Modifying Silicates for Better Dispersion in Nanocomposites

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained

Polymer/Silicate Nanocomposites Developed for Improved Thermal Stability and Barrier Properties

The nanoscale reinforcement of polymers is becoming an attractive means of improving the properties and stability of polymers. Polymer-silicate nanocomposites are a relatively new class of materials with phase dimensions typically on the order of a few nanometers. Because of their nanometer-size features, nanocomposites possess unique properties typically not shared by more conventional composites. Polymer-layered silicate nanocomposites can attain a certain degree of stiffness, strength, and barrier properties with far less ceramic content than comparable glass- or mineral-reinforced polymers. Reinforcement of existing and new polyimides by this method offers an opportunity to greatly improve existing polymer properties without altering current synthetic or processing procedures

Polymer/Silicate Nanocomposites Used to Manufacture Gas Storage Tanks With Reduced Permeability

Over the past decade, there has been considerable research in the area of polymer-layered silicate nanocomposites. This research has shown that the dispersion of small amounts of an organically modified layered silicate improves the polymer strength, modulus, thermal stability, and barrier properties. There have been several reports on the dispersion of layered silicates in an epoxy matrix. Potential enhancements to the barrier properties of epoxy/silicate nanocomposites make this material attractive for low permeability tankage. Polymer matrix composites (PMCs) have several advantages for cryogenic storage tanks. They are lightweight, strong, and stiff; therefore, a smaller fraction of a vehicle's potential payload capacity is used for propellant storage. Unfortunately, the resins typically used to make PMC tanks have higher gas permeability than metals. This can lead to hydrogen loss through the body of the tank instead of just at welds and fittings. One approach to eliminate this problem is to build composite tanks with thin metal liners. However, although these tanks provide good permeability performance, they suffer from a substantial mismatch in the coefficient of thermal expansion, which can lead to failure of the bond between the liner and the body of the tank. Both problems could be addressed with polymersilicate nanocomposites, which exhibit reduced hydrogen permeability, making them potential candidates for linerless PMC tanks. Through collaboration with Northrop Grumman and Michigan State University, nanocomposite test tanks were manufactured for the NASA Glenn Research Center, and the helium permeability was measured. An organically modified silicate was prepared at Michigan State University and dispersed in an epoxy matrix (EPON 826/JeffamineD230). The epoxy/silicate nanocomposites contained either 0 or 5 wt% of the organically modified silicate. The tanks were made by filament winding carbon fibers with the nanocomposite resin. Helium permeability was measured by Northrop Grumman, showing that the leak rate/day of the nanocomposite matrix tank was approximately 80-percent less than that of the neat epoxy matrix tank

Polymer/Silicate Nanocomposites Developed for Improved Strength and Thermal Stability

Over the past decade, polymer-silicate nanocomposites have been attracting considerable attention as a method of enhancing polymer properties. The nanometer dimensions of the dispersed silicate reinforcement can greatly improve the mechanical, thermal, and gas barrier properties of a polymer matrix. In a study at the NASA Glenn Research Center, the dispersion of small amounts (less than 5 wt%) of an organically modified layered silicate (OLS) into the polymer matrix of a carbon-fiber-reinforced composite has improved the thermal stability of the composite. The enhanced barrier properties of the polymer-clay hybrid are believed to slow the diffusion of oxygen into the bulk polymer, thereby slowing oxidative degradation of the polymer. Electron-backscattering images show cracking of a nanocomposite matrix composite in comparison to a neat resin matrix composite. The images show that dispersion of an OLS into the matrix resin reduces polymer oxidation during aging and reduces the amount of cracking in the matrix significantly. Improvements in composite flexural strength, flexural modulus, and interlaminar shear strength were also obtained with the addition of OLS. An increase of up to 15 percent in these mechanical properties was observed in composites tested at room temperature and 288 C. The best properties were seen with low silicate levels, 1 to 3 wt%, because of the better dispersion of the silicate in the polymer matrix

High Temperature Thermosetting Polyimide Nanocomposites Prepared with Reduced Charge Organoclay

The naturally occurring sodium and calcium cations found in bentonite clay galleries were exchanged with lithium cations. Following the cation exchange, a series of reduced charge clays were prepared by heat treatment of the lithium bentonite at 130 C, 150 C, or 170 C. Inductively coupled plasma (ICP) analysis showed that heating the lithium clay at elevated temperatures reduced its cation exchange capacity. Ion exchange of heat-treated clays with either a protonated alkyl amine or a protonated aromatic diamine resulted in decreasing amounts of the organic modifier incorporated into the lithium clay. The level of silicate dispersion in a thermosetting polyimide matrix was dependent upon the temperature of Li-clay heat treatment as well as the organic modification. In general, clays treated at 150 C or 170 C, and exchanged with protonated octadcylamine or protonated 2,2'-dimethlybenzidine (DMBZ) showed a higher degree of dispersion than clays treated at 130 C, or exchanged with protonated dodecylamine. Dynamic mechanical analysis showed little change in the storage modulus or T(sub g) of the nanocomposites compared to the base resin. However, long term isothermal aging of the samples showed a significant decrease in the resin oxidative weight loss. Nanocomposite samples aged in air for 1000 hours at 288 C showed of to a decrease in weight loss compared to that of the base resin. This again was dependent on the temperature at which the Li-clay was heated and the choice of organic modification

