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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts

Abstract An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29 Si solid state NMR and Ti K -edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29 Si NMR shows that in both Ti-bearing Na 2 O•4SiO 2 (NS4) and Na 2 O•8SiO 2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q 4 peak in the 29 Si NMR spectra reflecting Ti nearest neighbors for Si in Q 4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29 Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5] Ti atoms and the formation of [5] Ti clusters at relatively low Ti concentrations, with no evidence for Ti–Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q 4 speciation (no significant Na– [4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.

Ackerson, Michael R.↗
DOE OSTI2021

Increasing melt efficiency and secondary alloy usage in aluminum die casting

In this project, the focus was to develop thermodynamic and kinetic models for the aluminum melting process involving secondary alloys, refractory materials and flux materials. The major research outcome of this study is 1) the refractory composition of CaO (8-12%), microsilica (1-3%), BaSO 4 and/or BaO (no more than 5%), B 2 O 3 (5%) and Al 2 O 3 (balance) effectively reduced the reactions with liquid Al and alloying/impurity elements and heat transfer during melting and holding process. 2) a flux composition of NaCl-KCl-(1-10%)KAlF 4 exhibited an effective covering effect and prevented the dross formation during melting of Al process. 3) A high Fe (0.44%) content recycled Al alloy with compatible mechanical properties was developed based on the impurities control methods, which provides great potential to replace the commercial structural alloys from primary Al and increase the usage of secondary alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Filament Formation and Melt Spinning of Coal-Based Mesophase Pitch for Carbon Fiber Production

High-performance carbon fibers excel as high specific strength and modulus materials, and are utilized in composites applications ranging across aerospace, automotive, energy, infrastructure, and sports equipment sectors. Compared to PAN-based carbon fiber, mesophase pitch-based carbon fiber has lower tensile strength but provides a higher modulus, higher thermal conductivity, and a lower cost potential. However, challenges in stable, continuous melt spinning processing are a serious limiting factor. Unlike typical melt spinning of long, linear chain polymers, mesophase pitch is a comprised of relatively shorter polycyclic aromatic hydrocarbons which form a liquid crystal. In its ‘green’ or ‘as-spun’ state, the fibers are very fragile. Moreover, its temperature of processing is quite high, often approaching 400ºC. Complex flow dynamics combined with short length and time scale heat transfer render its melt spinning a formidable processing challenge. Improved understanding of the root causes for nascent filament breakage and spinning instabilities are needed. This work aims to determine fundamental phenomena that govern mesophase pitch filament formation by comparison of required draw force and uninterrupted spinning minutes with applied draw down ratio. The effect of perturbations on spinning stability are analyzed using capillary rheometry, microscopy of elongating filaments, and filtration.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Predicting Selective Laser Printing Print Quality of Polymer Powders through Melt Flow Index

Selective Laser Sintering (SLS) uses a precisely controlled laser to fuse polymer powder to build complex 3D shapes. While SLS covers a wide application space, the processing knowledge of polymer powder is limited, restricting the number of commercial powders available. This study serves to expand the processing knowledge of polypropylene and polyethylene in parallel with a “mature” SLS feedstock, nylon, through melt flow index (MFI) characterization. Differential Scanning Calorimetry (DSC) was used to explore the sintering window of the polymers. Polyethylene and polypropylene exhibited a relatively narrow sintering window between 4 – 5 °C, whereas the sintering window of nylon was much wider, between 23 – 24 °C. This suggests that the print quality between polyethylene and polypropylene would be similar; however, X-ray computed tomography revealed a higher volume of print defects, voids, and de lamination in polyethylene than in polypropylene. MFI analysis provided additional insight into the difference in print quality, as the MFI of polyethylene was 7.16 g/10 min, 9.95 g/10 min for polypropylene, and 17.23 g/10 min for nylon. MFI is inversely correlated to melt viscosity, and a low melt viscosity is desired for proper coalescing between the layers and particles. These results suggest that MFI is a promising tool, in conjunction with traditional thermal analysis, for screening candidate powder feedstocks for SLS and optimization of print parameters for novel powders.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Melting and Re-Freezing Leads to Irreversible Changes in the Morphology and Molecular-Level Dynamics of Pfizer-BioNTech COVID-19 Vaccine

