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In situ X-ray absorption fine structure studies of a manganese dioxide electrode in a rechargeable MnO{sub 2}/Zn alkaline battery environment

Description: Electronic and structural aspects of a MnO{sub 2} electrode in a rechargeable MnO{sub 2}/Zn battery environment have been investigated by in situ Mn K-edge X-ray absorption fine structure (XAFS). The relative amplitudes of the three major Fourier transform shells of the EXAFS (extended XAFS) function of the rechargeable MnO{sub 2} electrode in the undischarged state were found to be similar to those found for ramsdellite, a MnO{sub 2} polymorph with substantial corner-sharing linkages among the basic MnO{sub 6} octahedral units. The analyses of the background-subtracted pre-edge peaks and absorption edge regions for the nominally 1-e{sup {minus}} discharged electrode were consistent with Mn{sup 3+} as being the predominant constituent species, rather than a mixture of Mn{sup 4+} and Mn{sup 2+} sites. Furthermore, careful inspection of both the XANES (X-ray absorption near edge structure) and EXAFS indicated that the full recharge of MnO, which had been previously discharged either by a 1- or 2-equivalent corner-sharing linkages compared to the original undischarged MnO{sub 2}.
Date: December 31, 1996
Creator: Mo, Y.; Hu, Y.; Bae, I.T.; Miller, B.; Scherson, D.A. & Antonio, M.R.
Partner: UNT Libraries Government Documents Department

In situ synchrotron x-ray studies of LiMn{sub 2}O{sub 4} cathodes

Description: LiCoO{sub 2} cathodes are now used in most commercial lithium ion batteries. LiMn{sub 2}O{sub 4} is an attractive low cost alternative. However, it is difficult to make reproducibly. At Brookhaven National Laboratory two in situ synchrotron x-ray techniques, that are available at the National Synchrotron Light Source (NSLS), have been used to investigate LiMn{sub 2}O{sub 4}. The techniques are x-ray absorption and high resolution x-ray diffraction. With x-ray absorption it is possible to follow the changes in the Mn oxidation state and the changes in the Mn-O and Mn-Mn bond lengths on cycling. Also it is possible to detect amorphous phases. The high energy x-rays at the diffraction Beam Lines at the NSLS (up to 24 KeV) permit in situ x-ray diffraction, in the transmission mode, in thin lithium and lithium ion cells. The evolution of the structural chances that occur on cycling can be followed. These in situ measurements were done on Li/LiMn{sub 2}O{sub 4} cells with a liquid electrolyte (1 M LiPF{sub 6} in a 1:1:3 PC:EC:DMC solvent).
Date: May 1997
Creator: McBreen, J.; Mukerjee, S. & Yang, X. Q.
Partner: UNT Libraries Government Documents Department

Symmetry breaking at magnetic surfaces and interfaces

Description: Examples represented of how symmetry breaking enters into consideration of the physical properties of magnetic surfaces and ultrathin films. The role of magnetic anisotropy is discussed to understand: (i) the existence of two-dimensional (2D) magnetic long-ranged order at finite temperature, (ii) magnetization scaling behavior at the Curie transition, (iii) the 2D spin reorientation transition, and (iv) step-induced magnetic behavior. Experimental examples cited include ultrathin magnetic Fe and Co overlayer and wedge structures grown onto single crystal substrates that are either flat or curved to produce vicinal surfaces with a continuous gradient in the step density. Also included is an example of an atomically flat manganite intergrowth that appears as a stacking fault in a bulk single crystal of a naturally layered structure.
Date: November 20, 1998
Creator: Qiu, Z. Q.
Partner: UNT Libraries Government Documents Department

Thin-film rechargeable lithium batteries with amorphous Li{sub x}Mn{sub 2}O{sub 4} cathodes

Description: Cathode films of amorphous Li{sub x}Mn{sub 2}O{sub 4} have been grown by rf magnetron sputtering on unheated substrates. A low process gas pressure and a positive substrate bias were found to give the most conductive cathodes. The batteries were completed with subsequent deposition of a lithium phosphorous oxynitride electrolyte and Li anode. These cells were cycled at 25-100 C between 4.5 and 1.5 V which corresponds to {approximately}0 to 2 Li per Mn{sub 2}O{sub 4}. The amorphous cathodes have a highs pecific capacity and a low capacity loss per cycle.
Date: January 1, 1996
Creator: Dudney, N.J.; Bates, J.B.; Lubben, D. & Hart, F.X
Partner: UNT Libraries Government Documents Department

