Five series of PT-30/organoclay (Cloisite 10A, Cloisite 30B, Nanomer I.28E, Nanomer I.30E and Nanomer I.44PA) composites were prepared and characterized. The dispersion of clay tactoids in PT-30 resin was studied by XRD and TEM. XRD analyses determined that the d-spacings of each nanoclays of these were expanded upon dispersing in the PT-30 matrix versus the as-received clay. TEM micrographs further demonstrated that the intercalation of clay layers by PT-30 occurred during the curing process. Histograms of clay tactoids distributions were generated based on the combination of XRD and TEM results. The glass transition temperatures (Tg) of selected PT-30/clay composites were measured by DSC and compared. Partial clay exfoliation with some resin intercalation was demonstrated. The average flexural strengths and flexural moduli of all composites were obtained using three-point bending tests.

Tomorrow’s lightweight, high-performance composite systems will be made of structures built with materials that have unprecedented intrinsic properties for performing a wide range of functions, such as EMI shielding, thermal management, flame resistance, lightning strike protection, acoustic damping, and health-monitoring. Current structures require parasitic components, e.g., metal strips, copper wire meshes, strain gauges, and heat sinks to provide these functions. By eliminating parasitic components, future high-performance multifunctional systems can achieve the intended objectives, while maintaining optimum weight, reliability, cost, and fuel efficiency. With the continuing growth of polymer composites in industries, such as aerospace, automotive, and wind energy, research and development on lightweight, high-performance composites that possess extraordinary properties for future multifunctional systems has generated considerable interest and excitement. Recent advances in nanomaterial synthesis and functionalization have shown that tailored property combinations are possible with reduced parasitic content to achieve multifunctionality. Cyanate ester (CE), a class of high-performance thermosetting resins (high T [subscript g], >250°C), has received considerable attention due to its good mechanical properties, thermal stability, flammability properties, ease of process, and volatile-free curing process. Multiwall carbon nanotubes were selected due to their unique combination of excellent mechanical, electrical, and thermal properties. The principal objective of this work is to determine the extent to which several different processing techniques will affect the MWNT dispersion and corresponding nanocomposite properties, such as thermal, flammability, mechanical, and electrical properties. A processing-structure-property relationship, as well as performance of this class of carbon-based CE nanocomposite, will be established. Therefore, a major scientific contribution of this study will be the development and characterization of a novel, multifunctional CE nanocomposite. Different mixing instruments, such as high shear mixer, ultrasonicator, planetary centrifugal mixer, etc. were used to disperse the nanotubes in the cyanate ester resin matrix. Microstructural morphology characterizations by SEM, STEM, and TEM show that various degrees of dispersions of MWNTs were obtained by the different mixing techniques. An attempt to quantify the MWNT dispersion was made. Electrical resistivity of samples processed by both stand mixer and three-roll mill passes the ESD requirement; however, the MWNT percolation thresholds by the two techniques are different. Thermal analysis shows that the addition of the Fe³+ catalyst or the coupling agent lowers the glass transition temperature and degrades the mechanical properties (e.g., storage modulus, tangent of phase angle delta) of the CE resin. On the other hand, processing techniques only affect the mechanical properties of the resin. Thermal stability of CE is only slightly affected by different processing techniques, as well as the addition of MWNTs. Much more significantly, flammability characterization shows that the incorporation of either the Fe³+ catalyst or the coupling agent substantially increases the peak heat release rate (PHRR) relative to the neat CE resin value. / text

