Glassy Dynamics of Epoxy-Amine Thermosets Containing Dynamic, Aromatic Disulfides
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Broderick Lewis↗
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Superposition of dynamic mechanical properties in the glassy state
Glassy state beta transition temperatures in cured epoxy resins, showing diglycidyl ether of bisphenol A /DGEBA/ dependence
Cuddihy, E. F.↗
Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)
Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.
Hurwitz, F. I.↗
Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers
Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).
Jaffe, Richard↗
Dynamical States of Low Temperature Cirrus
Low ice crystal concentration and sustained in-cloud supersaturation, commonly found in cloud observations at low temperature, challenge our understanding of cirrus formation. Heterogeneous freezing from effloresced ammonium sulfate, glassy aerosol, dust and black carbon are proposed to cause these phenomena; this requires low updrafts for cirrus characteristics to agree with observations and is at odds with the gravity wave spectrum in the upper troposphere. Background temperature fluctuations however can establish a dynamical equilibrium between ice production and sedimentation loss (as opposed to ice crystal formation during the first stages of cloud evolution and subsequent slow cloud decay) that explains low temperature cirrus properties. This newly-discovered state is favored at low temperatures and does not require heterogeneous nucleation to occur (the presence of ice nuclei can however facilitate its onset). Our understanding of cirrus clouds and their role in anthropogenic climate change is reshaped, as the type of dynamical forcing will set these clouds in one of two preferred microphysical regimes with very different susceptibility to aerosol.
Barahona, D.↗
Thermal Ablation Modeling for Silicate Materials
A general thermal ablation model for silicates is proposed. The model includes the mass losses through the balance between evaporation and condensation, and through the moving molten layer driven by surface shear force and pressure gradient. This model can be applied in the ablation simulation of the meteoroid and the glassy ablator for spacecraft Thermal Protection Systems. Time-dependent axisymmetric computations are performed by coupling the fluid dynamics code, Data-Parallel Line Relaxation program, with the material response code, Two-dimensional Implicit Thermal Ablation simulation program, to predict the mass lost rates and shape change. The predicted mass loss rates will be compared with available data for model validation, and parametric studies will also be performed for meteoroid earth entry conditions.
Ablation↗
Thermal Ablation Modeling for Silicate Materials
A thermal ablation model for silicates is proposed. The model includes the mass losses through the balance between evaporation and condensation, and through the moving molten layer driven by surface shear force and pressure gradient. This model can be applied in ablation simulations of the meteoroid or glassy Thermal Protection Systems for spacecraft. Time-dependent axi-symmetric computations are performed by coupling the fluid dynamics code, Data-Parallel Line Relaxation program, with the material response code, Two-dimensional Implicit Thermal Ablation simulation program, to predict the mass lost rates and shape change. For model validation, the surface recession of fused amorphous quartz rod is computed, and the recession predictions reasonably agree with available data. The present parametric studies for two groups of meteoroid earth entry conditions indicate that the mass loss through moving molten layer is negligibly small for heat-flux conditions at around 1 MW/cm(exp. 2).
Ablators↗
Dynamics of hard sphere colloidal dispersions
Our objective is to perform on homogeneous, fully equilibrated dispersions the full set of experiments characterizing the transition from fluid to solid and the properties of the crystalline and glassy solid. These include measurements quantifying the nucleation and growth of crystallites, the structure of the initial fluid and the fully crystalline solid, and Brownian motion of particles within the crystal, and the elasticity of the crystal and the glass. Experiments are being built and tested for ideal microgravity environment. Here we describe the ground based effort, which exploits a fluidized bed to create a homogeneous, steady dispersion for the studies. The differences between the microgravity environment and the fluidized bed is gauged by the Peclet number Pe, which measures the rate of convection/sedimentation relative to Brownian motion. We have designed our experiment to accomplish three types of measurements on hard sphere suspensions in a fluidized bed: the static scattering intensity as a function of angle to determine the structure factor, the temporal autocorrelation function at all scattering angles to probe the dynamics, and the amplitude of the response to an oscillatory forcing to deduce the low frequency viscoelasticity. Thus the scattering instrument and the colloidal dispersion were chosen such as that the important features of each physical property lie within the detectable range for each measurement.