Anomalous Hall effect in Gd-doped La{sub 2/3}Ca{sub 1/3}MnO{sub 3}

Description: Ceramic samples of (La{sub 1-x}Gd{sub x}){sub 2/3}Ca{sub 1/3}MnO{sub 3} were prepared and used as targets to grow films onto LaAlO{sub 3} substrates by pulsed laser deposition. Electrical resistance and thermopower, measured vs temperature and applied magnetic fields indicate transport dominated by positive small polarons in the high temperature paramagnetic state. The Hall effect was measured in 0.5 {mu}m thick films of composition x=0 and x=0.25. No evidence for extraordinary hall effect was found in the paramagnetic regime. Instead, the magnitude of the Hall coefficient decreases exponentially with temperature. This behavior and its anomalous negative sign are interpreted to result from face-diagonal hopping of small polarons in the Mn sublattice.
Date: October 1, 1996
Creator: Jaime, M.; Hardner, H.; Salamon, M.B.; Rubinstein, M.; Dorsey, P. & Emin, D.
Partner: UNT Libraries Government Documents Department

Effects of magnetization on hole localization and MnO{sub 6} octahedra disorder in hole-doped lanthanum manganese perovskites

Description: The authors review the distortions of the MnO{sub 6} octahedra reduced by magnetization in hole-doped lanthanum manganese perovskites. The systems they consider include the colossal magnetoresistance (CMR) samples La{sub 1{minus}x}Ca{sub x}MnO{sub 3} (x = 0.21, 0.25, 0.30), La{sub 0.76}Ba{sub 0.33}MnO{sub 3}, and a poorer quality La{sub 0.76}Pb{sub 0.33}MnO{sub 3} sample. They also report preliminary work on three samples of oxygen-doped LaMnO{sub 3+{delta}} and a lanthanum-deficient La{sub 0.9}MnO{sub 3} sample. They find the same exponential relationship between the removal of the distortion and the sample magnetization in the Ba- and Pb-doped CMR samples as was found previously for the Ca doped samples. The MnO{sub 6} distortion in the oxygen-doped materials is found to slightly reduce below the magnetic transition, although much less so than in the CMR samples. Above T{sub C}, the antiferromagnetic LaMnO{sub 3.006} sample shows a softer temperature dependence of the Mn-O bond length distribution broadening. Surprisingly, even this sample shows deviations from thermal (Debye) behavior near T{sub N}, possibly due to FM coupling within MnO planes.
Date: December 31, 1998
Creator: Booth, C.H.; Brosha, E.L.; Kwei, G.H.; Bridges, F. & Neumeier, J.J.
Partner: UNT Libraries Government Documents Department

Effects of dynamic Jahn-Teller distortions by Raman spectroscopy in the layered CMR manganite La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7}, x = 0.36

Description: The close interplay among charge, spin, and lattice degrees of freedom in the colossal magnetoresistive (CMR) manganite oxides is believed to play an important role in the transport mechanism in these itinerant ferromagnets. While the work on CMR materials has concentrated on the 3D perovskite manganites, the discovery of the layered compounds La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7} as another class of CMR oxides provides a rich opportunity to explore the relationship between structure and transport properties on varying length and time scales in reduced dimensions. The crystal structure of the layered CMR compounds La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7} is comprised of perovskite bilayers of corner-linked MnO{sub 6} octahedra forming infinite sheets. Doping of divalent cations such as Sr{sup 2+} gives rise to a mixed valent system were Jahn-Teller (JT) active Mn{sup 3+} and JT-inactive Mn{sup 4+} co-exist on the lattice. Among the current theoretical models of transport in the three-dimensional perovskite materials is the role of JT. This transport mechanism plays a fundamental role above the Curie temperature (T{sub c}). Indeed, localized lattice distortions have been observed experimentally above T{sub c} in the (La,Ca)MnO{sub 3} perovskite system. In this communication, the authors report resonant Raman spectroscopic measurements on a micro-crystalline sample of La{sub 1.28}Sr{sub 1.72}Mn{sub 2}O{sub 7} (x = 0.36). The measurements suggest discrete phonon modes for the Mn{sup 3+} and Mn{sup 4+} lattice sites, which may arise from either dynamic or static localization and the presence of Mn{sup 2+} defects in the lattice.
Date: December 1, 1998
Creator: Bordallo, H. N.; Argyriou, D. N.; Mitchell, J. F. & Strouse, G. F.
Partner: UNT Libraries Government Documents Department

