have stick-slip occur in regions of positive or zero slope of the friction velocity curve. While the mechanism of stick-slip is not known for all of the elastomeric specimens, stick-slip of the butyl specimens appear to be related to Schallamach waves traversing the interface. For the natural rubber elastomers the critical velocity for stick-slip is dependent on the amount of carbon black. Decreasing amounts of carbon black decreases the critical velocity. The carbon black greatly increases the stiffness of the specimen while not appreciably shifting the frequency of the viscoelastic maxima. In addition, it was shown that a reduction in stiffness of the elastomeric specimen in the direction of sliding, by hollowing it out caused the critical velocity to decrease. Thus the critical velocity for stick-slip could be changed without changing the viscoelastic properties. / Ph. D.

In this thesis, the effect of interphase bonding on the cohesiveness of domain structure was addressed. The interchain attractive forces between rigid segments and the phase separation between hard and soft segments have been improved by introducing either urea groups or ionic units. The urea linkages have the possibility of extensive hydrogen bonding while ionic units interact with each other by coulombic interactions, which provide even stronger interchain associations than the hydrogen bonding effects. This thesis addressed the preparation and characterization of polytetrahydrofuran based segmented polyurethane-urea and ionene elastomers. The urea linkages were effectively introduced to the polyurethane elastomers through an unconventional route which was based on carbamate-isocyanate interactions. The carbamates were generated principally from isocyanate functional prepolymers and tertiary alcohols. The carbamates were rearranged thermally and/or catalytically to produce amines which were rapidly converted to ureas. The effects of varying the size of the rigid and flexible segments in polyurethane elastomers on physical behavior were investigated. The importance of hydrogen bonding interactions in promoting phase separation of hard and soft segments and the cohesiveness of hard segment domain structure was demonstrated. Living, difunctional polytetrahydrofuran dioxonium ions were prepared via triflic anhydride initiation. The direct coupling of these "living" polytetrahydrofuran dioxonium ions with a ditertiary amine was used to produce a novel segmented ionene elastomer. The ionenes thus synthesized displayed interesting solution behavior and could be molded, or cast to produce good physical properties. Photochromic as well as thermochromic phenomena were also noticed in these systems. / Ph. D.

Soft materials have attracted much scientific and technical interest in recent years. In this thesis, attention has been placed on the underpinning relations between molecular structure and properties of one type of soft matter - main chain liquid crystalline elastomers (MCLCEs), which may have application as shape memory or as auxetic materials. In this work, a number of siloxane-based MCLCEs and their linear polymer analogues (MCLCPs) with chemical variations were synthesized and examined. Among these chemical variations, rigid p-phenylene transverse rod and flat-shaped anthraquinone (AQ) mesogenic monomers were specifically incorporated. Thermal and X-ray analysis found a smectic C phase in most of our MCLCEs, which was induced by the strong self-segregation of siloxane spacers, hydrocarbon spacers and mesogenic rods. The smectic C mesophase of the parent LCE was not grossly affected by terphenyl transverse rods. Mechanical studies of MCLCEs indicated the typical three-region stress-strain curve and a polydomain-to-monodomain transition. Strain recovery experiments of MCLCEs showed a significant dependence of strain retentions on the initial strains but not on the chemical variations, such as the crosslinker content and the lateral substituents on mesogenic rods. The MCLCE with p-phenylene transverse rod showed a highly ordered smectic A mesophase at room temperature with high stiffness. Mechanical properties of MCLCEs with AQ monomers exhibit a strong dependence on the specific combination of hydrocarbon spacer and siloxane spacer, which also strongly affect the formation of ð-ð stacking between AQ units. Poisson s ratio measurement over a wide strain range found distinct trends of Poisson s ratio as a function of the crosslinker content as well as terphenyl transverse rod loadings in its parent MCLCEs.

No description available.

