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At least 811 records · Page 45

Creep-rupture of polymer-matrix composites

An accelerated characterization method for resin matrix composites is reviewed. Methods for determining modulus and strength master curves are given. Creep rupture analytical models are discussed as applied to polymers and polymer matrix composites. Comparisons between creep rupture experiments and analytical models are presented. The time dependent creep rupture process in graphite epoxy laminates is examined as a function of temperature and stress level.

Brinson, H. F.↗

A Raman Study of Carbonates and Organic Contents in Five CM Chondrites

Carbonates comprise the second most abundant class of carbon-bearing phases in carbonaceous chondrites after organic matter (approximately 2 wt.%), followed by other C-bearing phases such as diamond, silicon carbide, and graphite. Therefore, understanding the abundances of carbonates and the associated organic matter provide critical insight into the genesis of major carbonaceous components in chondritic materials. Carbonates in CM chondrites mostly occur as calcite (of varying composition) and dolomite. Properly performed, Raman spectroscopy provides a non-destructive technique for characterizing meteorite mineralogy and organic chemistry. It is sensitive to many carbonaceous phases, allows the differentiation of organic from inorganic materials, and the interpretation of their spatial distribution. Here, with the use of Raman spectroscopy, we determine the structure of the insoluble organic matter (IOM) in the matrix and carbonate phases in five CM chondrites: Jbilet Winselwan, Murchison, Nogoya, Santa Cruz, and Wisconsin Range (WIS) 91600, and interpret the relative timing of carbonate precipitation and the extent of the associated alteration events.

Chan, Q. H. S.↗

Studies on Hot-Melt Prepregging of PMR-II-50 Polyimide Resin with Graphite Fibers

A Second generation PMR (in situ Polymerization of Monomer Reactants) polyimide resin, PMR-II-50, has been considered for high temperature and high stiffness space propulsion composites applications for its improved high temperature performance. As part of composite processing optimization, two commercial prepregging methods: solution vs. hot-melt processes were investigated with M40J fabrics from Toray. In a previous study a systematic chemical, physical, thermal and mechanical characterization of these composites indicated that poor resin-fiber interfacial wetting, especially for the hot-melt process, resulted in poor composite quality. In order to improve the interfacial wetting, optimization of the resin viscosity and process variables were attempted in a commercial hot-melt prepregging line. In addition to presenting the results from the prepreg quality optimization trials, the combined effects of the prepregging method and two different composite cure methods, i.e., hot press vs. autoclave on composite quality and properties are discussed.

Shin, E. Eugene↗

Studies on Hot-Melt Prepregging on PRM-II-50 Polyimide Resin with Graphite Fibers

A second generation PMR (in situ Polymerization of Monomer Reactants) polyimide resin PMR-II-50, has been considered for high temperature and high stiffness space propulsion composites applications for its improved high temperature performance. As part of composite processing optimization, two commercial prepregging methods: solution vs. hot-melt processes were investigated with M40J fabrics from Toray. In a previous study a systematic chemical, physical, thermal and mechanical characterization of these composites indicated the poor resin-fiber interfacial wetting, especially for the hot-melt process, resulted in poor composite quality. In order to improve the interfacial wetting, optimization of the resin viscosity and process variables were attempted in a commercial hot-melt prepregging line. In addition to presenting the results from the prepreg quality optimization trials, the combined effects of the prepregging method and two different composite cure methods, i.e. hot press vs. autoclave on composite quality and properties are discussed.

Shin, E. Eugene↗

$In-situ$ synchrotron x-ray diffraction and thermal expansion of TiB2 up to ~3050 °C

There is an increasing interest in understanding the performance and properties of ultra-high temperature ceramics due to their high melting points (<3000 °C) that make them promising for extreme environment applications. In-situ high temperature X-ray diffraction experiments were performed on TiB 2 beads up to ~3050 °C. For these experiments, TiB 2 powders were fabricated into spherical beads via gel casting methods and densified in a high temperature graphite furnace. These sample beads were then levitated in a conical nozzle levitator with reducing atmosphere (3% H 2 -Ar) while being heated using a 400 W CO 2 laser. During levitation a collimated synchrotron X-ray source was used to perform in-situ, temperature-dependent structural characterizations. The anisotropic coefficients of thermal expansion of TiB 2 were characterized as a function of temperature up to ~3050 °C. Elucidation of these properties are critical for the advancement of TiB 2 ceramics and other transition metal di-borides for use in high temperature applications such as hypersonic platforms, nuclear reactors, and atmospheric re-entry.

