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All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

Magnetic Stirling cycles - A new application for magnetic materials

There is the prospect of a fundamental new application for magnetic materials as the working substance in thermodynamic cycles. Recuperative cycles which use a rare-earth ferromagnetic material near its Curie point in the field of a superconducting magnet appear feasible for applications from below 20 K to above room temperature. The elements of the cycle, advanced in an earlier paper, are summarized. The basic advantages include high entropy density in the magnetic material, completely reversible processes, convenient control of the entropy by the applied field, the feature that heat transfer is possible during all processes, and the ability of the ideal cycle to attain Carnot efficiency. The mean field theory is used to predict the entropy of a ferromagnet in an applied field and also the isothermal entropy change and isentropic temperature change caused by applying a field. Results are presented for J = 7/2 and g = 2. The results for isentropic temperature change are compared with experimental data on Gd. Coarse mixtures of ferromagnetic materials with different Curie points are proposed to modify the path of the cycle in the T-S diagram in order to improve the efficiency or to increase the specific power.

Brown, G. V.↗
NASA NTRS1983

Magnetic heat pumping

The method employs ferromagnetic or ferromagnetic elements, preferably of rare-earth based material, for example gadolinium, and preferably employs a regenerator. The steps comprise controlling the temperature and applied magnetic field of the element to cause the state of the element as represented on a temperature-magnetic entropy diagram repeatedly to traverse a loop. The loop may have a first portion of concurrent substantially isothermal or constant temperature and increasing applied magnetic field, a second portion of lowering temperature and constant applied magnetic field, a third portion of isothermal and decreasing applied magnetic field, and a fourth portion of increasing temperature and constant applied magnetic field. Other loops may be four sided, with, for example, two isotherms and two adiabats (constant entropy portions.

Brown, G. V.↗
NASA NTRS1984

High-temperature thermoelectric energy converstion. I - Theory

The high-temperature thermoelectric energy-conversion theory is examined. It is shown that semiconductors are the logical choices for high-figure of merit-value materials, but the requirements for optimization differ depending on whether the material is classed as a broad-band or narrow-band semiconductor. Optimization is discussed as a function of temperature. Phonon scattering mechanisms are considered; and for the reduction of thermal conductivity, basic material guidelines are given. Although experimental results indicate that ZT (where Z is the figure of merit and T is the temperature) of about 1 represents an upper limit, there is in fact, no theoretical limitation. It is unlikely that the Z values will be significantly reduced by radiation transfer at temperatures lower than 2000 K. The current status of materials research is also considered. The rare-earth chalcogenides which behave as n-type semi-conductors and the boron-rich borides which exhibit hopping p-type conductivity behavior are the materials that show promise for high-temperature Z values. The reasons for low thermal conductivities in these materials is discussed.

Wood, C.↗
NASA NTRS1972

The lunar interior

The compressional velocities are estimated for materials thought to be important in the lunar interior and compared with lunar seismic results. The lower lunar crust has velocities appropriate for basalts or anorthosites. Anorthosite is preferred if lunar basalts result from a small degree of partial melting. The high velocities associated with the uppermost mantle imply high densities and a change to a lighter assemblage at depths of the order of 120 km. Ca- and Al-rich minerals are important components of both the lower crust and the upper mantle. Most of the moon may have accreted from refractory material rich in Ca, Al, U, and the rare-earth elements. The important mineral of the upper mantle is garnet; possible accessory minerals are kyanite, spinel and rutile. If the seismic results stand up, the high-velocity layer in the moon is more likely to be a high-pressure form of anorthosite than eclogite, pyroxenite, or dunite.

Anderson, D. L.↗
NASA NTRS1983

Refractory materials for high-temperature thermoelectric energy conversion

Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.

Wood, C.↗
NASA NTRS1984

Refractory materials for high-temperature thermoelectric energy conversion

Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimaiation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.

Wood, C.↗
NASA NTRS1972

Luna 16 - Some Li, K, Rb, Sr, Ba, rare-earth, Zr, and Hf concentrations.

Concentrations of Li, K, Rb, Sr, Na, rare-earths, Zr and Hf have been determined for some Luna 16 core materials by mass-spectrometric isotope-dilution. Two regolith fines samples from different depths in the core, and four rock-chips, including both igneous rocks and breccias, have similar trace-element concentrations. The Luna 16 materials have general lunar trace-element characteristics but differ from other returned lunar samples in a manner that suggests the presence of excess feldspar. Unless the Luna 16 igneous rocks are fused soils, they appear to represent either partial plagioclase cumulates or the least differentiated igneous material yet returned from the moon. The similarity in trace-element concentrations of the igneous rocks and the fines would then suggest largely local derivation of the Luna 16 regolith.

