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By J. W. Walkiewicz

The Bureau of Mines investigated alloys containing lanthanum (La), praseodymium (Pr), neodymium (Nd), cobalt (Co), copper (Cu), iron (Fe), and magnesium (4g) as possible components of a permanent magnet mate¬rial utilizing a cerium-free synthetic mischmetal (M) as a substitute for scarce samarium (Sm) metal. Magnets containing M-Co-Cu-Mg and M-Co-Cu-Fe-Mg were fabricated by powder metallurgy techniques and evaluated. A synthetic mischmetal (M20) containing 20 pct La, 60 Pr, and 20 Nd yielded the best overall magnetic properties. The M20-Co-Cu-Mg alloys had energy products as high as 13.2 MGOe, remanences as high as 7.89 kG, normal coercivities as high as 6.26 kOe, and intrinsic coercivities as high as 13.4 kOe. The best value of intrinsic coercivity, 22.9 kOe, was obtained with an M-Co-Cu-Mg magnet in which the synthetic misch¬metal contained 30 pct La, 50 Pr, and 20 Nd. These values compare favorably with those of the Sm-Co magnets fabricated and measured at the Bureau's Reno Research Center, which had energy product of 15.1 MGOe, remanence of 7.8 kG, normal coercivity of 7.5 kOe, and intrinsic coercivity of 27.4 kOe. Iron substitution for part of the cobalt resulted in a decrease of magnetic properties, although several percent iron can be added before a drastic loss of magnetic properties occurs.

Jan 1, 1983

By Alla D. Mah

Relatively pure aluminum nitride (AIN) recently has been prepared in sufficiently large amounts to permit a variety of experimental studies.4/ Several mechanical and chemical properties have been investigated, which show that this substance has good potentialities as a container for liquid aluminum, gallium, and boric oxide. The present work by the Bureau of Mines was undertaken to obtain thermo-dynamic data pertinent to the calculations regarding thermal stability and reactivity of aluminum nitride. The following measurements were made: (1) determination of the heat of formation from the elements at 298.15° K.; (2) determinations of the heat capacity over the temperature range 51° to 298.15° K. and the evaluation of the entropy at 298.15° K. therefrom; and (3) determinations of the heat content over the temperature range 298.15° to 1,800° K. These data are combined to obtain free energies of formation from the elements between 298.15° and 2,000° K.

Jan 1, 1961

By W. W. Weller

Heat capacities of ferrous molybdate (FeMoO4) and ferrous tungstate (FeWO4) were measured over the temperature range 51° to 298.15° K. Ferrous tungstate has a lambda type heat capacity anomaly at 74° K. The 298.15° K entropies are FeMoO4) 30.9 cal/deg mole and FeW04) 31.5 cal/deg mole.

Jan 1, 1966

By D. P. Lindroth

The thermal diffusivity above 298 K, up to 400 K and at pressures from ambient down to 10-10 torr was measured for the following six igneous rock types: tholeiitic basalt, obsidian, rhyolite, granodiorite, gabbro, and dunite. The thermal diffusivity data were obtained by the laser flash method. Extreme values range from a low of 5.3X10-3 cmF/sec for rhyolite at 383 K and 2X10-7 torr to a high of 13.4x10-3 crrf/sec for dunite at 298 K and 760 torr. Data are also included on a commercial fused silica, which was used as a standard.