36 MATERIALS SCIENCE↗

HTGR Dust Safety Issues and Needs for Research and Development

This report presents a summary of high temperature gas-cooled reactor dust safety issues. It draws upon a literature review and the proceedings of the Very High Temperature Reactor Dust Assessment Meeting held in Rockville, MD in March 2011 to identify and prioritize the phenomena and issues that characterize the effect of carbonaceous dust on high temperature reactor safety. It reflects the work and input of approximately 40 participants from the U.S. Department of Energy and its National Labs, the U.S. Nuclear Regulatory Commission, industry, academia, and international nuclear research organizations on the topics of dust generation and characterization, transport, fission product interactions, and chemical reactions. The meeting was organized by the Idaho National Laboratory under the auspices of the Next Generation Nuclear Plant Project, with support from the U.S. Nuclear Regulatory Commission. Information gleaned from the report and related meetings will be used to enhance the fuel, graphite, and methods technical program plans that guide research and development under the Next Generation Nuclear Plant Project. Based on meeting discussions and presentations, major research and development needs include: generating adsorption isotherms for fission products that display an affinity for dust, investigating the formation and properties of carbonaceous crust on the inside of high temperature reactor coolant pipes, and confirming the predominant source of dust as abrasion between fuel spheres and the fuel handling system.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Highly Ordered Hierarchical Anodes for Extreme Fast Charging Batteries (Final Report)

The goal of this project is to enable extreme fast charging (XFC) of Li-ion batteries, which was accomplished through a combination of 1) rational design and manufacturing of hierarchically structured anode architectures; 2) blending graphite/hard carbon into a bulk hybrid anode; 3) engineering artificial solid-electrolyte interphase (SEI) coatings with reduced interphase impedance; 4) computational modeling of coupled transport, kinetic, and electrochemical phenomena; and 5) improved fundamental understanding of lithium plating through operando analysis. This work integrated structural, compositional, and surface modification of graphite anodes, multi-physics modeling of ion transport, electrochemical activity, and heat transfer, advanced strategies to detect Li plating, and semi-automated roll-to-roll cell assembly. The unique facilities at the University of Michigan (UM) and Sandia National Laboratories (SNL) were leveraged to manufacture, prototype, and characterize commercially relevant >2Ah and >180 Wh/kg cells with a target of <20% capacity fade over 500 XFC cycles.

25 ENERGY STORAGE↗

Direct Production of Ferrochrome by Segregation Reduction of Chromite in the Presence of Calcium Chloride

A solid reduction process is described whereby chromite is reduced with the help of calcium chloride to produce ferrochrome alloy powders with high metal recovery. The process involves segregation reduction of chromite using graphite as the reductant and calcium chloride as the segregation catalyst. Experiments were performed in the temperature range of 1200–1400 °C to evaluate the influences of various design parameters using both a thermogravimetric analyzer and an electric tube furnace with continuous off-gas analysis. The reduced products were characterized by scanning electron microscopy, X-ray powder diffraction, synchrotron X-ray absorption spectroscopy, and were subjected to wet chemical analysis. It was concluded that the addition of calcium chloride not only accelerated the carbothermic reduction of chromite but also promoted the formation and growth of individual ferrochrome alloy particles. The alloy formation within chromite particles was minimized, enabling the effective separation of ferrochrome alloy particles from the unwanted gangue without the need for fine grinding. Majority of the calcium chloride remained in a recoverable form, with a small percentage (<10 wt %) consumed by reacting with the siliceous gangue forming wadalite. Pure ferrochrome alloy powders were successfully produced with high metal recovery using elutriating separation.

36 MATERIALS SCIENCE↗

Integral throat entrance development, qualification and production for the Antares 3 nozzle

Although design analyses of a G-90 graphite integral throat entrance for the Antares 3 solid rocket motor nozzle indicated acceptable margins of safety, the nozzle throat insert suffered a thermostructural failure during the first development firing. Subsequent re-analysis using properties measured on material from the same billet as the nozzle throat insert showed negative margins. Carbon-carbon was investigated and found to result in large positive margins of safety. The G-90 graphite was replaced by SAI fast processed 4-D material which uses Hercules HM 10000 fiber as the reinforcement. Its construction allows powder filling of the interstices after preform fabrication which accelerates the densification process. Allied 15V coal tar pitch is then used to complete densification. The properties were extensively characterized on this material and six nozzles were subjected to demonstration, development and qualification firings.