Zhu, J. X.↗
REACTER: A Versatile Tool for Large-Scale Reactive Molecular Dynamics
Accurately describing reactive events over long length and time scales remains a grand challenge of computational materials science. REACTER is a general protocol for modeling chemical reactions using classical force fields, and is implemented in the popular molecular dynamics software LAMMPS. REACTER has a growing user base and has been used as a model-building tool for a variety of materials, including thermoplastics, thermosets, glassy materials and composites. The method has also been applied to accelerated modeling of reversible chemical reactions, such as the formation of electrochemical components for batteries. Recently, the REACTER protocol has received some major upgrades to enhance its ability to predict when reactions occur and to make it easier to use. Force field parameters can now be automatically assigned to newly created bonds, angles and other interactions. Advanced reaction constraints have also been added, including an Arrhenius constraint to enforce an effective activation energy, a root-mean-square-deviation option for complex geometrical constraints, and a constraint based on the total potential energy of the atoms involved in a reactive site. This potential energy constraint allows for the accurate reproduction of DFT-based tight-binding (DFTB3) predicted bond dissociation curves for mechanically induced bond breaking.
polymer simulations, molecular dynamics↗
Analytical ultrasonics for characterization of metallurgical microstructures and transformations
The application of contact (piezoelectric) and noncontact (laser generation and detection) ultrasonic techniques for dynamic investigation of precipitation hardening processes in aluminum alloys, as well as crystallization and phase transformation in rapidly solidified amorphous and microcrystalline alloys is discussed. From the variations of the sound velocity and attenuation the precipitation mechanism and kinetics were determined. In addition, a correlation was established between the observed changes in the velocity and attenuation and the mechanical properties of age-hardenable aluminum alloys. The behavior of the elastic moduli, determined ultrasonically, were found to be sensitive to relaxation, crystallization and phase decomposition phenomena in rapidly solidified metallic glasses. Analytical ultrasonics enables determination of the activation energies and growth parameters of the reactions. Therefrom theoretical models can be constructed to explain the changes in mechanical and physical properties upon heat treatment of glassy alloys. The composition dependence of the elastic moduli in amorphous Cu-Zr alloys was found to be related to the glass transition temperature, and consequently to the glass forming ability of these alloys. Dynamic ultrasonic analysis was found to be feasible for on-line, real-time, monitoring of metallurgical processes.
Rosen, M.↗
The effect of physical aging on the time-dependent properties of carbon-fiber-reinforced epoxy composites
Annealing in nitrogen below the glass transition temperature T(g) is found to affect the matrix-dominated physical properties of postcured, (+ and -45)2s specimens of Thornel 300 carbon fiber/Fiberite 934 epoxy composite as well as neat Fiberite 934 epoxy resin. The damping behavior, stress-relaxation rate and enthalpic state of the matrix material are found to decrease as functions of annealing time. The time-dependent change in physical properties is explained on the basis of free-volume collapse related to the physical aging of the nonequilibrium glassy network of epoxy. Such physical aging in network epoxy has been demonstrated to be thermoreversible through the monitoring of its kinetics by differential scanning calorimetry, stress relaxation tests, and dynamic mechanical analysis.
Kong, E. S. W.↗
Influence of physical aging on the time-dependent properties of network epoxies and epoxy-matrix composites
The matrix-dominated properties of a network epoxy and its carbon fiber-reinforced composite are noted to be affected by sub-glass transition temperature T(g) annealing in a nitrogen atmosphere. The damping behavior, stress relaxation rate, and enthalpic state of the matrix material were found to decrease as functions of sub-T(g) annealing time. This time-dependent change in physical properties is explained on the basis of a free-volume collapse which is related to the recovery process of the nonequilibrium glassy network of the epoxy. The physical aging in network epoxies has been demonstrated to be thermoreversible. Aging kinetics are studied by means of differential scanning calorimetry, stress relaxation tests, dynamic mechanical analysis, and thermomechanical analysis.
Kong, E. S. W.↗
Mass Spectrometric Measurement of Martian Krypton and Xenon Isotopic Abundance
The Viking gas chromatograph mass spectrometer experiment provided significant data on the atmospheric composition at the surface of Mars, including measurements of several isotope ratios. However, the limited dynamic range of this mass spectrometer resulted in marginal measurements for the important Kr and Xe isotopic abundance. The Xe-129 to Xe-132 ratio was measured with an uncertainty of 70%, but none of the other isotope ratios for these species were obtained. Accurate measurement of the Xe and Kr isotopic abundance in this atmosphere provides an important data point in testing theories of planetary formation and atmospheric evolution. The measurement is also essential for a stringent test for the Martian origin of the SNC meteorites, since the Kr and Xe fractionation pattern seen in gas trapped in glassy nodules of an SNC (EETA 79001) is unlike any other known solar system resevoir. Current flight mass spectrometer designs combined with the new technology of a high-performance vacuum pumping system show promise for a substantial increase in gas throughput and the dynamic range required to accurately measure these trace species. Various aspects of this new technology are discussed.