As an mRNA-based vaccine, the Pfizer-BioNTech COVID-19 vaccine has stringent cold storage requirements to preserve functionality of the mRNA active ingredient. To this end, lipid components of the vaccine formulation play an important role in stabilizing and protecting the mRNA molecule for long-term storage. The purpose of the current study was to measure molecular-level dynamics as a function of temperature in the Pfizer-BioNTech COVID-19 vaccine to gain microscopic insight into its thermal stability. Materials and Methods: We used quasielastic and inelastic neutron scattering to probe (1) the vaccine extracted from the manufacturer-supplied vials and (2) unperturbed vaccine in the original manufacturer-supplied vials. The latter measurement was possible due to the high penetrative power of neutrons. Upon warming from the low-temperature frozen state, the vaccine in its original form exhibits two-step melting, indicative of a two-phase morphology. Once the melting is completed (above 0 °C), vaccine re-freezing cannot restore its original two-phase state. This observation is corroborated by the changes in the molecular vibrational spectra. The molecular-level mobility measured in the resulting single-phase state of the re-frozen vaccine greatly exceeds the mobility measured in the original vaccine. Even a brief melting (above 0 °C) leads to an irreversible alteration of the two-phase morphology of the original vaccine formulation. Re-freezing of the vaccine results in a one-phase morphology with much increased molecular-level mobility compared to that in the original vaccine, suggesting irreversible deterioration of the vaccine’s in-storage stability. Neutron scattering can be used to distinguish between the vibrational spectra characteristic of the original and deteriorated vaccines contained in the unperturbed original manufacturer-supplied vials.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Frank–Kasper Phases of Diblock Copolymer Melts: Self-Consistent Field Results of Two Commonly Used Models

We constructed phase diagrams of conformationally asymmetric diblock copolymer A-B melts using the polymer self-consistent field (SCF) calculations of both the dissipative particle dynamics chain (DPDC) model (i.e., compressible melts of discrete Gaussian chains with the DPD non-bonded potential) and the “standard” model (i.e., incompressible melts of continuous Gaussian chains with the Dirac δ-function non-bonded potential) in the χN-ε plane, where χN and ε characterize, respectively, the repulsion and conformational asymmetry between the A and B blocks, at the A-block volume fraction f = 0.2 and 0.3. Consistent with previous SCF calculations of the “standard” model, σ and A15 are the only stable Frank–Kasper (FK) phases among the five FK (i.e., σ, A15, C14, C15 and Z) phases considered. The stability of σ and A15 is due to their delicate balance between the energetic and entropic contributions to the Helmholtz free energy per chain of the system, which, within our parameter range, increases in the order of σ/A15, Z, and C14/C15. While in general the SCF phase diagrams of these two models are qualitatively consistent, A15 is not stable for the DPDC model at the copolymer chain length N = 10 and f = 0.3; any differences in the SCF phase diagrams are solely due to the differences between these two models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Determination of work functions near melting points of refractory metals by using a direct-current arc

Effective work functions of refractory metals at temperatures near their melting points were determined by using a direct-current arc. A metal wire connected as the cathode was melted by striking an arc discharge in an argon atmosphere. A melted sphere was formed with a definite emitting area which was calculated from the sphere diameter measured after terminating the arc. Effective work functions were calculated from the Richardson-Dushman equation by using this emission area. The procedure is experimentally advantageous because surface cleanliness of the specimen is not critical, high vacuum is not required, and the anode-cathode spacing is not critical.

Gordon, W. A.↗
NASA NTRS1972

Shock melting and vaporization of lunar rocks and minerals.

