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By R. D. Groves

Laboratory research has demonstrated that high - grade copper powders can be produced under controlled conditions from cement copper products . The technique should enable small producers to prepare a directly marketable product by means other than smelting and electrolytic purification . A continuous drum- type precipitator was the preferred unit for producing fine - sized particles of cement copper that were further processed by chemical digestion in a copper sulfate solution , by reduction and sintering in a hydrogen atmosphere , and by grinding to a powder . The effects of variables related to all stages of the process were investigated . Treatment of leach solutions from three different sources resulted in copper powders containing 99.2 to 99.8 pct Cu , apparent densities of 1.97 to 2.25 grams per cu cm , good powder flow rates , and a size distribution of 54.9 to 60.1 pct minus 325 - mesh material .

Jan 1, 1964

By L. H. Adami, E. G. King

The heats of formation of four sulfides --MnS ( alabandite ) , FeS ( hexagonal pyrrhotite ) , ZnS ( wurtzite ) , and CdS ( greenockite ) -- were determined by hydrochloric acid solution calorimetry . The heats of formation from the metals and rhombic sulfur at 298.15 ° K are , respectively , -51.01 ± 0.19 , -23.81 ± 0.24 , -45.86 ± 0.20 , and -35.70 ± 0.30 kcal /mole . The corresponding free energies of formation were calculated from the heats of formation and the pertinent entropy values .

Jan 1, 1964

By J. B. Zink, M. J. Peterson

A semiquantitative spectrochemical method was developed and applied to the analysis of ash of U.S. coals . A low- temperature ashing procedure was used to minimize the loss of volatile elements . The analytical procedure provides for the estimation of 68 elements including major , minor , and trace constituents . Standards for the trace elements were prepared in a synthetic base mixture that approximates the average composition of U.S. coal ashes . Excitation was achieved with a d- c arc , spectra were recorded photographically , and interpretation was made by visual comparison of spectra of unknowns with spectra of graded standards series . Thirty- six trace elements were found in the analysis of 900 samples . Details of the procedure are presented , including sample and standards preparation , excitation and exposure conditions , spectral lines used , and approximate limits of detectability .

Jan 1, 1964

By R. L. Crosby, L. W. Higley

Magnesium- rich magnesium- aluminum- zirconium alloys in the cast and in the extruded and heat- treated condition were studied to identify the phases present and to determine phase distribution . In cast alloys , two intermetallic compounds were identified : ZrAla by X- ray diffraction ; and Mg₁ Al₁₂ by microscopical observation . Based on microscopical comparisons between the known phases in the cast structures and the phases in the structures of extruded and heat - treated rods , ZrAl₂ and Mg1 , Al12 were identified in the structure of the latter . The presence of these intermetallic compounds in rod specimens could not be confirmed by X- ray diffraction . ZrAl₂ was observed in the structure of extruded and heat - treated rod specimens containing as little as 0.01 weight - percent zirconium . The presence of aluminum restricts the solubility of zirconium in magnesium because of the strong tendency to form ZrAla . This intermetallic compound segregated in clusters of small particles in the matrix of cast alloys , and only slight improvement in distribution was noted when the alloying techniques were varied .

Jan 1, 1964

By W. J. Boone, Will E. DeVaney, Lowell Stroud

This report is the fifth in a series presenting equilibrium vapor - liquid data for helium- bearing natural gases . It covers a 0.41 - mole - percent - helium natural gas that may be processed in the Department of the Interior's longrange helium conservation program . A Bureau of Mines phase equilibrium apparatus was used to obtain 139 samples of equilibrium vapor and liquid phases at 85 experimental conditions at temperatures from 0 ° to -299 ° F and at pressures from 100 to 500 psia . An appendix covers phase data at 100 , 200 , and 300 psia and at temperatures from -125 ° to -275 ° F for the dehydrated gas containing its original concentration ( 0.2 mole - percent ) of carbon dioxide , and the effect of a preliminary hydrocarbon trap upon subsequent vapor - liquid compositions .