Cyanate ester (PT-15, Lonza Corp) composites containing the inorganic-organic hybrid polyhedral oligomeric silsesquioxanes (POSS), octaaminophenyl(T8)POSS (C6H4NH2)8(SiO1.5)8, cyanopropylheptacyclopentyl(T8)POSS, (C5H9)7(SiO1.5)8(CH2) 3CN or TriSilanolPhenylPOSS (C42H38O12Si7), were synthesized respectively. These PT-15/POSS composites were characterized by FT-IR, X-ray diffraction (XRD), small-angle neutron scattering (SANS), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and three-point bending flexural tests. XRD, TEM and IR data are all consistent with molecular dispersion of octaaminophenyl(T8)POSS and TriSilanolPhenylPOSS due to the chemical bonding of the POSS macromer into the continuous cyanate ester network phase. In contrast to octaaminophenyl(T8) POSS and TriSilanolPhenylPOSS, cyanopropylheptacyclopentyl (T8)POSS has a low solubility in PT-15 and does not react with the resin before or during the cure. The TriSilanolPhenylPOSS (C42H38O12Si7) was incorporated into the aliphatic epoxy (Epoxy 9000, Clearstream Products, Inc.) in 99/1, 97/3, 95/5, 90/10 and 85/15 w/w ratios and cured. This same epoxy resin was also blended with an equal weight (50/50 w/w) of cyanate ester resin (PT-15, Lonza Corp) and TriSilanolPhenylPOSS was added in resin/POSS weight ratios of 99/1, 97/3, 95/5, 90/10 and 85/15 and cured. Both sets of composites were characterized by FT-IR, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), dynamic mechanical thermal analysis (DMTA) and three-point bending flexural tests. TriSilanolPhenyl-POSS was first thoroughly dispersed into the uncured liquid epoxy resin or the epoxy/PT-15 blend. XRD and X-EDS measurements after curing were consistent with partial molecular dispersion of the POSS units in the continuous matrix phase, while the remainder forms POSS aggregates. TEM and SEM show that POSS?enriched nanoparticles are present in the matrix resins of both the epoxy/POSS and epoxy-PT-15/POSS composites.

Cyanate ester thermosetting resins are a novel family of materials for high technology and aerospace applications. The high glass transition temperatures available from cured cyanate ester networks and subsequently, their resistances to corrosive materials make these resins attractive for harsh environmental applications. These features of cyanate ester resins presented a threefold opportunity for investigation, namely: 1) establish a characterization technique for the long term mechanical properties of the cured resins, 2) develop a method for determining the effect of physical and chemical aging on these mechanical properties, and 3) evaluate the AroCy® B-10 cyanate ester resin from Ciba-Geigy for use in applications where temperatures could easily reach 177°C (300°F). Dynamic mechanical analysis used in a step isothermal mode was developed to characterize the mechanical properties of the cured resin and a family of isothermal modulus curves was established. These data were then shifted, following WLF theory, to create a master curve of storage modulus with respect to measurement frequency. The resultant master curves allowed the prediction of long term mechanical behavior of the resin networks via short duration, accelerated experimental tests. The test methodology and experimental procedures were especially useful in determining the effects of physical and chemical aging on the mechanical properties of the resin. Cured resins were aged in oxidative and inert atmospheres (air and nitrogen, respectively) for varying time and temperature to study the suitability of cyanate ester resins for harsh environmental applications. After aging, the samples were tested by DMA, DSC and TGA and master curves of their mechanical behavior were generated. The results were then grouped to form a family of master curves as a function of atmosphere, time and temperature. This approach allowed for the separation of the competing chemical and physical degradation processes and established the practical application conditions for this class of cross-linked polymers. Using the techniques established above, a model cyanate ester resin was selected based upon its chemical simplicity and availability. AroCy® B-10 cyanate ester resin manufactured commercially by Ciba-Geigy was evaluated for its application where temperatures could easily reach 177C. While this material was clearly unacceptable for the stated application conditions (especially in an oxygen rich atmosphere), its investigation provided experimental confirmation of the techniques developed. The test procedures and performance evaluation techniques described allow for the systematic assessment of not only the cyanate ester class of networking polymers, but any glass forming material, and a separation methodology for their concomitant chemical and physical degradation pathways. / Ph. D.

C.I. Beard and B.P. Dailey. / "August 17, 1948." / Bibliography: p. 17. / Army Signal Corps Contract No. W36-039-sc-32037 Project No. 102B. Dept. of the Army Project No. 3-99-10-022.