Clayton, F. I.↗

Mechanical property characterization and impact resistance of selected graphite/PEEK composite materials

To use graphite/PEEK material on highly curved surfaces requires that the material be drapable and easily conformable to the surface. The mechanical property characterization and impact resistance results are presented for laminates made from two types of graphite/PEEK materials that will conform to a curved surface. These laminates were made from two different material forms. These forms are: (1) a fabric where each yarn is a co-mingled Celion G30-500 3K graphite fiber and PEEK fiber; and (2) an interleaved material of Celion G30-500 3K graphite fiber interleaved with PEEK film. The experimental results from the fabric laminates are compared with results for laminates made from AS4/PEEK unidirectional tape. The results indicate that the tension and compression moduli for quasi-isotropic and orthotropic laminates made from fabric materials are at least 98 pct. of the modulus of equivalent laminates made from tape materials. The strength of fabric material laminates is at least 80 pct. of laminates made from tape material. The evaluation of the fabric material for shear stiffness indicates that a tape material laminate could be replaced by a fabric material laminate and still maintain 89 pct. of the shear stiffness of the tape material laminate.

Baker, Donald J.↗

Investigating the AGN-201M research reactor's unique dominance ratio

The AGN-201M reactor is a small, thermal spectrum reactor located at the University of New Mexico (UNM). It is moderated by polyethylene, reflected by graphite, with fuel comprised of uranium microspheres embedded in polyethylene plates that are separated by an aluminum baffle. The dominance ratio of a multiplying system is the ratio of the first higher-mode eigenvalue to the fundamental, k{sub 1}/k{sub 0}. It is a key parameter in characterizing the rate of convergence, analyzing system stability, and determining how tightly coupled the system's neutron fission is. The purpose of this paper is to investigate the system's unusually low dominance ratio of 0.632. This investigation varied the reactor's physical parameters, such as the fuel geometry, fuel density, and reflector thickness, and examined their impact on the reactor's dominance ratio. Additionally, this study examined neutronically similar systems in hopes of identifying common causes for systems with low dominance ratios. The reason why the dominance ratio of the reactor is small compared to larger thermal reactors was determined to be because of its significantly smaller geometry and the composition of the fuel plates. The reflector's effect on the dominance ratio is small in comparison to the other factors, but was found to have a non-zero effect. Furthermore, the AGN-201M was found to have a significantly lower dominance ratio than systems in which it shares a very high (c{sub k} >95%) degree of neutronic similarity.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Laser Speckle Pattern Stability in Hypersonic Regimes for Experimental Mechanics and Metrological Studies

Here, an empirical study assessing the suitability of laser speckle patterns for use in experimental mechanics research conducted at hypersonic conditions is presented. Speckle patterns generated via coherent optical scattering from a gold-coated graphite surface inserted into a Mach 10 air stream were collected and analyzed using Computer-Aided Speckle Interferometry using two methodologies: a typical spanwise approach involving increasing temporal span between image pairs, and a sequential approach that utilizes a combination of temporal re-referencing and spatial resampling. Results were characterized for spatial-temporal stability and variance. Our observations demonstrate that optical methods relying on stable and properly formed speckle patterns can be used in a hypersonic regime at various Reynolds numbers and common camera frame rates, but the technique is sensitive to the conditions of the airflow and the processing methodology chosen.

42 ENGINEERING↗

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverse problems in heterogeneous and fractured media using peridynamics

The following work presents an adjoint-based methodology for solving inverse problems in heterogeneous and fractured media using state-based peridynamics. We show that the inner product involving the peridynamic operators is self-adjoint. The proposed method is illustrated for several numerical examples with constant and spatially varying material parameters as well as in the context of fractures. We also present a framework for obtaining material parameters by integrating digital image correlation (DIC) with inverse analysis. This framework is demonstrated by evaluating the bulk and shear moduli for a sample of nuclear graphite using digital photographs taken during the experiment. The resulting measured values correspond well with other results reported in the literature. Lastly, we show that this framework can be used to determine the load state given observed measurements of a crack opening. Furthermore, this type of analysis has many applications in characterizing subsurface stress-state conditions given fracture patterns in cores of geologic material.

97 MATHEMATICS AND COMPUTING↗

Effect of matrix resin on the impact fracture characteristics of graphite-epoxy laminates

The effect of resin chemistry on basic impact energy absorbent mechanisms exibited by graphite-epoxy composites was investigated. Impact fracture modes and microscopic resin deformation characteristics were examined for 26 NASA-impacted graphite epoxy laminates with different resin chemistries. Discrete specimen fracture modes were identified through cross sectional examination after impact, and subsequently compared with measured glass transition temperatures, cure cycles, and residual impact capabilities. Microscopic resin deformation mechanisms and their overall relationship to impact loading conditions, voids, and resin content were also characterized through scanning electron microscopic examination of separated fracture surfaces.