Philpotts, J. A.↗
NASA NTRS1979

The origin of KREEP

KREEP is a lunar material having very high concentrations of incompatible elements; its name is an acronym for the incompatibles K, rare-earth elements (REE), and P. Although a few pristine (endogenously igneous) KREEPy samples were returned from the Apollo 15 and 17 sites, most KREEPy samples are polymict breccias. Most models of KREEP petrogenesis have been based on partial melting of a variety of sources. Such models fail to explain the veritable absence of variations in incompatible element patterns over the sampled portion of the moon. We have defined a KREEP component based on the average composition of Apollo 14 breccias having extremely high concentrations of incompatible elements. Normalization of accurate incompatible data for KREEPy samples from the Apollo 12, 14, 15, 16, and 17 sites to this component virtually always shows no resolvable fractionation (e.g., <10% variation in the La/Lu ratio), whereas partial melting models typically produce larger fractionations (±20–25% in La/Lu) from a factor of 2 difference in degree of partial melting. Required is a single major source that could provide KREEP to widely separated locations on the nearside of the moon. The anorthositic crust of the moon is commonly attributed to the flotation of plagioclase on a deep, moon-wide magma ocean. Fractional crystallization of this magma ocean would have produced large enrichments of incompatibles in a residual liquid. No other plausible major source of incompatibles has been proposed. We borrow the German prefix ur—meaning primeval and designate this residual liquid ‘urKREEP.’ We propose that all KREEPy rocks originated by dilution of urKREEP with crustal or mantle materials during assimilation, or zone-refining (pristine samples), or impact-induced brecciation (breccias and melt rocks). The formation of urKREEP cannot be dated precisely. Correction of breccia Rb-Sr model ages for Rb loss or gain during the early intense bombardments yields ages that cluster in the range 4.4–4.5 Gy. This implies that crystallization of the magma ocean was essentially complete at this time and is in general agreement with U-Pb evidence indicating crustal formation at 4.4 Gy. Assuming that the moon had the composition of an H-group chondrite depleted in Fe-Ni and FeS and that half the incompatibles fractionated into materials other than urKREEP, the thickness of a moon-wide urKREEP layer was <2 km. Thorium concentrations determined by gamma ray spectroscopy indicate that about 4% of the incompatibles in an H chondritic moon are now in the outermost kilometer.

Paul H. Warren↗
NASA NTRS1977

UH cosmic rays and solar system material - The elements just beyond iron

The nucleosynthesis of cosmic-ray elements between the iron peak and the rare-earth region is examined, and compositional changes introduced by propagation in interstellar space are calculated. Theories on the origin of elements heavier than iron are reviewed, a supernova model of explosive nucleosynthesis is adopted for the ultraheavy (UH) cosmic rays, and computational results for different source distributions are compared with experimental data. It is shown that both the cosmic-ray data and the nucleosynthesis calculations are not yet of sufficient precision to pinpoint the processes occurring in cosmic-ray source regions, that the available data do provide boundary conditions for cosmic-ray nucleosynthesis, and that these limits may apply to the origin of elements in the solar system. Specifically, it is concluded that solar-system abundances appear to be consistent with a superposition of the massive-star core-helium-burning s-process plus explosive-carbon-burning synthesis for the elements from Cu to As and are explained adequately by the s- and r-processes for heavier elements.

Wefel, J. P.↗
NASA NTRS1973

Rare earths, other trace elements and iron in Luna 20 samples.

The results of the analysis by neutron activation of six samples from the Luna 20 mission and one sample of less than 1 mm fines from Apollo 16 are reported. The concentrations of the rare-earth elements (REE) in the samples of fines from Luna 20 and Apollo 16 are less than those found for corresponding materials from the mare areas but a negative Eu anomaly is still present. The concentrations of the REE in fines from Luna 20 are only about two-thirds as great as in the sample of Apollo 16 fines, but the concentration of Co, Sc and Cr are greater by factors ranging from 1.5 to 2.3.

Helmke, P. A.↗
NASA NTRS1973

Major and trace elements in igneous rocks from Apollo 15.