Jan 1, 1964

By D. J. Donaven, Manuel Gomez, W. S. Landers

Bulk density tests were made on a Western U.S. coke oven plant blend to obtain bulk density control data that would be directly transferable to plant practice . Maximum bulk density values were obtained at zero surface moisture . Increase in surface moisture to about 6 percent decreased the bulk density to a minimum value . Increase in the fine grinding of the blend , at constant surface moisture , decreased the bulk density . The effect of oil on bulk density was observed with five oils at concentrations ranging from 1/8 to 1-1 / 2 gallons per ton . Maximum bulk densities were obtained within the 1 / 2- to 1 - gallon - per - ton range . Essentially the same bulk densities were obtained with petrolatum- and nonpetrolatum- containing oils . Storage effects were observed on samples tested at selected intervals from 0 to 56 days . No significant change in bulk density took place if no surface moisture was lost during storage .

Jan 1, 1964

By R. V. Lundquist, H. Leitch

Sodium aluminate is the principal aluminum compound formed in the sinters prepared by the lime - soda sinter process for recovering aluminum from silicate source materials . The properties and characteristics of this compound were studied to improve the efficiency of the process . Crystalline sodium aluminate was prepared by sintering stoichiometric quantities of soda ash and calcined alumina for 1 hour at 1,250 ° C. The extent of aluminum extraction from sodium aluminate was determined in water and in solutions of NaOH and Na₂ CO3 . Nearly complete extraction of aluminum from sodium aluminate was achieved only in solutions containing free NaOH in excess of that supplied by the salt through hydrolysis . About 42.2 to 68.8 percent of the aluminum was extracted in water or in solutions of Na₂ CO . The precipitation of alumina trihydrate from sodium aluminate solutions was shown to be part of a continuous , reversible reaction according to the equation Al (OH ) A1 (OH )3 + OHThe reverse reaction dissolves alumina trihydrate in NaOH solutions to produce sodium aluminate . Approximate equilibrium concentrations were determined for the reaction at 30° , 50 ° , and 70 ° C. False apparent equilibrium conditions for the dissolution reaction appear when only a small excess of alumina trihydrate is present in the NaOH solutions . A large excess of alumina trihydrate must be present before the true equilibrium point is assured . The engineering significance of the data is summarized , showing controls that should be exercised for a successful and efficient process .

Jan 1, 1964

By Michael G. Zabetakis, Aldo L. Furno, George H. Martindill

Hydrazine vapor is flammable in the absence of air at elevated temperatures and atmospheric pressure . The minimum concentrations of benzene , toluene , m- xylene , cumene , and n- heptane needed to inhibit flame propagation through vapor mixtures of hydrazine and hydrocarbon were determined at 125 ° C and atmospheric pressure . These concentrations can be correlated with either the heat of formation or the heat capacity of the hydrocarbon .

Jan 1, 1964

By R. A. Beall, S. L. Ausmus

The development of a completely water - free expendable graphite mold material , useful for reactive metal castings , has been detailed . Mixing and curing variables have been evaluated both by physical testing of the material itself and by castings of titanium , zirconium , and hafnium . The blend of powdered graphite , cornstarch , dextrin , cereal binder , linseed oil , and Carbowax -4000 is a successful mix when mulled in a carbon dioxide atmosphere , and properly cured and fired . The primary advantage of this material is its adaptability to standard foundry techniques ; i . e . , core blowing and hand ramming . Temperatures in the curing and firing cycles do not exceed 960 ° C , and no vacuum firing is required .

Jan 1, 1964

By K. K. Kelley, W. W. Weller

This report contains experimentally determined heat capacity data for four crystalline sulfides -- AsS , GeS , NiS , and Ni3 S₂ -- over the temperature range from 50 ° to 298.15 ° K. The heat capacity data were used to evaluate the entropies of the sulfides at 298.15 ° K. Entropies of formation from the metals and rhombic sulfur and from the metals and diatomic sulfur gas are also included .

Jan 1, 1964

By J. B. Zadra, J. M. Gomes, Don H. Baker

Electrolytic deposition at 1,000 ° C in an electrolyte essentially consisting of 7 parts sodium pyrophosphate , 2 parts sodium chloride , and 1 part sodium tetraborate yielded tungsten of 99.9 percent purity . Scheelite concentrates containing 25 to 73 percent WO, and varying quantities of iron , lime , and silica were used as feed materials for the electrolysis . The metal contained less than 0.01 weight - percent each of iron , calcium , silicon , aluminum , carbon , and oxygen . Modification of the electrolyte permitted deposition of equal - quality metal from scheelite concentrates containing higher quantities of iron , calcium , and silica . The electrolytic separation of molybdenum and tungsten was accomplished by minor variations in the operating procedures .