Jan 1, 1974

By J. M. Stuve

Low temperature and high-temperature calorimetric measurements were made by the Federal Bureau of Mines on high-purity samples of Re02(s) and Re03(s) to determine heat capacities and enthalpies. The temperature range of heat capacity measurements was 5 to 310 K for Re02 and 8 to 309 K for Re03. High-temperature enthalpy measurements alone were determined for pure Re207(s,1). The derived standard entropies are S°298 = 11.43±0.01 cal/deg mole for Re02(s) and S298 = 16.55±0.02 cal/deg mole for Re03(s). High-temperature enthalpy equations expressed in calories per mole are as follows: Re02 (s) , H-H298.15 = 16.002T + 1.600 X 10-3T2 + 3.522 X 105T-1 - 6,095 (298 to 1,400 K); Re03 (s) , H-H298.15 = 20.293T + 3.238 X 10-3T2 + 3.950 X 105 T-1 - 7,664 (298 to 1,000 K); Re207 (s) , H-H298.15 = 38.437T + 10.309 X 10-3T2 + 4.315 X 105 T-1 - 13,824 (298 to 413 K); Re207 (s) , H-H298.15 = 30.181 + 17.713 X 10-3T2 - 10,612 (413 to 600 K) ; Re207 (1) , H-H298.19 = 66.101T - 10,092 (600 to 700 K). Gibbs energy of formation (?Gf°) data and related functions over the temperature ranges investigated are tabulated for the three oxides.

Jan 1, 1976

By L. B. Pankratz

Low-temperature heat capacities, high-temperature enthalpy increments, and the enthalpy of formation at 298° K were determined calorimetrically for vanadium subnitride (VN0.465). The low-temperature investigation gave S°298.15 = 6.379 ±0.005 cal/deg mole, and a combustion calorimeter investiga¬tion provided ?Hf°298.15 = -31.80 ±0.60 kcal/mole. The two quantities were combined with the high-temperature data to give standard values of enthalpies of formation and free energies of formation above 298° K. These and related thermodynamic functions were tabulated to 1,800° K. Similar data are included in the range of 298° to 1,600° K for the mononitride, VN.

Jan 1, 1971

By M. J. Ferrante

Low-temperature heat capacities and high-temperature enthalpies were determined calorimetrically for Na2Cr04, A reversible transition was found at 700° K with an isothermal heat of transition of 2,263 cal/mole. High-temperature X-ray diffraction analysis showed that the transition was a crystal change from the low-temperature orthorhombic form to the high-temperature hexagonal form. At 795° K the hexagonal form had the parameters a, = 5.691 and co = 7.478 A. Powder diffraction data for the high-temperature form are given and possible structures discussed. The melting point was determined to be 1,065° K with a heat of fusion of 5,810 cal/mole. Enthalpy and entropy increments from this investigation were combined with other data from the literature to calculate enthalpies of formation, free energies of formation, and equilibrium constants of formation from 298° to 1,400° K. Equations that represent enthalpies above 298° K are given.

Jan 1, 1972

By E. G. King

Strontium sulfide and barium sulfide occur as intermediates in commercial treatments of the impure natural sulfates to produce pure strontium and barium chemicals. Thermodynamic considerations involving these sulfides have been hampered by lack of basic data, such as the entropies at 298.15°K. This paper reports the results of heat capacity measurements of strontium sulfide and barium sulfide in the temperature range 50°-298°K. The entropies at 298.15°K. were derived from the heat capacity values. Free energies of formation at 298.15°k. were computed from the entropies and literature values of the heats of formation. Strontium sulfide and barium sulfide are thermo-dynamically less stable than calcium sulfide, but more stable than magnesium sulfide.

Jan 1, 1960

By J. W. Walkiewicz

The Bureau of Mines investigated alloys containing mischmetal (MM), cobalt, copper, magnesium, and iron for use in permanent magnets in place of the scarce samarium-cobalt alloys. The magnetic properties of MM-Co, MM-Co-Cu, MM-Co-Cu-Mg, and MM-Co-Cu-Fe-Mg alloys were evaluated. Magnets were fabricated by powder metallurgy consisting of arc-melting the metals, crushing and grinding the resultant alloys, alining and compacting the powder, and sintering the compacts. Magnetic values of MHc = 4.7 kOe, BHc = 4.07 kOe, Br = 6.81 kG, and (BH)max = 10.0 MGOe were obtained with a MM-Co alloy containing 36±0.5 wt-pct MM. By substituting copper and magnesium for part of the cobalt, the values for MHc and BHc were increased to 29.0 kOe and 5.89 kOe, respectively. This intrinsic coercivity value exceeded that of Sm-Co alloy obtained in our laboratory. The addition of iron to MM-Co-Cu-Mg alloys resulted in an increase of Br to 6.90 kG and (BH)max to 10.3 MGOe. Copper and magnesium contents of these alloys were optimized to obtain maximum values of MHc.