The concentrations of major and trace elements have been determined in igneous rocks from Apollo 15. All materials analyzed have typical depletions of Eu except for minerals separated from sample 15085. Four samples have concentrations of trace elements that are similar to those of KREEP. The samples of mare basalt from Apollo 15 have higher concentrations of FeO, MgO, Mn, and Cr and lower concentrations of CaO, Na2O, K2O, and rare-earth elements (REE) as compared to the samples of mare basalt from Apollos 11, 12, and 14. The samples can be divided into two groups on the basis of their normative compositions. One group is quartz normative and has low concentrations of FeO while the other is olivine normative and has high concentrations of FeO. The trace element data indicate that the samples of olivine normative basalt could be from different portions of a single lava flow.

Helmke, P. A.↗
NASA NTRS1973

Apollo 16 returned lunar samples - Lithophile trace-element abundances

Lithium, K, Rb, Sr, Ba, rare-earth, Zr, and Hf abundances have been determined by mass-spectrometric isotope-dilution for Apollo 16 soils, anorthosite 61016, and 'basalt' 68415 whole-rock and separated pyroxene and plagioclase. Our sample of 61016 is similar to some other lunar anorthosites in lithophile trace-element concentrations but at a slightly lower level. It was probably accumulated from a little differentiated basalt. Basalt 68415 might be a homogeneous mixture of KREEP and anorthosite material; it appears to have crystallized under conditions as reducing as those holding for mare-basalts. The soil fines cover only a limited compositional range. No obvious chemical differences were noted between the Descartes and Cayley formations. Most of the compositional variation of the soils can be accounted for in terms of the addition of plagioclase. The existence of very high alumina basalt as an independent magma-type appears debatable in view of its KREEP-like lithophile trace-element relative concentrations and the observed lunar radioactivity distribution.

Philpotts, J. A.↗
NASA NTRS1981

Hard permanent magnet development trends and their application to A.C. machines

The physical and magnetic properties of Mn-Al-C, Fe-Cr-Co, and RE-TM (rare earth-transition metal intermetallics) in polymer and soft metal bonded or sintered form are considered for ac circuit machine usage. The manufacturing processes for the magnetic materials are reviewed, and the mechanical and electrical properties of the magnetic materials are compared, with consideration given to the reference Alnico magnet. The Mn-Al-C magnets have the same magnetic properties and costs as Alnico units, operate well at low temperatures, but have poor high temperature performance. Fe-Cr-Co magnets also have comparable cost to Alnico magnets, and operate at high or low temperature, but are brittle, expensive, and contain Co. RE-Co magnets possess a high energy density, operate well in a wide temperature range, and are expensive. Recommendation for exploring the rare-earth alternatives are offered.

Mildrum, H. F.↗
NASA NTRS1973

Suitability of the rare-earth compounds Dy2Ti2O7 and Gd3Al5O12 for low temperature (4K-20K) magnetic refrigeration cycle

Measurements were made of the magnetic entropy and magnetization of powered samples of the compounds Dy2Ti2O7 and Gd3Al5O12. The magnetization was measured for temperatures at and below 4.2 K, in applied fields ranging to 7.0 tesla. Isothermal changes in magnetic entropy were measured for temperatures from 1.2 to 20 K, in applied fields up to 10 tesla. The results of the measurements are consistent with a doublet ground state for Dy2Ti2O7, and an eight-fold degenerate ground state for Gd3Al5O12. Absolute values of magnetic entropy have been obtained at the lower temperatures, permitting the isotherms to be properly located in the S-H plane with the use of adiabatic magnetization data. The iso-field lines in the S-T plane were determined. The results indicate that Dy2Ti2O7 can absorb a maximum of 71 + or - 4 joules/kg of heat at 4.2 K, while Gd3Al5O12 can absorb 233 + or - joules/kg at the same temperature. The large difference between the two is most likely a result of crystal field interactions in the dysoprosium compound. Both materials can be cycled adiabatically between 4.2 and 20 K.

Flood, D. J.↗
NASA NTRS1978

Rare-earth abundances in chondritic meteorites

Fifteen chondrites, including eight carbonaceous chondrites, were analyzed for rare earth element abundances by isotope dilution. Examination of REE for a large number of individual chondrites shows that only a small proportion of the analyses have flat unfractionated REE patterns within experimental error. While some of the remaining analyses are consistent with magmatic fractionation, many patterns, in particular those with positive Ce anomalies, can not be explained by known magmatic processes. Elemental abundance anomalies are found in all major chondrite classes. The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibrium or were introduced at a late stage of chondrite formation. Large-scale segregation of gas and condensate is implied, and bulk variations in REE abundances between planetary bodies is possible.

Evensen, N. M.↗