Brandenburgische Techn. Universiẗat, Diss., 2003--Cottbus.

The objective of this investigation was to characterize two cyanate ester resins and a eight harness satin (8HS) graphite fabric for use in resin film infusion (RFI) processing. Two cyanate ester resin systems were characterized to determine their cure-kinetics, and viscosities during cure. A 8HS graphite fabric was tested in compaction and through the thickness permeability. A one-dimensional, through the thickness, flow and cure computer simulation was run. The resin cure-kinetics models predicted the curing behavior of the resins as functions of time, temperature, and degree of cure. The proposed viscosity models determined the resin viscosity as a function of temperature and degree of cure. The 8HS graphite fabric was tested in compaction and through the thickness permeability to determine the effect of compaction pressure on fiber volume fraction and in turn on through the thickness permeability. The one-dimensional RFI flow and cure simulation combined the cure-kinetics and viscosity models of the resins with the characteristics of the graphite fabric and determined resin infiltration and cure times. The proposed cure-kinetics and viscosity models were more than adequate in modeling the cure and flow behavior of the cyanate ester resin systems. Power law curve fits accurately represented the compaction and through the thickness permeability of the 8HS graphite fabric. Finally, the one-dimensional RFI flow and cure simulation showed that resin viscosity was the major influence on the infiltration times. / Master of Science

Cette thèse de doctorat aborde de nouvelles conceptions de films à base de résines d’ester de cyanate (CER) en présence de liquides ioniques (LIs) en tant qu'agents multifonctionnels : catalyseurs, agents de modification réactifs, renforts ou agents porogènes. Les liquides ioniques de structures et de concentrations variables accélèrent de manière significative la polycyclotrimérisation du dicyanate d’ester de bisphenol E, en l'absence de tout solvant organique supplémentaire ou additif. Les réseaux de polycyanurates resultants dopés avec des liquides ioniques aprotiques peuvent constituer des matériaux prometteurs pour la production de structures photosensibles. De tels systèmes nanocomposites permettent la séparation, larécupération et le recyclage aisés des LIs par simple extraction, ce qui permet finalement l'obtention de films nanoporeux thermostables. Les caractéristiques de la porosité de ces matériaux dépendent de la concentration des LIs dans les précurseurs CERs. Les LIs protoniques contenant des groupements fonctionnels >NH et -OH, indépendamment de leurmasse molaire, de la structure chimique du cation et de l'anion, sont incorporés chimiquement dans le réseau polycyanurate. Ainsi, les matériaux hybrides obtenus avec des fragments de liquides ioniques pourraient fournir d’excellents candidats pour des recherches futures sur les ionomères et les nanocomposites. / This PhD thesis addresses new designs of cyanate ester resin (CER) films in the presence of ionic liquids as multifunctional agents: catalysts, reactive modifiers, fillers or porogens. It should be emphasized that ionic liquids (ILs) of varying structures and concentrations significantly accelerate the polycyclotrimerization of dicyanate ester of bisphenol E, in the absence of any additional organic solvent or additive. The resulting polycyanurate networks doped with aprotic ionic liquids can be promising materials for producing photosensitive structures. Such nanocomposite systems allow for easier separation, recovery, and recycling of ILs by mere extraction, which eventually affords thermally stable nanoporous films. The porosity features of these materials depend on the concentration of ILs in the CER precursors.Protic ILs containing functional >NH and -OH groups, regardless of molar mass, chemical structure of cation and anion, chemically incorporate into the polycyanurate network, thus the resulting hybrid materials with fragments of ionic liquids could provide excellent candidates for future research in ionomers and nanocomposites.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