Biomass feedstock is a viable alternative to finite fossil fuel resources to provide many of the same—plus others that petrochemicals cannot—chemical building blocks required to fabricate durable and high-performance materials. We demonstrate here for the first time a new generation of synthesized elastomers, namely bio-based engineering elastomers (BEE). These are of particular significance because they are synthesized from monomers derived from biomass, by routes which are suitable for large scale production, and they exhibit thermo-mechanical properties at least equivalent to current commercial petrochemical-derived elastomers. Bio-based monomers in large scale production, such as sebacic acid, itaconic acid, succinate acid, 1,3-propanediol, and 1,4 butanediol are chosen to generate the first synthetic BEE matrix through melting polycondensation—a comparatively simple reaction scheme offering good control and the potential for low cost, large-scale production. A novel linear BEE, an almost non-crystalline copolyester elastomer with low glass transition temperature (Tg) containing double bonds is designed and synthesized using multiple monomers (to help suppress crystallization). Silica nanoparticles are then introduced into the BEE matrix to achieve significant strengthening and improved environmental stability. Chemical crosslinks formed by peroxide and the pendant double bonds in the copolyester macromolecules endow the BEE with both the necessary high elasticity and required environmental stability. The BEE nanocomposites obtained exhibit excellent thermomechanical properties, such as an ultimate tensile strength of 20 MPa.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Due to numerous accidents involving munitions, recent interest has focused on the development and use of insensitive munitions (IM). Polymeric materials are used in insensitive munitions as binders or plasticizers. Most of the polymeric binders used are based on polycondensation reaction via using urethane linkages. The main aim of this study was the synthesis and characterization of selected energetic thermoplastic elastomers binder based on utilizing controlled free radical polymerization. This was achieved by using hydroxyl terminated poly (epichlorohydrin) (PECH-diol) and hydroxyl terminated glycidyl azide polymer (GAP-diol) as starting materials, and the subsequent synthesis of different macroinitiators. These macro-initiators were used to polymerize methyl methacrylate (MMA) to obtain thermoplastic elastomers. PECH-diol was prepared by cationic ring-opening polymerization (CROP) based on using borontrifluoride etherate (BF3-etherate) as catalyst and a low molecular weight diol as initiator. GAP-diol was synthesized by the reaction of PECH-diol with sodium azide in organic solvent.. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) block copolymers were prepared by free radical polymerization of MMA monomer in presence of PECH and GAP macro-azoinitiator (MAI). The MAIs were prepared by the polycondensation reaction of hydroxyl terminated groups of elastomer with 4,4' azobis (4-cyanopentanoyl chloride) (ACPC). The phase behavior of blends of amorphous PMMA/PECH-diol and PMMA/GAP-diol was also investigated. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) graft copolymers were synthesized by photopolymerization of MMA in presence of PECH and GAP with pendant N,Ndiethyldithiocarbamate groups as macro-photoiniferters. . Photopolymerization of MMA proceeded in a controlled fashion. A macro RAFT agent, based on the reaction of PECH with pendent dithiobenzoate was prepared. The macro-RAFT agent was used in the controlled thermal bulk polymerization of methyl methacrylate. Finally, living/controlled radical polymerization of MMA with four different photoiniferters, namely benzyl diethyl dithiocarbamate (BDC), 2-(N,N-diethyldithiocarbamyl) propionic acid (PDC), 2-(N,Ndiethyldithiocarbamyl) isobutyric acid (DTCA), and diethyl dithiocarbamateepichlorohydrin was achieved.

Laser Sintering is an Additive Manufacturing technology that uses digital files to construct 3-dimensional parts by depositing and consolidating layers of powdered material. Application of the technology for metal and ceramic powders is common but the focus of this work was on polymer laser sintering. A significant drawback for polymer laser sintering is the limited selection of materials currently available for use compared with more conventional processes such as injection moulding. This constrains the usefulness of the technology for designers and engineers. A primary reason for this is a lack of detailed understanding of the development process for new materials for laser sintering. This PhD investigation examines some of the key attributes and requirements needed for successfully implementing new polymer-based laser sintering materials. A strategic method for characterizing and identifying new polymer materials was created utilizing thermal measurements, practical and analytical methods to quantify sintering rate, and degradation studies. Validation of this work occurred through the successful integration of a new laser sintering material at industrial project partner Burton Snowboards. Thermal degradation as a result of the laser sintering process was studied in detail and resulted in the creation of a proposed new parameter: Stable Sintering Region (SSR). The term acknowledges and defines the region above the melting point that is the minimum requirement for sintering to occur and an upper limit beyond which polymer deterioration impedes on mechanical properties. A quantitative approach to define the SSR was developed and explored with three different laser sintering materials, two of which were flexible elastomers. The ability to specifically interpret laser sintering process parameters from thermal degradation characterization was created and used to explore the effects of high energy input on tensile properties and molecular weight. The results of these tests showed the potential to identify an Optimum Sintering Range based on maximizing mechanical properties through the control of energy input and molecular weight. This thesis makes a significant contribution to the knowledge and understanding of polymer laser sintering, especially in the context of materials development. Novel concepts such as the Stable Sintering Region were developed using a theoretical approach and practical measurements and were also thoroughly explored for verification. Additionally, a new method to use a powder characterization technique to predict the actual machine parameters of a material in the laser sintering process was quantified. This has several implications for testing new materials for laser sintering and efficiently identifying appropriate processing conditions.