Jan 1, 1964

By L. B. Pankratz, R. Barany, W. W. Weller

Experimental determinations were made of the heats of formation at 298.15 ° K of cuprous ferrite and cupric ferrite ; the heat capacity of cuprous ferrite was measured over the temperature range from 50 ° to 298 ° K and the entropy at 298.15 ° K was evaluated ; the heat contents of cuprous ferrite and cupric ferrite above 298.15 ° K were measured to 1,500 ° K and 1,100 ° K , respectively . These thermodynamic values were combined with other pertinent data to obtain heat and free energy of formation values at high temperatures . The stability of the two ferrites with respect to their constituent oxides is discussed . Thermodynamic values are included for the decomposition of cupric ferrite to form cuprous ferrite , magnetite , and oxygen .

Jan 1, 1964

By F. E. Joyce, Charles Prasky

This report describes the response to high- temperature sulfatization of a variety of manganese minerals and companion compounds which may occur either as a principal component or as a gangue material in low- grade manganese deposits . Fourteen manganese samples representing oxide , carbonate , and silicate minerals as well as seven compounds which might occur as gangue with manganese minerals were tested batchwise in a bench- scale apparatus under conditions which would be favorable for the sulfatization of manganese . The manganese minerals substantiated thermodynamic predictions and responded to sulfatization but to varying degrees . The gangue materials , MgO , MgCO,, CaO , and CaCO3 , were sulfatized readily in contrast to the iron oxides and the aluminacontaining material which were not .

Jan 1, 1964

By John Nagy, Austin R. Cooper, Murray Jacobson

Data obtained in the Bureau's study of dust explosions of 313 elemental metals , alloys , catalysts , and ores comprising 54 types of material are summarized . Information is given on ignition temperature , spark energy for ignition , minimum explosion concentration , explosion pressure , rate of pressure rise , and in some instances , the admixed inert dust and oxygen concentration in an atmosphere required to prevent ignition of dust dispersions . The effects of particle diameter on explosibility and pyrophoricity are also discussed .

Jan 1, 1964

By Alla D. Mah

The energies of combustion of zirconium carbide and hafnium carbide were measured by combustion calorimetry and the heats of combustion and formation. of zirconium carbide and hafnium carbide were derived . The results are-- ZrC AH298.15 ( combustion) = -308.60 ± 0.55 kcal /mole , AH298.15 ( formation) -47.0 ± 0.6 kcal /mole , AH298.15 = HfC (combustion ) = -306.08 ± 0.20 kcal/mole , AH298.15 ( formation) -52.3 ± 0.4 kcal /mole . = INTRODUCTION This report contains the results of calorimetric measurements to obtain the heats of formation of zirconium carbide ( ZrC) and hafnium carbide ( HfC) . The work was conducted as part of a Bureau of Mines program for determining the heats of formation of oxides , carbides , and nitrides by combustion calorimetry . Combustion calorimetry is one of the most precise calorimetric techniques . The chief obstacle to obtaining accurate heat of formation values for carbides , and the chief reason for the variation in the results of different investigators , is the lack of purity of the carbide samples . Corrections for impurities always involve assumptions which lead to uncertainties . In general , a large impurity correction is accompanied by a large uncertainty in the final result .

Jan 1, 1964

By Robert K. Koch, Henry E. Blake

Laboratory tests were made to determine if aluminum fluoride of commercial grade could be synthesized by reacting alumina hydrate with dilute ( 25 to 75 grams per liter of fluorine ) aqueous fluoride solutions . • Products containing up to 90 percent aluminum fluoride ( A1F ) were synthesized by reaction of alumina trihydrate ( A120 3H2O) with either dilute hydrofluoric acid ( HF ) or ammonium fluoride ( NHF) solutions , the ammonium fluoride solution resulting from ammonia ( NH ) desilication of a hydrofluoricfluosilicic acid ( HF - H₂ SiF ) solution . Fluorine recoveries of over 80 percent were obtained with either type of solution . The hydrated precipitates of AlF, and ( NH4 ) , A1F ( ammonium aluminum fluoride ) obtained by reacting hydrated alumina with these solutions were subsequently converted to anhydrous AlF, by controlled heating .