High-temperature magnetic anomalies in Sr-doped La manganite structures

Description: The temperature dependence of the magnetization M, susceptibility {chi}, and magnetoresistance MR for 3 perovskite-variant manganite structures were studied: monoclinic (x=0.075) and orthorhombic (x=0. 125) La{sub 1-x}Sr{sub x}MnO{sub 3}, and tetragonal layered La{sub 2- 2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7} (x=0.4) with x also indicating the nominal fraction of Mn{sup 4+}. In each case, evidence is found for unusual magnetic states at temperatures T above their primary magnetic transitions. In the first case, the high-T {chi} deviates from Curie-Weiss expectations, in the second case the MR extends to high T, and in the last, M and {chi} exhibit short-range anomalies at high T. This suggests that a key feature of these systems is the existence of multiple magnetic energy scales, independent of structure, dimensionality, or doping levels.
Date: November 1996
Creator: Potter, C. D.; Swiatek, M.; Mitchell, J. F.; Hinks, D. G.; Jorgensen, J. D.; Bader, S. D. et al.
Partner: UNT Libraries Government Documents Department

5-Volt and 4.6 V plateaus in LiMn{sub 2}O{sub 4} thin films

Description: Additional plateaus with median voltages of {similar_to}4.6 V, and {similar_to}5 V have been observed on charging thin film lithium batteries with crystalline LiMn{sub 2}O{sub 4} cathodes to 5.3 V. Total charge extracted from the 4 V and the two additional plateaus corresponded to about 1Li/Mn{sub 2}O{sub 4}, but the distribution of capacity among the three plateaus varied from film to film. It is speculated that the additional plateaus result from formation of mixed spinel structures in which a fraction of the 8a sites areoccupied by Mn{sup 2+} or Mn{sup 4+} ions and a fraction of the Li{sup +} ions occupy the 16d sites. After charging to 5.3 V, the 4.6 V plateau disappeared, and the capacity of the 4 V plateau increased at the expense of that of the 5 V plateau. The latter change is attributed to movement of Mn{sup 3+} or Mn{sup 5+} ions from 8a to 16d sites.
Date: January 1, 1996
Creator: Bates, J.B.; Lubben, D.; Dudney, N.J.; Zuhr, R.A. & Hart, F.X.
Partner: UNT Libraries Government Documents Department

Zero-field {mu}{sup +}SR study of the collossal magnetoresistance material La{sub 0.67}Ca{sub 0.33}MnO{sub 3}

Description: Zero-field {mu}{sup +}SR and resistivity experiments on La{sub 0. 67}Ca{sub 0.33}MnO{sub 3} powder shows that the ferromagnetic transition temperature (Tc = 274 K) and resistivity peak temperature coincide to within 1K, about 10 K higher that T{sub c} determined from the bulk magnetization. The sublattice magnetization v{sub mu}(T) is well described for T {<=} T{sub c} by (1-T/T{sub c}){sup beta}, where {beta} = 0.345 {+-} 0.015. Unusual relaxational dynamics suggest a wide distribution of Mn-ion correlation times. These results are discussed in terms of the effects of polarons on the spin and charge dynamics.
Date: April 1, 1996
Creator: Heffner, R.H.; Le, L.P. & Hundley, M.F.
Partner: UNT Libraries Government Documents Department

Crystal chemistry and electronic properties of the n=2 Ruddlesden-Popper manganates: unconventional CMR materials

