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By D. Bienstock, J. H. Field, M. J. Lempel

A computer program is presented to perform the detailed and numerous calculations required for determining the interface temperatures and steady - state heat flow through a furnace wall composed of several refractories in layers . A method is developed that will allow the designer to determine the various thicknesses for each refractory layer to minimize either the total wall thickness or the cost of the wall per unit of area . A sample problem is presented and analyzed to illustrate the techniques involved .

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 R. L. Hopkins, H. T. Rall

A continuous method has been developed for preparing thiolacetic acid . Acetic anhydride and hydrogen sulfide are passed concurrently over an amine ion- exchange resin , under 20 - psi pressure . The thiolacetic acid , a product of the reaction , is flashed continuously from the crude reaction mixture and is purified by fractional distillation . The yield of thiolacetic acid is in excess of 80 percent based on the acetic anhydride charged . INTRODUCTION In the synthesis of reference compounds needed in the identification of sulfur compounds in petroleum , thiolacetic acid has become an important reagent because of its use in the synthesis of thiols by addition to appropriate olefins : R - CH = CH₂ + CH3 - COSH R- CH2 - CH2 - S - COCH R - CH2 - CH₂ - SH + CH3COONa NaOH (1 ) The commonly used procedures for its preparation , as described by Clark and Hartman (1 )4 and by Ellingboe (2 ) , are based on the batchwise reaction of acetic anhydride with hydrogen sulfide :

Jan 1, 1964

By Oren C. Baptist, Carlon S. Land, Eliot J. White

The water sensitivity of the oil - gas - producing sandstones in three fields in the Patrick Draw area of southwestern Wyoming was estimated by laboratory testing . The tests used to estimate sensitivity , which is a measure of the loss of well productivity if the producing formation is invaded by fresh water , are : Porosity ; permeability to gas , water , and brines ; saturation characteristics with air displacing water from the samples and by mercury injection ; and identification of clay minerals by X - ray diffraction . Laboratory results indicate that the degree of water sensitivity of the sands in the Patrick Draw, Table Rock , and Desert Springs fields vary , in that order , from moderately sensitive to highly sensitive . The main cause of the sensitivity appears to be the movement of fine particles in the pores , but the swelling of a small amount of an expandible clay mineral may also contribute to the permeability reduction observed in the samples . Laboratory results further indicate that the permeability of the sands to fresh water is seriously reduced if they are first flushed with sodium chloride brine ; calcium chloride brine is less harmful to the sands than sodium chloride brine . The low original permeability of the oil sand in the Patrick Draw field , together with its moderate sensitivity , indicate that the rate of water injection for the secondary recovery of oil will be low . Limited field experience in two pilot - injection wells confirms this prediction .

Jan 1, 1964

By D. K. Deardorff, Laurance L. Oden, H. Kato, M. I. Copeland

The equilibrium relationship of hafnium and tantalum was studied to facilitate alloy and property investigations . The data obtained are presented graphically as the equilibrium diagram . Alloys were prepared from high - purity components by nonconsumabletungsten- electrode arc melting . Data for the equilibrium diagram were obtained by optical pyrometry , metallography , X- ray diffraction of heat treated specimens , X- ray diffraction using a high- temperature camera , and differential thermal analysis . During the investigations , a casting apparatus was constructed , and the existing melting - point apparatus was improved . The bcc allotrope of hafnium forms a continuous series of solid solutions , called beta , with tantalum which exhibit a minimum melting point at 20 wt pct tantalum and 2,110 ° C. At 24 wt pct tantalum and 1,050 ° C , hafnium- rich beta decomposes in a monotectoid reaction to yield alpha and tantalum- rich beta . The monotectoid isotherm extends from 5.5 to 60 wt pct tantalum . The twophase region , in which hafnium- rich and tantalum- rich beta solid solutions are immiscible , rises to a maximum temperature of 1,265 ° C at 38 wt pct tantalum . The solubility of hafnium in tantalum decreases from 40 wt pct at the monotectoid temperature to 20 wt pct at 750 ° C.