Jan 1, 1981

By M. J. Ferrante

Enthalpy and entropy increments above 298.15° K were determined for cop-per sulfate between 298° and 1,000° K and for copper oxysulfate between 2980 and 1,146° K by the method of copper-block drop calorimetry. Enthalpies, entropies, and heat capacities are tabulated for both compounds. In addition, free-energy functions are tabulated for the sulfate. Equations representing the enthalpies are given for each compound.

Jan 1, 1972

By John W. Adams

The present status of the National Bureau of Standards program is that many magnetic tapes of analog data have been recorded in four major mines. Each mine uses different types of equipment. In addition, some surface measurements of noise have been made at two additional mines. Two types of recordings have been made: (1) broadband measurements for spectral plots and (2) narrowband measurements for amplitude probability density (APD) plots. Only data from one mine (Robena #4) has been processed and was, presented at this workshop. The short-term goals are: (1) finish processing data from the other mines, (2) establish or reduce measurement system uncertainties, (3) put Robella report into final form for distribution, and (4) hold a review to determine what has been done, to distribute and to interpret the preliminary data, and to determine what still needs to be done. Long-term goals are: (1) complete final reports on each of the mine trips, (2) establish techniques for predicting noise in mines already visited and establish uncertainty bounds for these predictions, and (3) establish techniques for predicting noise in mines that have not been visited (but that use similar equipment to those visited) and also establish uncertainty bounds for these predictions. Specific factors or formats to be presented include: (A) For underground broadband measurements: 1. 300 Hz to 100 kHz spectral plots 2. 300 Hz to 384 kHz spectral plots 3. 300 Hz to 192 kHz spectral plots 4. 300 Hz to 6kHz (subject to change to 3 or 12 kHz) spectral plots (B) For surface broadband measurements: 1. 300 Hz to 6 kHz (or 12 kHz) spectral plots 2. 300 Hz to 3 kHz spectral plots (C) For underground narrowband measurements : 1. APD plots at 12 frequencies from 10 kHz to 32 mHz of magnetic field strength 2. R. M.S. and average values will be calculated based on time averaging for these plots (D) Sample spectral measurements of: 1. Roof-bolt voltages 2. Trolley wire-to-rail voltages 3. Phone line currents

Jan 1, 1973

By Peter C. Wood

This report describes research directed toward the preparation of chemical oxygen (02) sources which exhibited improved 02 storage and reaction characteristics when compared to potassium superoxide (KO2). The initial focus of the research was the preparation of calcium superoxide (Ca(02)2) by the disproportionation of calcium peroxide diperoxyhydrate. The Ca(02)2) was characterized by chemical, thermal, and x-ray analyses. Several methods for scaling up the Ca(02)2 synthesis process were studied. Next, the reactivity of Ca(02)2 toward humidified carbon dioxide (C02) was evaluated and was compare o that of K02 under flow-test conditions approximating those existing in portable breathing apparatus. The reactivities of mixtures of K02 and Ca(02)2 or lithium peroxide towards humidified CO2 were also studied. Finally, an analysis of two commercial, K02-based, self-contained self-rescuers was conducted to determine the potential weight and volume savings which would be possible if Ca(02)2 or a mixture of K02 and Ca(02)2 were used as a replacement for K02.

Jan 1, 1983

By J. J. Cummins

Green River oil shale previously extracted by benzene was heated at 150°, 200°, 250°, 300°, and 350° C for 0.5 to 360 days to determine the rate at which kerogen degrades to thermal products, the types of thermal products formed, and the effect of prolonged low-temperature heating (preheating) upon subsequent assay yields. Thermal decomposition of kerogen at 150° to 350° C is treated as a first-order reaction. The specific reaction rate for kerogen decomposition increases from 2.2 X 10-4 per day at 150° C to 2.0 X 10-1 per day at 350° C. The calculated kerogen activation energy is 19 kcal. Variations in the rate of formation of individual type components of the pyrolytic products were found. Carbon balances show an increase in the amount of kerogen converted to bitumen and oil (from assay of preheated oil shale) as the temperature of preheating increased from 150° to 350° C. Total product from shale preheated at temperatures of 150° and 200° C gave less than 100 percent of Fischer assay yields while the total products from shale preheated at temperatures of 250° to 350° C gave greater than 100 percent of Fischer assay yields.