The entropy associated with the thermodynamic states produced by hypervelocity meteoroid impacts at various velocities are calculated for a series of lunar rocks and minerals and compared with the entropy values required for melting and vaporization. Taking into account shock-induced phase changes in the silicates, we calculate that iron meteorites impacting at speeds varying from 4 to 6 km/sec will produce shock melting in quartz, plagioclase, olivine, and pyroxene. Although calculated with less certainty, impact speeds required for incipient vaporization vary from 7 to 11 km/sec for the range of minerals going from quartz to periclase for aluminum (silicate-like) projectiles. The impact velocities, which are required to induce melting in a soil, are calculated to be in the range of 3 to 4 km/sec, provided thermal equilibrium is achieved in the shock state.

Ahrens, T. J.↗
NASA NTRS1972

Effects of additives on volume change on melting, surface tension, and viscosity of liquid aluminum oxide

The effects of various oxide additives on the volume change on melting, the surface tension, and the viscosity of liquid Al2O3 were studied. Additives of Sm2O3, MgO, and Y2O3 which form solid solutions, compounds, and multiphase solids with Al2O3 were studied. A review of the property data for Al2O3 and Al2O3 containing oxide additives is presented. Oxide additives to Al2O3 reduce the volume change on melting and with the exception of SiO2 lower the viscosity; surface tensions change with oxide additives, but changes vary with different container material. Viscosity and volume change on melting appeared to be significantly more important for studying the properties of liquid oxides than surface tension. Supercooling of 270 K of yttrium aluminum garnet was observed.

Bates, J. L.↗
NASA NTRS1973

Segregation effects during solidification in weightless melts

Two types of melt segregation effects were studied: (1) evaporative segregation, or segregation due to surface evaporation; and (2) freezing segregation, or segregation due to liquid-solid phase transformation. These segregation effects are closely related. In fact, evaporative segregation always precedes freezing segregation to some degree and must often be studied prior to performing meaningful solidification experiments. This is particularly true since evaporation may cause the melt composition, at least at the critical surface regions or layers to be affected manyfold within seconds so that the surface region or layer melting point and other thermophysical properties, nucleation characteristics, base for undercooling, and critical velocity to avoid constitutional supercooling, may be completely unexpected. An important objective was, therefore, to develop the necessary normal evaporation equations for predicting the compositional changes within specified times at temperature and to correlate these equations with actual experimental data collected from the literature.

Li, C.↗
NASA NTRS1974

Rock melting technology and geothermal drilling

National awareness of the potential future shortages in energy resources has heightened interest in exploration and utilization of a variety of geothermal energy (GTE) reservoirs. The status of conventional drilling of GTE wells is reviewed briefly and problem areas which lead to higher drilling costs are identified and R and D directions toward solution are suggested. In the immediate future, an expanded program of drilling in GTE formations can benefit from improvements in drilling equipment and technology normally associated with oil or gas wells. Over a longer time period, the new rock-melting drill bits being developed as a part of the Los Alamos Scientific Laboratory's Subterrene Program offer new solutions to a number of problems which frequently hamper GTE drilling, including the most basic problem - high temperature. Two of the most favorable characteristics of rock-melting penetrators are their ability to operate effectively in hot rock and produce glass linings around the hole as an integral part of the drilling process. The technical advantages to be gained by use of rock-melting penetrators are discussed in relation to the basic needs for GTE wells.

Rowley, J. C.↗
NASA NTRS1975

Flows of impact melt at lunar craters

Lavalike materials that were emplaced in a fluid state occur in and around lunar impact craters whose diameters range from 3 km to more than 200 km and whose ages span a time interval of at least 3.5 billion years. The distribution of the lavalike deposits conforms to asymmetries of other ejecta from the same craters, and the material is concentrated downrange to distances as great as a crater radius. The character and distribution of the lavalike materials support the idea that they formed by impact melting rather than by volcanism. Returned samples indicate that materials with appropriate physical characteristics are generated by partial melting of feldspathic rocks by impact. The geologic evidence at lunar craters suggests that there is more melt rock in and near the craters than is predicted by experiment and theory.