Jan 1, 1964

By Richard F. Hewlett

An attempt has been made to fit assay data from an underground copper deposit to a three-dimensional polynomial surface as a means of expressing assay points in terms of their mine coordinates by a mathematical equation. The resulting equation was evaluated to predict the grade trend of the deposit. Although the fit obtained by this initial experiment is not considered accurate enough to provide good predictions about the deposit, the methodology is presented in this preliminary report to show the potential usefulness of the technique in mineral deposit evaluation. The technique also should be useful in determining the grade of blocks of ore for production scheduling and blending problems in open pit operations. Further experimentation is needed to increase the reliability of the computer program, to increase the precision of the method, and to make the solution more flexible for use on other mineral deposits.

Jan 1, 1964

By P. L. Woolf, N. Bernstein, M. M. Fine

Continuous experimentation utilizing a 3- by 36 - foot rotary kiln was conducted to demonstrate the feasibility of simultaneous induration and reduction of magnetic taconite concentrate . Lignite , or lignite - anthracite mixtures , and green magnetite pellets (64.2 percent Fe , dry basis ) were heated in a rotary kiln to about 2,100 ° F. After separation from excess reductant , the product pellets were found to be highly reduced and acceptably hard . A total of 140 tons of prereduced pellets with an average Fe content of 79.0 percent was produced at Minneapolis and smelted in the Bureau's experimental blast furnace at Bruceton , Pa . Two additional supplies of prereduced pellets were obtained from The Steel Company of Canada , Ltd. , Hamilton , Ontario , which contained 83.8 and 91.3 percent Fe , respectively . Smelting of prereduced pellets was compared with that of unreduced pellets obtained from The Hilton Mines , Shawville , Quebec , and from the Erie Mining Co. , Hoyt Lakes , Minn . Blast furnace tests established that a substantial decrease in coke rates and higher production result from the use of prereduced pellets .

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 R. D. Berkenkotter

This report describes a weighted method for evaluating the mean and variance of assay data from samples of different length . The method , which produces unbiased estimates from which valid confidence limits can be computed , is appropriate for bedded deposits of variable bed thickness and for vein deposits of variable vein width . Assay data from the bedded Florida phosphate deposit is used to illustrate the procedure .

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

By W. P. Haynes, J. W. Mulvihill, G. B. Taylor, S. Katell

Capital and operating costs have been estimated for separating methane and hydrogen in gas - separating plants designed to produce 90 million scf per day of product gas containing a minimum of 90 percent methane . After a preliminary literature review of various separation techniques , three different processes --moving - bed adsorption using active carbon , oil absorption , and liquefaction -- were chosen for the cost estimates . Three different methane feed gas concentrations , 5 , 20 , and 50 percent ( cases 1 , 2 , and 3 , respectively ) , were chosen as representative methane concentrations for the separation estimates . Capital and operating costs were lowest for the moving - bed adsorption process in all three cases investigated . Operating costs declined from $ 0.24 to $ 0.06 per 1,000 cu ft of product gas , and capital costs declined from $47,490,800 to $7,411,200 as the percentage of methane in the feed gas increased from 5 to 50 percent .

Jan 1, 1964

By John Ward Smith, Neil B. Young

Shale specific - gravity to oil - yield relationships were developed for black shales of the New Albany Formation of Kentucky from data collected on core samples representing the complete section of the formation in three counties . Linear equations for estimating oil yield from measured specific gravity and for estimating specific gravity from measured oil yield were shown to be applicable within small error limits to all the sites tested . Variation in pyrite content is the largest source of error .