Mahaffy, P.↗
Slow crack growth in sintered silicon nitride
The strength and crack growth characteristics of a sintered silicon nitride were studied at 1000 C. Fractographic analysis of material failing in dynamic fatigue revealed the presence of slow crack growth (SCG) at stressing rates below 6 ksi/min. This material can sustain a 40-ksi flexural stress at 1000 C for 400 h or more but is susceptible to both SCG and creep deformation at higher stress levels. The crack velocity exponent (N) determined both from dynamic and static fatigue experiments lies in a range from 13 to 22. The subcritical crack growth and creep behavior at 1000 C is primarily controlled by the deformation of an intergranular glassy phase.
Khandelwal, P. K.↗
Comparison of dynamic fatigue behavior between SiC whisker-reinforced composite and monolithic silicon nitrides
The dynamic fatigue behavior of 30 vol percent silicon nitride whisker-reinforced composite and monolithic silicon nitrides were determined as a function of temperature from 1100 to 1300 C in ambient air. The fatigue susceptibility parameter, n, decreased from 88.1 to 20.1 for the composite material, and from 50.8 to 40.4 for the monolithic, with increasing temperature from 1100 to 1300 C. A transition in the dynamic fatigue curve occurred for the composite material at a low stressing rate of 2 MPa/min at 1300 C, resulting in a very low value of n equals 5.8. Fractographic analysis showed that glassy phases in the slow crack growth region were more pronounced in the composite compared to the monolithic material, implying that SiC whisker addition promotes the formation of glass rich phases at the grain boundaries, thereby enhancing fatigue. These results indicate that SiC whisker addition to Si3 N4 matrix substantially deteriorates fatigue resistance inherent to the matrix base material for this selected material system.
Choi, Sung R.↗
Rb-Sr and Sm-Nd Isotopic Studies of Lunar Green and Orange Glasses
Lunar volcanic glassy beads have been considered as quenched basaltic magmas derived directly from deep lunar mantle during fire-fountaining eruptions [1]. Since these sub-mm size glassy melt droplets were cooled in a hot gaseous medium during free flight [2], they have not been subject to mineral fractionations. Thus, they represent primary magmas and are the best samples for the investigation of the lunar mantle. Previously, we presented preliminary Rb- Sr and Sm-Nd isotopic results for green and orange glassy samples from green glass clod 15426,63 and orange soil 74220,44, respectively [3]. Using these isotopic data, initial Sr-87/Sr-86 and Nd ratios for these pristine mare glass sources can be calculated from their respective crystallization ages previously determined by other age-dating techniques. These isotopic data were used to evaluate the mineralogy of the mantle sources. In this report, we analyzed additional glassy samples in order to further characterize isotopic signatures of their source regions. Also, we'll postulate a relationship between these two major mare basalt source mineralogies in the context of lunar magma ocean dynamics.
Shih, C.-Y.↗
Formation conditions of pyroxene-olivine and magnesian olivine chondrules
Dynamic crystallization experiments performed on a Type I and an intermediate Type II/III composition demonstrate chondrule texture is controlled by the abundance of heterogeneous nuclei. This factor is controlled by the maximum initial temperature relative to the olivine disappearance temperature for the given heating time. Glassy and excentroradial textures form from superheated melts with no nuclei, and barred textures form with initial temperatures near the olivine disappearance temperature. Porphyritic and granular textures form with initial temperatures below the liquidus with abundant nuclei. Comparison of zoning characteristics of experimental olivines with those in natural porphyritic olivine chondrules indicates cooling rates of 100 to 1000 C/h, whereas olivine morphology indicates barred olivines cooled at rates of 250 to 1000 C/h. Texture/composition relationships suggest chondrules experienced initial temperatures below 1750 C. These observations are consistent with the idea that chondrules formed by transient heating in dust-rich regions (i.e., in the midplane) of the solar nebula.
Radomsky, Patrick M.↗
Chondrule formation in lightning discharges
Chondrules represent a significant mass fraction of primitive meteorites. These millimeter-sized glassy droplets appear to be the products of intensive transient heating events. Their size distribution, chemical and mineral composition, texture, isotope composition suggest that chondrules were produced as a result of short-duration melting followed by rapid cooling of solid precursor particles. Gas-dynamics heating, magnetic reconnection, and electrostatic discharges are thought to be the leading candidates to explain chondrule formation. In this paper we summarize our recent theoretical progress on the effects of 'lightning' in the early solar system and also report on preliminary results from our laboratory experiments. Differential settling of various sized dust particles toward the midplane of the nebula is suspected to build large-scale charge separations that episodically relax via the electric breakdown of the nebular gas. The electrostatic discharge os analogous to lightning in the Earth's atmosphere.
Horanyi, M.↗