<p align=\"justify\">As propriedades de fluorescência da 2,4-(1H,3H)-quinazolinediona, produto da reação entre o íon cianato e o ácido 2-aminobenzóico possibilitaram o desenvolvimento de um método simples, sensíveis, seletivo e reprodutível para a análise de íons cianato em meio aquo etanólico. O método foi aplicado a análises de íons cianato em diferentes frações do destilado de cana e os dados sugerem uma forte correlação entre a presença de ureia no vinho, e as concentrações de íons cianato e de carbamato de etila (CE) no destilado. A citrulina apresenta-se também como uma fonte de íons cianato, tendo como um de seus produtos o CE na presença do etanol. Acompanhando-se no destilado recém-obtido as variações nas concentrações de íons cianato e de carbamato de etila em função do tempo, observa-se que à medida que diminui a concentração de íons cianato há um aumento na concentração de carbamato de etila. Foram estudados os aspectos cinéticos e termodinâmicos da formação de CE por meio da reação entre íons cianato e o etanol. Os valores das constantes de velocidade para o consumo do íon cianato e para a de formação de CE são de (8&sbquo;0 &plusmn; 0&sbquo;4) &times; 10-5 e de (8&sbquo;90 &plusmn; 0&sbquo;4) &times; 10-5 s-1, respectivamente, a 25 &deg;C em solução etanólica 48% (v&frasl;v) com pH 4&sbquo;5. Nas condições experimentais, as constantes de velocidade são independentes das concentrações de etanol e dos íons cianato, porém são dependentes da acidez pH e apresentam os valores dos parâmetros de ativação de &Delta;H&#8225; &#61; 19&sbquo;4 &plusmn; 1 kcal&frasl;mol, &Delta;S&#8225; &#61; -12&sbquo;1 &plusmn; 1 cal&frasl;K e &Delta;G&#8225; &#61; 23&sbquo;0 &plusmn; 1 kcal&frasl;mol. Cálculos computacionais empregando-se teoria do funcional de densidade (DFT) sugerem que os valores calculados de &Delta;H&#8225;1 &Delta;S&#8225;1 e &Delta;G&#8225;1 estão de acordo com os obtidos experimentalmente e condizem com o mecanismo proposto. Observa-se que íons de Cu(II) catalisam a oxidação de íons cianeto à cianato promovendo a formação de CE. Além disso, íons de Cu(II) pode se coordenar com alguns precursores de CE. / <p align=\"justify\">Based on the fluorescence properties of 2,4-(1H,3H)-quinazolinedione, a product of the reaction between cyanate and 2-aminobenzoic acid, a simple, sensitive, selective, and reproducible method for the cyanate analysis in aqueous ethanolic media is proposed. The method was applied to cyanate analysis in different fractions of sugarcane distillate and the data strongly suggest a correlation between the presence of urea in wine, and cyanate and ethyl carbamate (EC) concentrations in the spirit. Citrulline also presents itself as a cyanate source, having EC as one of its products in the presence of ethanol. Monitoring changes in cyanate and EC concentrations as function of the time in freshly distilled sugar cane spirit, it was observed that as the cyanate concentration decreases, the EC concentration increases. Thermodynamic and kinetic aspects of EC formation through the reaction between cyanate and ethanol were investigated. The rate constant values for cyanate ion decay and EC formation are (8.0 &plusmn; 0.4) &times; 10-5 s-1 and (8.90 &plusmn; 0.4) &times; 10-5 s-1, respectively, at 25 &deg;C in 48% ethanolic solution at pH 4.5. Under the investigated experimental conditions, the rate constants are independent of the ethanol and cyanate concentrations but increase as the temperature increases &Delta;H&#8225; &#61; 19.4 &plusmn; 1 kcal&frasl;mol, &Delta;S&#8225; &#61; -12.1 &plusmn; 1 cal&frasl;K and &Delta;G&#8225; &#61; 23.0 &plusmn; 1 kcal&frasl;mol) and decrease as pH solution increases. According to molecular modeling (DFT) that was performed to analyze the reaction mechanism, Isocyanic acid is the active EC precursor. The calculated &Delta;H&#8225;1 &Delta;S&#8225;1 and &Delta;G&#8225;1 values are in very good agreement with the experimental ones. The copper effect on EC formation reaction was also studied. Copper acts on the cyanide oxidation reaction and could coordinate with some EC precursors.