Jan 1, 1964

By Gus Pantages, Bernard D. Blaustein, Charles Zahn, Irving Wender

Oils from coal hydrogenation have been examined at the Bureau of Mines to learn whether any centers of the optical activity reported in coal would survive catalytic hydrogenation at 450-525 ° C and about 8,000 psig pressure , and , if so , to obtain information about the nature of the active products . Oils from carbonization tars also were examined . Optical activity was found in the majority of the distillate fractions of the hydrogenation oils and in almost all distillates from the carbonization tars . No activity was observed in the tar - acid and tar - base fractions examined . Methods for isolating optically active concentrates included distillation through a packed column , liquid chromatography on silica gel , and adduction with urea . For the materials so processed , the optical activity segregated mainly in the paraffin - naphthenic and the hydroaromatic fractions . Although the specific compounds responsible for the optical activity were not isolated , experimental and spectrometric findings indicate that alkylsubstituted cycloalkane , cycloalkene , and hydroaromatic structures are most likely responsible for the optical activity of the concentrates . The optically active centers probably derived mainly from the steroids and terpenes in the biological materials that participated in the formation of coal .

Jan 1, 1964

By H. O. Poppleton, F. E. Block

This investigation was made to develop a method of preparing high - purity thorium metal in quantities up to 20 kilograms per batch . Several methods for the preparation , purification , and reduction of thorium tetrachloride are discussed . Thorium tetrachloride was prepared by chlorination of decomposed thorium nitrate or oxalate with carbon tetrachloride or phosgene . tion of the crude tetrachloride was achieved by multiple distillations or by filtration of the molten chloride . It was found that high - purity thorium metal could be prepared by sodium reduction of thorium tetrachloride if chloride of sufficient purity were available . Byproduct salts and excess reductant were removed by vacuum distillation , and the resultant thorium metal sponge was consolidated by consumable - electrode or fixed - electrode arc melting . It was demonstrated that metal prepared by this method could be fabricated into bar , rod , or sheet , at room temperature .

Jan 1, 1964

By R. V. Lundquist, H. Leitch

The solubility characteristics of three calcium aluminates , 12Ca0 · 7A120½ 3Ca0 A1203 , and 4Ca0 A12 03 Fe2O3 , were determined in water and in solutions of NaOH and Na₂ CO₂ to more clearly define their role in relation to the recovery of aluminum by the lime sinter and the lime - soda sinter processes . The calcium aluminates were prepared by sintering stoichiometric mixtures of CaCO3 , Al2O3 3H20, and Fe 0 at 1,375 ° C. The rates and extent of aluminum extractions were determined . The aluminum extractions from the aluminates were dependent on the presence of carbonate ions in the leach solutions , temperature , time , leach solution composition , and solid - liquid ratio of the slurry . The aluminum extracted from the calcium aluminates in water and in NaOH solutions varied from 4.6 to 22.9 percent . Virtually , complete extraction could generally be obtained for 12Ca0.7A120 and 4Ca0.A12 03 • Fe₂ 03 ; in one instance it was obtained for 3Ca0.A1203 , when an excess of carbonate ions was present over that required for the conversion of all of the calcium in the aluminates into CaCO3 . In some cases of poor aluminum recoveries , extractions could be improved by regrinding and releaching the solid residues .

Jan 1, 1964

By J. A. Ruppert, P. M. Sullivan

A study was made of filtration techniques for recovering the major part of the tin contained in iron - tin alloys known as hardhead . Special smallscale filtering apparatus and a three - stage cyclic process were developed . Eighty- seven percent of the tin contained in an alloy of 82 percent tin and 17 percent iron was recovered as pure metal by pressing at 975° C followed by a second pressing at 800 ° C and a final filtering at 250 ° C. Small amounts of Sb , Cu , and Fe impurities were removed by adding Al to the molten product and performing another filtration at 250 ° C.

Jan 1, 1964