Hertzberg, P. E.↗

New Materials for EMI Shielding

Graphite fibers intercalated with bromine or similar mixed halogen compounds have substantially lower resistivity than their pristine counterparts, and thus should exhibit higher shielding effectiveness against electromagnetic interference. The mechanical and thermal properties are nearly unaffected, and the shielding of high energy x-rays and gamma rays is substantially increased. Characterization of the resistivity of the composite materials is subtle, but it is clear that the composite resistivity is substantially lowered. Shielding effectiveness calculations utilizing a simple rule of mixtures model yields results that are consistent with available data on these materials.

Gaier, James R.↗

Pouch cells with 15% silicon calendar-aged for 4 years

Small amounts of high-capacity silicon-based materials are already used in the anode of commercial Li-ion batteries, helping increase their energy density. Despite their remarkable storage capability, silicon continu-ously reacts with the electrolyte, accelerating time-dependent cell performance fade. Nevertheless, very limited information is available on the specific consequences of this reactivity for the calendar aging of Li-ion cells. Here, we analyze aging effects on 450 mAh pouch cells containing 15 wt% of Si (and 73 wt% graphite) after storage at 21 °C for four years. We show that severe losses of Si capacity occurred due to particle isolation when cells were stored at high states of charge (SOC), but not when cells were fully discharged prior to storage. Impedance rise was also significantly higher when cells were kept at high SOCs and was mostly due to phenomena taking place at the cathode; the continuous electrolyte reduction at the anode did not lead to a major increase in bulk electrode resistance. A series of post-test characterization provided additional information on the effects of time and SOC on the calendar aging of Si-containing cells. In conclusion, our study highlights the many challenges posed by Si during calendar aging and can inform future studies in the field.

25 ENERGY STORAGE↗

Final Report: Characterization of Hydrogen Adsorption in Carbon-Based Materials by NMR

In support of DOE/EERE's Fuel Cell Technologies Program Hydrogen Sorption Center of Excellence (HSCoE), UNC conducted Nuclear Magnetic Resonance (NMR) measurements that contributed spectroscopic information as well as quantitative analysis of adsorption processes. While NMR based Langmuir isotherms produce reliable H2 capacity measurements, the most astute contribution to the center is provided by information on dihydrogen adsorption on the scale of nanometers, including the molecular dynamics of hydrogen in micropores, and the diffusion of dihydrogen between macro and micro pores. A new method to assess the pore width using H2 as probe of the pore geometry was developed and is based on the variation of the observed chemical shift of adsorbed dihydrogen as function of H2 pressure. Adsorbents designed and synthesized by the Center were assessed for their H2 capacity, the binding energy of the adsorption site, their pore structure and their ability to release H2. Feedback to the materials groups was provided to improve the materials’ properties. To enable in situ NMR measurements as a function of H2 pressure and temperature, a unique, specialized NMR system was designed and built. Pressure can be varied between 10-4 and 107 Pa while the temperature can be controlled between 77K and room temperature. In addition to the 1H investigation of the H2 adsorption process, NMR was implemented to measure the atomic content of substituted elements, e.g. boron in boron substituted graphitic material as well as to determine the local environment and symmetry of these substituted nuclei. The primary findings by UNC are the following: • Boron substituted for carbon in graphitic material in the planar BC3 configuration enhances the binding energy for adsorbed hydrogen. • Arrested kinetics of H2 was observed below 130K in the same boron substituted carbon samples that combine enhanced binding energy with micropore structure. • Hydrogen storage material made from activated PEEK is well suited for hydrogen storage due to its controlled microporous structure and large surface area. • A new porosimetry method for evaluating the pore landscape using H2 as a probe was developed. 1H NMR can probe the nanoscale pore structure of synthesized material and can assess the pore dimension over a range covering 1.2 nm to 2.5 nm, the size that is desired for H2 adsorption. • Analysis of 1H NMR spectra in conjunction with the characterization of the bonding structure of the adsorbent by 13C NMR distinguishes between a heterogeneous and homogeneous pore structure as evidenced by the work on AX21 and activated PEEK. • Most of the sorbents studied are suited to hydrogen storage at low temperature (T < 100K). Of the materials investigated, only boron substituted graphite has the potential to work at higher temperatures if the boron content in the favorable planar BC3 configuration that actively contributes to adsorption can be increased.

08 HYDROGEN↗