Jan 1, 1972

By R. K. Koch

The vapor pressures of liquid molybdenum and liquid zirconium were determined by the Langmuir free-evaporation method. An electron-beam furnace with a water-cooled copper crucible was used for melting. Temperature was measured with a two-color ratio pyrometer. The vapor-pressure data led to the following equations: [log p (atm) = 5.429 - 28,380 T for liquid molybdenum in the range 2,890° to 2,990° K, and log p (atm) = 6.521 - 30,940 T for liquid zirconium in the range 2,229° to 2,795° K.] Third-law evaluations of each data set gave mean heats of sublimation (298.15° K) of 157.6 ± 1.8 kcal/mole and 148.4 ± 2.4 kcal/mole for molybdenum and zirconium, respectively, where the uncertainties are two standard devia¬tions. Second-law standard heats of sublimation determined from sigma plots and tabulated enthalpies were 143.5 ± 2.7 kcal/mole and 149.2 ± 3.8 kcal/mole for molybdenum and zirconium, respectively. The better agreement in heats of sublimation for zirconium is attributed to the 566° K temperature range studied which permitted a more accurate definition of the vapor pressure curve than could be obtained from the 100° K span for molybdenum. This supposition was verified by making a sigma-prime plot which utilized solid vapor pressure data for molybdenum to extend the evaluation range by 800° K. This gave a standard heat of sublimation of 155.2 ± 1.6 kcal/mole which is in good agree¬ment with the third-law value. The plot also gave a standard entropy of sublimation (298.15° K) of 35.73 ± 0.48 eu.

Jan 1, 1968

By Joan C. Biordi

[Composition profiles for atomic, radical, and stable species, as well as temperature and area expansion ratio profiles, have been determined for a nearly stoichiometric CH4-02-Ar flame and one to which 0.3 percent CF5Br inhibitor had been added. Net reaction rate profiles were calculated for all the observed species. For the normal flame, these and the mole fraction profiles gave rate coefficient information about the elementary reactions in the methane flame, for example, CH. + 0 4- H2CO 0 H, k4 = 1.05 X 1014CM3 mole-1sec-1 for 1,550§T 0,725' K; CO + OH 4 C02 + H, k6= 4.7 X 1011 for 1,350{T X1,750° K. Comparison between the inhibited and normal flame showed that A] and [CH3] were significantly reduced at the lower temperatures in the inhibited flame even though in the hot gas region the [E] [OH!, and [0] were essentially the same in both flames. The CF3Br disappears very early in the flame, relative to the fuel, and the reaction primarily responsible for its disappearance is H v CF3Br 4 HBr + CF3, where k7 is found to be 2.2 X 1014 exp(-9460/RT) for 700-1,550° K. Reaction of the inhibitor with methyl radicals provides for the relatively small amounts of CH3Br observed, but CH3 + Br2 - CHs Br + Br must also occur. The HBr formed reacts rapidly with H atoms to form H2 and Br, but the reaction is soon "balanced" in the flame as may be demonstrated by calculation of the equilibrium constant at various temperatures. The fluoro-carbon fragment produced in reaction (7) also reacts rapidly, in part with methyl radicals to give the observed elimination product CH2CF2 Later in the flame, above -1,400' K, F2CO is formed from the reaction CH2CF2 + 0 P F2CO + CH2 and k., -1.5 X 1013 at 1,600° K. The rather slow decay of carbonyl fluoride is attributed to reaction with H atoms according to the sequence F2CO I H - HF + FCO and FCO + H HF + CO.]