Properties of PMR Polyimides Improved by Preparation of Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites

The field of hybrid organic-inorganic materials has grown drastically over the last several years. This interest stems from our ever-increasing ability to custom-build and control molecular structure at several length scales. This ability to control both the composition and structure of hybrid materials is sometimes broadly referred to as nanocomposite systems. One class of hybrid (organic-inorganic) nanostructured material is polyhedral oligomeric silsesquioxane (POSS), shown in the preceding diagram. The hybrid composition gives POSS materials dramatically enhanced properties relative to traditional hydrocarbons and inorganics. An important benefit of this technology is that it makes possible the formulations of nanostructured chemicals with excellent thermal and oxidative stability. This is largely due to the inorganic component

Graphite Sheet Coating for Improved Thermal Oxidative Stability of Carbon Fiber Reinforced/PMR-15 Composites

Expanded graphite was compressed into graphite sheets and used as a coating for carbon fiber reinforced PMR-15 composites. BET analysis of the graphite indicated an increase in graphite pore size on compression, however the material was proven to be an effective barrier to oxygen when prepegged with PMR-15 resin. Oxygen permeability of the PMR-15/graphite was an order of magnitude lower than the compressed graphite sheet. By providing a barrier to oxygen permeation, the rate of oxidative degradation of PMR-15 was decreased. As a result, the composite thermo-oxidative stability increased by up to 25%. The addition of a graphite sheet as a top ply on the composites yielded little change in the material's flexural strength or interlaminar shear strength

Anomalous Thermostat and Intraband Discrete Breathers

We investigate the dynamics of a macroscopic system which consists of an anharmonic subsystem embedded in an arbitrary harmonic lattice, including quenched disorder. Elimination of the harmonic degrees of freedom leads to a nonlinear Langevin equation for the anharmonic coordinates. For zero temperature, we prove that the support of the Fourier transform of the memory kernel and of the time averaged velocity-velocity correlations functions of the anharmonic system can not overlap. As a consequence, the asymptotic solutions can be constant, periodic,quasiperiodic or almost periodic, and possibly weakly chaotic. For a sinusoidal trajectory with frequency $\Omega$ we find that the energy $E_T$ transferred to the harmonic system up to time $T$ is proportional to $T^{\alpha}$. If $\Omega$ equals one of the phonon frequencies $\omega_\nu$, it is $\alpha=2$. We prove that there is a full measure set such that for $\Omega$ in this set it is $\alpha=0$, i.e. there is no energy dissipation. Under certain conditions there exists a zero measure set such that for $\Omega \in this set the dissipation rate is nonzero and may be subdissipative$(0 \leq \alpha < 1)$or superdissipative$(1 <\alpha \leq 2)$. Consequently, the harmonic bath does act as an anomalous thermostat. Intraband discrete breathers are such solutions which do not relax. We prove for arbitrary anharmonicity and small but finite coupling that intraband discrete breathers with frequency$\Omega$exist for all$\Omega$in a Cantor set$\mathcal{C}(k)$of finite Lebesgue measure. This is achieved by estimating the contribution of small denominators appearing in the memory kernel. For$\Omega\in\mathcal{C}(k)$the small denominators do not lead to divergencies such that this kernel is a smooth and bounded function in$t$.Comment: Physica D in prin

Genetic testing of children for adult-onset conditions: opinions of the British adult population and implications for clinical practice

This study set out to explore the attitudes of a representative sample of the British public towards genetic testing in children to predict disease in the future. We sought opinions about genetic testing for adult-onset conditions for which no prevention/treatment is available during childhood, and about genetic 'carrier' status to assess future reproductive risks. The study also examined participants' level of agreement with the reasons professional organisations give in favour of deferring such testing. Participants (n=2998) completed a specially designed questionnaire, distributed by email. Nearly half of the sample (47%) agreed that parents should be able to test their child for adult-onset conditions, even if there is no treatment or prevention at time of testing. This runs contrary to professional guidance about genetic testing in children. Testing for carrier status was supported by a larger proportion (60%). A child's future ability to decide for her/himself if and when to be tested was the least supported argument in favour of deferring testing.European Journal of Human Genetics advance online publication, 5 November 2014; doi:10.1038/ejhg.2014.221