Description: The crystallography and electronic properties of the Ln[sub 2- x]Sr[sub 1+x]Mn[sub 2]O[sub 7] manganese oxides adopting the n=2 Ruddlesden-Popper (RP) structure are discussed, focusing on the structural phase diagrams and electronic properties in the vicinity of the Mn +3.5 oxidation state and in particular the ease of synthesis of single phases of these materials.
Date: December 31, 1996
Creator: Battle, P.D.; Green, M.A.; Millburn, J.E.; Spring, L.E.; Vente, J.F.; Blundell, S.J. et al.
Partner: UNT Libraries Government Documents Department

Structure and Electrochemical Properties of LiMn2O4 Thin Films

Description: The structure and electrochemical properties of LiMn{sub 2}O{sub 4} films depend upon the deposition and annealing conditions. Films which were deposited by rf magnetron sputtering of LiMn{sub 2}O{sub 4} in Ar + N{sub 2} gas mixtures and annealed in O{sub 2} at temperatures between 400 to 1000{degrees}C had the cubic spinel structure with an a-axis length that increased linearly from 8.13 to 8.25 {Angstrom} with increasing anneal temperature. Thin-film lithium cells with cathodes of different a-axis lengths exhibited marked differences in their voltage profiles. In particular, the ratio of the capacities at 4 V and 3 V increased with the a-axis length. A defect model of LiMn{sub 2}O{sub 4} which is consistent with the structural and electrochemical data is represented by [Li{sub 1-y+z}Mn{sup 2+}{sub y-z}]{sub 8a}[Mn{sup 2+}{sub z}]{sub 16c}[Li{sub x}Mn{sub 2-x}]{sub 16d}O{sub 4}. Based on this model and the results of in-situ XRD measurements, it is proposed that Mn ions migrate from 8(a) tetrahedral sites to 16(c) octahedral sites on charging the cells in the 5V plateau.
Date: November 1, 1998
Creator: Bates, J.B.; Ueda, A. & Zuhr, R.A.
Partner: UNT Libraries Government Documents Department

Synthesis, tailored microstructures and `colossal` magnetoresistance in oxide thin films

Description: We have grown La{sub 1-x}Sr{sub x}MnO{sub 3} films, using both pulsed laser deposition and a polymeric sol-gel route. These two growth techniques result in different microstructures, but in both cases the texture (epitaxy or polycrystallinity) can be controlled by choice of substrates and growth conditions. The crystallography and microstructure of these films were studied using XRD and high- resolution TEM. The magnetic/magnetotransport properties of these films are discussed in context of their growth and microstructural parameters.
Date: September 1, 1996
Creator: Krishnan, K.M.; Modak, A.R.; Ju, H. & Bandaru, P.
Partner: UNT Libraries Government Documents Department

Electronically configured battery pack

Description: Battery packs for portable equipment must sometimes accommodate conflicting requirements to meet application needs. An electronically configurable battery pack was developed to support two highly different operating modes, one requiring very low power consumption at a low voltage and the other requiring high power consumption at a higher voltage. The configurable battery pack optimizes the lifetime and performance of the system by making the best use of all available energy thus enabling the system to meet its goals of operation, volume, and lifetime. This paper describes the cell chemistry chosen, the battery pack electronics, and tradeoffs made during the evolution of its design.
Date: March 1, 1997
Creator: Kemper, D.
Partner: UNT Libraries Government Documents Department

Microengineered cathode interface studies

Description: The overpotential at the cathode/electrolyte interface has been recognized as an important limitation on the performance of solid oxide fuel cells (SOFCs). This project is an effort to gain a scientific understanding of which interface features and conditions contribute to cathode polarization in SOFCs. The paper discusses three possible rate-limiting factors in the cathode reaction. The paper studies the electronic conductivity in the electrolyte, the ionic conductivity in the cathode, cathode geometry near the interface, and cathode surface area.
Date: October 1, 1996
Creator: Kueper, T.; Doshi, R. & Krumpelt, M.
Partner: UNT Libraries Government Documents Department