In the past, the use of a fracture mechanics approach to describe crack growth in elastomers has been shown to work well for specimens of simple test geometry, simply loaded. This has been the case because elastic strain energy density (e.s.e.d.) functions could reliably be used to calculate both the magnitude of elastic stored energy available to drive a crack and the magnitude of the rate of release of such energy as the crack grows. The aim of this thesis was to investigate the applicability of such a methodology to situations of more complex loading. To this end two novel test-piece geometries were developed. The first consisted of a pure shear geometry with the sample having been pre-strained in the longitudinal direction to varying extents, hence introducing a type of bi-axial deformation. The second consisted of a pure shear geometry test-piece inclined at 30° to the horizontal and loaded in the vertical direction, hence inducing simultaneously pure shear and simple shear loading. Both types of test-piece were used to study the validity of the particular e.s.e.d. functions, the energetics and mechanics of crack growth and crack growth geometries on a macro and micro scale. The constants in particular e.s.e.d. functions were determined by uniaxially deforming in pure shear each of the carbon black reinforced materials used in this study. The resulting functions became progressively less good at predicting the elastic strain energy in the novel geometry test-pieces as the deformation modes became more complex. Anisotropy induced by deforming specimens in one direction was not easily removed even by an imposed large deformation in another direction. Nevertheless, the functions were successfully used to predict crack growth directions in the 30° inclined test-piece. However in the pre-strain pure shear test-pieces the functions significantly underestimated the elastic strain energy. Hence the real energies had to be determined from the forces and extensions measured during cyclic crack growth tests. In these tests crack growth rates for a given tearing energy (elastic energy release rate) increased as the magnitude of the pre-strain increased. This significant weakening was associated with the development of a strain induced molecular and carbon black anisotropy.

As próteses faciais e intraorais tem um importante papel na devolução da estética e de algumas funções para os pacientes. Por meio da restauração da imagem corporal é possível reintegrá-lo a sociedade, resgatando assim a identidade do indivíduo. A boa condição dessas próteses é primordial para que estas possam exercer suas funções adequadamente e manter o local, onde estão inseridas, livre de infecções e inflamações. Portanto, a não formação de colônias e biofilmes bacterianos em materiais eleitos para confecção dessas próteses, trarão benefícios aos pacientes reabilitados. Visando isso, a presente dissertação verificou a capacidade de inclusão e a eficiência bactericida do biocida policloreto de dialildimetilamônio (PDADMAC) em resina acrílica autopolimerizável (RAAQ) e termopolimerizável (RAAT), e silicone de uso médico. Os resultados mostraram que o biocida PDADMAC quando dissolvido no tetrahidrofurano apresentou boa incorporação tanto nas resinas acrílicas, quimicamente ativas e termo ativas, quanto no silicone de uso médico e que apenas os corpos de prova que receberam 2 mililitros do PDADMAC em massa polimérica tiveram uma resposta bactericida eficaz. / The facial and intraoral prosthesis has an important role in the aesthetics and return of some functions to patients. Through restoration of the body image can reistante to can society , thus recovering the individual\'s identity . The good condition of these prostheses is essential so they can perform their function properly and maintain the the area where the prostheses are inserted free of infection and inflammation. Therefore, no formation of bacteria colonies and biofilms in the chosen materials for making these prostheses , will bring benefits to patients rehabilitated. The present work evaluated the capability of inclusion and the bactericidal efficiency of the biocide poly(diallyldimethylammonium chloride) ( pDADMAC ) of acrylic resin autopolymmerized ( RAAQ ) and thermal polymerized ( RAAT ) , and silicone medical use. The results showed that the biocide pDADMAC when dissolved in tetrahydrofuran presented a good incorporation in both acrylic resins and in the medical grade silicone and that only the samples that received 2 ml of pDADMAC in polymer had an effective bactericidal response.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING / Vita. / Includes bibliographical references. / by Timothy George Peter Gutowski. / Ph.D.