Howard, K. A.↗
NASA NTRS1977

Effect of double vacuum melting and retained austenite on rolling-element fatigue life of AMS 5749 bearing steel

AMS 5749 steel combines the tempering, hot hardness, and hardness retention characteristics of AISI M-50 steel with the corrosion and oxidation resistance of AISI 440C stainless steel. The five-ball fatigue tester was used to evaluate the rolling-element fatigue life of AMS 5749. Double vacuum melting (vacuum induction melting plus vacuum arc remelting, VIM-VAR) produced AMS 5749 material with a rolling-element fatigue life at least 14 times that of vacuum induction melting alone. The VIM-VAR AMS 5749 steel balls gave lives from 6 to 12 times greater than VIM-VAR AISI M-50 steel balls. The highest level of retained austenite, 14.6 percent, was significantly detrimental to rolling-element fatigue life relative to the intermediate level of 11.1 percent.

Parker, R. J.↗
NASA NTRS1976

Thermal regimes in cratered terrain with emphasis on the role of impact melt

The distribution of bombardment energy in the moon's crust and the types of phase transformation resulting from this energy input are investigated. It is seen that the major significance of impact melts in the period of intense cratering is that they transfer most of the high-temperature heat following cratering and thus take part in many of the phase transformations on planetary surfaces. Energy partitioning studies suggest that of the projectiles' total kinetic energy, 23 to 35% is converted into heat by passage of the shock fronts, 43 to 53% transports ejecta and then is dissipated at modest temperature increases over a broad area, 8 to 24% is consumed comminuting country rock, and less than 1% becomes seismic and radiant energy. Subsequent to its formation, the melt is violently mixed with much colder debris to form the sheets of impact melt and the breccias.

Simonds, C. H.↗
NASA NTRS1976

Poikilitic KREEP impact melts in the Apollo 14 white rocks

A KREEP-rich fragment-laden melt series in the Apollo 14 white rocks is interpreted to be the result of impact into a source region possibly consisting of KREEP volcanic rock flows, underlain and surrounded by anorthositic-troctolitic highlands rocks. The melt groundmass is a high-alumina, high-K2O Fra Mauro basalt, enriched in plagioclase. A poikilitic texture is developed in the coarser members of the series, possibly as a result of the impact melt being seeded with relict plagioclase nuclei.

Ryder, G.↗
NASA NTRS1978

Manicouagan impact melt, Quebec. II - Chemical interrelations with basement and formational processes

The basement rocks of Manicouagan exhibit a wide compositional range (40-72% SiO2). Least squares mixing calculations indicate that the average composition of the Manicouagan melt sheet can be modeled for 9 major and 11 trace elements by a mixture of 4.5% anorthosite, 55.5% mafic gneiss, and 40.0% tan gneiss with a granitic-granodioritic composition. The underrepresentation of anorthosite relative to its present distribution is considered. The homogeneous composition of the melt (57.75 + or - 1.21% SiO2) relative to that of the postulated target is explained in a model outlining the dynamic conditions existing during the formation of the melt and its accompanying movement into the excavated cavity.

Grieve, R. A. F.↗
NASA NTRS1978

Rb-Sr isochron age of the Manicouagan melt sheet, Quebec, Canada

Rb-Sr isotopic data for mineral separates from a rock of the Manicouagan impact melt sheet define an isochron of age T = 214 + or - 5 (2 sigma) m.y. which agrees with the K-Ar age of 210 + or - 8 (2 sigma) calculated by Wolfe (1971). The initial Sr-87/Sr-86 ratio I is found to be 0.70991 + or - 0.00007 (2 sigma); four whole rock samples yield age-corrected I values ranging from 0.70965 to 0.71006. These high I values support the hypothesis that the melt sheet was derived by total melting of Grenville basement rocks during the impact event 214 m.y. ago.

Jahn, B.↗