3d-Metal Doped into LiMn2O4 Thin Films

Description: 3d-metal (Me) doped LiMn{sub 2}O{sub 4} thin films were deposited by rf magnetron sputtering of Li[Mn{sub 1.9}Me{sub 0.1}]O{sub 4} targets in Ar + N{sub 2} and Ar + O{sub 2} gas mixtures and annealed at 750{degrees}C in O{sub 2} for 1 h. From XRD measurements, the structure of the Me-doped thin film was dependent upon the element and the deposition conditions. The doping level of Me/Mn of cubic phase was less than 0.1 by EDX measurements. The Ti-LiMn{sub 2}O{sub 4} films exhibited a capacity close to theoretical for stoichiometric LiMn{sub 2}O{sub 4}. This improvement at 4 V comes at the expense of the capacity at 5 V. Cells with Ti-doped films exhibited the same low capacity fade as those with undoped LiMn{sub 2}O{sub 4} cathodes. Similar electrochemical changes were observed with the Cr- and Zn-LiMn{sub 2}O{sub 4} films. The discharge capacities above 4.5 V for the Ni-doped films were about equal to those below 4.5 V, and the thin-film cells could be cycled reversibility between 3.5 and 5.3 V.
Date: November 1, 1998
Creator: Bates, J.B.; Ueda, A. & Zuhr, R.A.
Partner: UNT Libraries Government Documents Department

Structural and electrochemical studies of alpha manganese dioxide ({alpha}-MnO{sub 2})

Description: The structural and electrochemical properties of alpha-MnO[sub 2], prepared by acid digestion of Mn[sub 2]O[sub 3], and its lithiated derivatives xLi[sub 2] O . MnO[sub 2] (where x is greater than or equal to zero and less than or equal to 0.25) have been investigated as insertion compounds in the search for new and viable cathode materials for rechargeable 3-V batteries. The alpha-MnO[sub 2] product fabricated by this technique contains water within the large (2x2) channels of the structure; the water can be removed from the alpha-MnO[sub 2] framework without degradation of the structure, and then at least partially replaced by Li[sub 2]O. The lithia-doped alpha-MnO[sub 2] electrodes, described generically as xLi[sub 2]O . Mno[sub 2], stabilize the structure and provide higher capacities on cycling than the parent material. The structures of these alpha- MnO[sub 2]-type electrode materials are described. and electrochemical data are presented for both liquid electrolyte and polymer electrolyte Li/alpha-MnO[sub 2] and Li/xLi[sub 2]O . MnO[sub 2] cells.
Date: August 1, 1996
Creator: Johnson, C.S.; Dees, D.W.; Mansuetto, M.F.; Thackeray, M.M.; Vissers, D.R.; Argyriou, D. et al.
Partner: UNT Libraries Government Documents Department

Hysteresis in Thin-Film Rechargeable Lithium Batteries

Description: Discharge - charge cycling of thin-film rechargeable lithium batteries with an amorphous or nanocrystalline LiXMn2.Y04 cathode reveals evidence for a true hysteresis in the lithium insertion reaction. This is compared with an apparent hysteresis attributed to a kinetically hindered phase transition near 3 V for batteries with either a crystalline or a nanocrystalline LiJ@Yo4 cathode.
Date: April 25, 1999
Creator: Bates, J.B.; Dudney, N.J.; Evans, C.D. & Hart, F.X.
Partner: UNT Libraries Government Documents Department

XPS study of Ni-Fe manganite thermistor material

Description: The resistivity of the as-fabricated thermistor material, nickel-iron-manganite, changes during initial aging in the temperature range of 150-300{degrees}C before becoming stable. X-ray photoelectron spectroscopy (XPS) was used to determine if any valency change or chemical shift of the cations or oxygen occurred after aging. The goal of the study was to identify any ionic changes that might affect thermistor stability. The only observed changes in 2p{sub 3/2} peaks due to aging were those related to Ni ions; the same peaks for Mn, Fe, and O remained unchanged. The changes in the Ni 2p{sub 3/2} peak may be related to: (a) the migration of Ni{sup 2+} ions from octahedral to tetrahedral sites, (b) subtle changes in the energy states of Ni{sup 2+} which promoted a more stable ionic structure, and/or (c) the presence of Ni{sup 3+} ions, some of which revert back to Ni{sup 2+}.
Date: March 1, 1995
Creator: Braski, D.N.; Osborne, N.R. & Zurbuchen, J.M.
Partner: UNT Libraries Government Documents Department

Unusual relaxation dynamics in La{sub 1-x}Ca{sub x}MnO{sub 3}(X=0.33 and 0.67)