Jan 1, 1975

By J. M. Stuve

Low-temperature heat capacities of chiolite (Na5Al3F14) were determined by adiabatic calorimetry in the temperature range 5.8 to 300 K. The derived standard entropy (S°, 298.15) was 115.6 ± 0.2 cal/deg-mole. High temperature enthalpies relative to 298.15 K were obtained by precision drop calorimetry up to 1,000 K. Tables of experimental data and related thermodynamic functions are given for the temperature range of experimental observations.

Jan 1, 1980

By G. Richards Gwinn

"Mica" is a group name for a number of orthosilicates of aluminum with magnesium, ferrous iron, and the alkalies. They are characterized by their high reflection and a basal cleavage so well developed that they can be split into exceedingly thin laminae, which are more or less tough, elastic, and transparent, according to variety. Barium, manganese, lithium, chromium, titanium, boron, and ferric iron occur in same varieties. Eight distinct species of true mica, which appear in the following table, are recognized by mineralogists, but only the first five are of commercial importance. [Species General Formula Muscovite H2KA13 (SiO4)3 Phlogopite [H,K, (MgF)]) Mg3A1 (Si04)3 Biotite (H,K)2(Mg,Fe)2(Al)Fe)2 (S104)3 Lepidolite K,Li Al(OH,F)2 Al (5103)3 Ros coalite H8K(Mg,Fe) (A1,V)4 (S103)12 Paragonite H2NaAl3(S104)3 Zinnwaldite (K)Li)3 FeAl3 Si5016(OH,F)2 Lepidomelene HK2F3IIIFe6III A13 (S104)9]

Jan 1, 1951

By M. J. Ferrante

Relative enthalpies of cuprous iodide (CuI) were measured at the Bureau of Mines to provide thermodynamic data for the advancement of min-eral technology. Enthalpy measurements between 298.15 and 1,396.3 K were made with a copper-block drop calorimeter. The temperatures of transition were measured by differential scanning calorimetry (DSC). Reversible transitions were determined at 643 K with a standard enthalpy of transition [(6Htr)] = 0.74 kca1/mol, at 679 K with a [6Htr = 0.65 kca1/mo1, and at 868 K] with a standard enthalpy of fusion [(6H~) = 1.895 kca1/mol.] Tabulated values are listed at selected temperature increments from 298.15 to 1,600 K for the standard relative enthalpy (HO -H298), heat capacity (CpO), entropy (SO), and Gibbs energy function [-(Go -H298)!T]. The enthalpy data are also given in the form of equations and combined with thermodynamic data from other investigations to derive values of standard entha1pies of formation [(~HfO)], Gibbs energies of formation [(6GfO)], and logarithms of the equilibrium constants of formation (log Kf).

Jan 1, 1987

By M. J. Ferrante

The Bureau of Mines determined the enthalpies of Ni3S2 relative to 298.15 K to provide new thermodynamic data for advancement of mineral science and technology. Enthalpies were measured with a copper-block calorimeter from 298.15 to 1,197 K. A solid-solid transition was found at 834±1 K, with an isothermal heat absorption of 13.32 kcal/mol. The temperature of this solid-solid transition was accurately measured by differential scanning calorimetry. Because Ni3S2 does not melt congruently, the heat of fusion of 4.70 kcal/mol was obtained by extrapolation of enthalpy measurements from the solid and liquid phases to approximately 1,064 K. Tabulated values are given for the relative standard enthalpy, heat capacity, entropy, and Gibbs energy function between 298.15 and 1,800 K. Enthalpies are also given in equation form and combined with data from the literature to derive values of standard enthalpies of formation and Gibbs energies of formation. Similar calculations were made for the reaction of crystalline and liquid nickel with gaseous diatomic sulfur for Ni3S-2(c, l).

Jan 1, 1982

By L. B. Pankratz

Heat content measurements were conducted for GaPo.996 and InPo.986 over the temperature range from 298° to 1,100° K, and for In2S2.897 over the range from 298° to 1,200° K. Both the actual experimental data and values adjusted to conform with the stoichiometric compositions (GaP, InP, and In2S3) were reported. Entropy increments above 298.15° K were calculated for the stoichiometric compounds, and heat content and heat capacity equations were derived.

Jan 1, 1965