Jan 1, 1964

By A. F. Colombo, R. T. Sorensen, D. W. Frommer

The Bureau of Mines developed a flotation method for concentrating spiral tailing produced from pilot plant tests on the Champion mine ore fines . The feed material contained about 49 percent Fe and 15 percent SiO2 and was posed mostly of specular hematite , muscovite , and chlorite . Bench- scale , batch flotation research developed a reagent suite composed of tall oil - fatty acid , fuel oil , sulfuric acid , sodium fluoride , and sodium silicate for recovery of iron minerals in the froth product . Concentrate made with the reagent suite contained 87.3 percent of the iron and analyzed 65.6 percent Fe and 1.9 percent SiO2 . Continuous flotation tests were made with a nominal feed rate of 400 lb /hr , but without middling recirculation . Using nearly the same amount and complement of reagents as in the batch tests , three similar continuous tests gave concentrates averaging 63.9 percent Fe and 3.1 percent Sio while recovering about 86 percent of the iron .

Jan 1, 1964

By Francis X. Cannaday

The purpose of this investigation was to find whether the moduli of elasticity obtained were the same for the following methods : ( 1 ) Deformation of a borehole in a prism subjected to uniaxial stress ; ( 2 ) deflection of a thin beam of uniform cross section uniformly loaded ; ( 3 ) sonic - pulse velocity measurements , and ( 4 ) strain measurements on a prism under uniaxial stress . The rock tested was chosen for its good elastic behavior and relatively good homogeneity and elastic isotropism . The same rock was used for all methods . Results indicate that for given environmental and stress conditions the moduli obtained by each of the four methods check one another within the limits of experimental error and that the differences introduced which are characteristic for each method are smaller than physical variations within the rock tested .

Jan 1, 1964

By C. J. Walker, Ray V. Huff

The feasibility of inert - gas cushions in underground gas storages was studied by the Bureau of Mines in accordance with a continuing program of cooperative research between the natural gas industry -- through the American Gas Association . As mixing of the inert - gas cushion with the stored natural gas is undesirable , the various mechanisms tending to bring about such mixing were the subjects of both theoretical and experimental studies . These studies indicated the practicability of such cushions is dependent upon both reservoir and operating conditions . Equations and tables of illustrative data relating the various reservoir and operating conditions to the expected time required for undesired mixing to occur in ideal reservoirs are presented . This information permits estimating the relationship of such factors in actual storage operations .

Jan 1, 1964

By M. H. Kersten, G. A. Brady, Jerry W. Ramsey

Anthracite samples were oxidized with nitric acid to prepare products representing intermediate stages of oxidation . Similar oxidizing conditions affected different anthracites to varying degrees as characterized by peptization behavior with 0.1 N NaOH . Techniques used in attempts to separate and characterize the products included esterification , absorption spectrophotometry , sublimation , chromatography , electrophoresis , metal salt formation , and solvent extraction . Mellitic acid , either free or in the form of metallic salts , was identified in the acid- soluble products from 10 tests in which the anthracite was treated with nitric acid for periods varying from 24 to 1,000 hours . pentacarboxylic acid was also found in some products . Other benzene carboxylic acids were not present in amounts detectable by the methods used in this study . The acid- insoluble residue from nitric acid treatment varied significantly in solubility behavior toward different classes of solvents . The most effective ones tried included polar oxygenated solvents and pyridine . Infrared spectra of the extracted material indicated that similar compounds were extracted by the different solvents . Aliphatic amines and aniline peptized the residue and o- toluidine reacted with it . Organic material separated from the residue by peptization with dimethylformamide contained 1 percent ash , consisting of more than 50 percent zirconium .

Jan 1, 1964

By D. J. Stoops, H. Kato, M. D. Carver

The effects of impurity elements silicon , aluminum, copper , nitrogen , and manganese , at 50 to 300 ppm, on properties of the zirconium alloy Zircaloy 2 were investigated . Variations in microstructure , mechanical properties , and corrosion behavior in some inorganic acid and salt solutions were observed with variations in level of impurity element . Corrodents were solutions of sulfuric acid , phosphoric acid , copper chloride , and iron chloride . Silicon was found to modify annealed microstructures by spheroidizing and dispersion of secondphase material throughout grains . Silicon or manganese improved ultimate and yield strength of the alloy without loss in ductility . All five elements affected corrosion rates of the alloy , the effect being generally different for each element .

Jan 1, 1964