Description: Muon spin relaxation studies on powders of this system show that the dynamic relaxation function changes from exponential above the magnetic transition temperature to stretched exponential below the critical temperature ({Tc}=274 K for x=0.33, T{sub N}=150 K for x=0. 67). This suggests a spatially inhomogeneous distribution of very slow Mn-ion correlation times characteristic of diffusive relaxational dynamics. An anomalously small applied field destroys the dynamical signature of the (ferro)magnetic transition in x=0.33, but not the (antiferro)magnetic transition in x=0.67. The x=0.67 system also shows evidence for a change in the magnetic phase in zero field near 75 K.
Date: July 1996
Creator: Heffner, R. H.; Le, L.; MacLaughlin, D. E.; Luke, G. M.; Kojima, K.; Nachumi, B. et al.
Partner: UNT Libraries Government Documents Department

In situ investigation of working battery electrodes using synchrotron x-ray diffraction

Description: The results of an in situ investigation of the structural changes that occur during the operation of working battery electrodes using synchrotron radiation are presented. Two types of electrodes were investigated: an AB{sub 2}-type Laves phase alloy anode with the composition Zr{sub x}Ti{sub 1-x}M{sub 2} and a proprietary cell based on a Li{sub x}Mn{sub 2}O{sub 4} spinel compound cathode made by Gould electronics. For the Laves phase alloy compositions with x=0.25 and 0.5 and M=V{sub 0.5}N{sub 1.1}Mn{sub 0.2}Fe{sub 0.2} were examined. Cells made from two different batches of Li{sub x}Mn{sub 2}O{sub 4} material were investigated. The relationships between battery performance and structural changes will be discussed. In the later case, we also discuss the role of over-discharging on the Li{sub x}Mn{sub 2}O{sub 4} structure and on battery operation.
Date: December 31, 1996
Creator: Jisrawi, N.M.; Thurston, T.R. & Yang, X.Q.
Partner: UNT Libraries Government Documents Department

Thin-film Li-LiMn{sub 2}O{sub 4} batteries

Description: Thin-film rechargeable Li-LiMn{sub 2}O{sub 4} batteries have been fabricated and characterized. Following deposition by electron beam evaporation of LiMn{sub 2}O{sub 4}, the amorphous as-deposited cathode films 1 cm{sup 2} in area by 0.3 to 4 {mu}m thick were annealed at 700{degree}C to 800{degree}C in oxygen in order to form the crystalline spinel phase. The capacity of the cells between 4.5 V to 3.8 V depended on the annealing conditions and ranged from 50 {mu}Ah/mg to 120 {mu}Ah/mg. When cycled over this range, the batteries exhibited excellent secondary performance with capacity losses as low as 0.001% per cycle. On charging to 5.3 V, a plateau with a median voltage of 5.1 V was observed. The total charge extracted between 3.8 V to 5.3 V corresponded to about 1Li/Mn{sub 2}O{sub 4}.
Date: November 1, 1994
Creator: Bates, J.B.; Lubben, D. & Dudney, N.J.
Partner: UNT Libraries Government Documents Department

Sign reversal of the MN-O bond compressibility in La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} below T{sub C}: Exchange striction in the ferromagnetic state

Description: The crystal structure of the layered perovskite La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} has been studied under hydrostatic pressure up to {approximately} 6 kbar, in the paramagnetic and ferromagnetic states, with neutron powder diffraction. The compressibility of the Mn-O apical bonds in the double layer of MnO{sub 6} octahedra changes sign from the paramagnetic insulator (PI) to the ferromagnetic metal (FM) state; in the Fm state the Mn-O-Mn linkage between MnO{sub 2} planes expands under applied pressure, whereas they contract in the PI state. This counterintuative behavior is interpreted in terms of exchange striction, which reflect the competition between super- and double-exchange. An increase of the Mn-moment with applied pressure in the FM state is consistent with a positive dT{sub C}/dP, as well as a cant angle {theta}{sub 0} between the magnetizations of neighboring MnO{sub 2} sheets that decreases with pressure.
Date: March 1997
Creator: Argyriou, D. N.; Mitchell, J. F.; Chmaissem, O.; Short, S.; Jorgensen, J. D. & Goodenough, J. B.
Partner: UNT Libraries Government Documents Department