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By Hamilton Wingate

In view of the fact that the fineness of the resultant bullion varies with the particular treatment to which the zinc-precipitate is subjected, and since there are considerable losses attributed to both methods, the following notes on the results obtained at the Waitekauri Extended mine, Maratoto, N. Z., may be of interest. The ordinary method of roasting the vacuum-dried precipitate was adopted instead of the treatment with sulphuric acid, the necessary facilities for the latter method not being available. Moreover, provided the ordinary method is carried out with the necessary care, it is questionable if it is not the most satisfactory where large quantities of precipitate have to be handled, and where (as is generally the case in this district) a considerable amount of silver is present. All the precipitate was first washed through a 40-mesh sieve. If it was necessary to recover the bullion at once from the accumulated short zinc, it was oxidized and melted separately; but, as a general rule, being heavily charged with bullion, it was placed on the bottom of the trays at, the top end of the extractor-boxes, where it acted as an excellent precipitant, the bullion being recovered at the next clean-up. After drying on a filter with the aid of a vacuum-pump, the precipitate was weighed and removed to the oxidizing furnace, which is similar to that generally in use in New Zealand, consisting essentially of an ordinary square tray of cast-iron, with 6-in. sides, built over a brick furnace. Wood is used as fuel. The tray is hooded over with sheet-iron, fitted with a sliding-door, and the fumes pass through a flue at the top into a dust-chamber, then into the open air. Oxidation of the Precipitate.—The oxidation was conducted first at a low temperature, which was gradually raised, until

Jan 1, 1903

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By F. C. Langenberg

DURING the course of some magnetic investigations which the authors have under way, six bars of 0.43-carbon steel were tested, a permeameter designed after the Hopkinson yoke type being used. The results obtained were of some interest and although far from complete serve at least to show the necessity for a careful investigation of the previous history of the samples under study as well as the chemical composition. A steel of given chemical composition may assume a great variety of structures, depending on its treatment. Professor Sauveur has devised a very clear and effective means of illustrating this point: The accompanying microphotographs show some of the possible structures assumed by a 0.30 carbon steel (Fig. 1). It is now a well-established fact that a structural change is accompanied by changes in the tensile strength, elastic limit, hardness, etc., and it seems reasonable to assume also, a change in the magnetic properties. Six bars of a 0.43-carbon steel were used, all the bars being taken from the same rod and treated as follows: Bar 1. Heated to 1,100° and cooled in the furnace. Bar 2. Heated to 1,000° and cooled in the furnace. Bar 3. Heated to 900° and cooled in the furnace. Bar 4. Heated to 1,000° and cooled in air. Bar 5. Heated to 900° and cooled in air. Bar 6. Untreated. The bars were then turned to 13 mm. diameter and tested by the Hopkinson yoke method. After testing, three specimens were taken from each bar, one from each end and one from the middle. The homogeneity of the. bars was tested in this manner and in no instance could any difference in structure be detected between the three specimens.1

Jan 2, 1915

By O. Jantti, Erkki Laurila, R. T. Hukki

INVESTIGATION of the methods of analyses for magnetite and ilmenite in the Otanmaki iron-titanium ore and respective mill products has resulted in certain improvements in the methods conventionally employed. The outcome of the investigations is summarized as follows: 1—Development of a diamond-drill core analyser for the determination of magnetic susceptibility of drill cores containing magnetic minerals. 2—Development of a magnetite-ilmenite analyser for pulverized products. 3—Development of a potentiometric method of chemical analysis for the determination of iron, vanadium, and titanium in succeeding steps from one test sample. 4—Proposal for a continuous and automatic magnetite assay method. Diamond-Drill Core Analyser The conventional method of assaying diamond-drill cores consists of splitting the cores, pulverizing them and running chemical analyses on representative samples. The physical properties of magnetic minerals, however, offer an entirely different approach to obtain similar final result by the measurement of respective magnetic susceptibilities in a properly designed instrument. This instrument is shown in Fig. 1. Essentially it consists of a magnetic unit, A, and of a meter unit, B. On top of A is a slot where a piece of diamond-drill core C is visible. The magnitude of disturbance in the original magnetic field caused by the magnetic minerals in the drill core can be observed from the microammeter. This reading is a function of the combined susceptibilities of all magnetic grains in the magnetic field. The magnetic unit is built of E-sheets of a shell transformer, as shown in Fig. 2. The primary coil and two identical secondary coils are wound around the central leg and end legs, respectively. The drill core under examination is placed into one of the air gaps as shown in Fig. 2. The number of ampere-turns of primary coil excited by 50 or 60-cycle ac give a maximum induction of about 600 gauss in the air gaps. The secondary coils are connected in series in the opposite direction. Thus their voltages compensate each other if no drill core exists in the air gap or if the susceptibility of the drill core is equal to zero. As soon as the susceptibility becomes greater than zero, the balance of the magnetic circuit is disturbed, resulting in increased voltage in the terminals of coil 1 and in a respective decrease of voltage in the terminals of coil 2. The voltage difference thus produced is a function of the effective susceptibility of the drill core. If the magnetic grains in the drill core are unevenly distributed, the voltage difference varies as the core is rotated around its own axis. The voltage difference is measured with a Bren-tan0 tube voltmeter. If extreme sensitiveness is desired, the established symmetry of the magnetic circuit does not allow reduction of the 0-voltage difference far enough. Therefore a compensatory voltage of a correct phase taken from the terminals

Jan 1, 1952

By A. E. Nehrenberg

R. A. Schmucker, Jr.—The writer wishes to point out that an acicular growth of austenite, similar to that described in the author's paper, was recently observed in an alloy steel of only 0.06 C content. This steel, which represents an 0.07 max C, 1.35 Cr, 0.55 Ni, 0.20 Mo analysis, combines the characteristics of minimum hardness in the annealed condition with maximum hardenability and is therefore suited primarily for cold-hobbing applications. The acicular austenite formation in this steel was observed accidentally during a determination of its Ac1 temperature. The samples used in this investigation represented as-forged bar stock which had been given a preliminary temper at 1300°F. The critical (Ac1) temperature was finally established at 1400 °F. Fig. 15 represents the microstructure of the sample which had been heated at 1450°F for ½ hr, water quenched, and tempered at 600°F for ½ hr (for the purpose of darkening the martensite). It will be observed from the distribution of the darkened areas of martensite that the parent austenite grains formed at 1450°F had grown in an acicular manner and still occupied only a small percentage of the total area. The remainder of the area contains the original equiaxed ferrite grains in which new austenite had as yet scarcely formed. However, the tiny isolated martensitic patches at several points where three or more ferrite grains intersect indicate that small austenite grains had formed and started to grow in an apparently equiaxed fashion. Fig. 16 represents the prior microstructure of an original sample in the as-forged and tempered condition, before it was heated -above the critical temperature. It is probable that there are two kinds of ferrite in this structure: (1) The equiaxed proeutectoid ferrite grains which separated from the austenite when the steel was cooled from the forging temperature, and (2) the acicular ferrite associated with the aggregate of fine carbide which is represented by the patches of

Jan 1, 1951

By R. E. H. Pomeroy

The statistical data given in this paper are taken from the actual performance of the No. 2 reverberatory furnace of the Nevada Consolidated Copper Co., Mc Gill, Nev., for a period of four months, from April to July, 1914. The principal furnace dimensions are: Length, 132 ft. % in. at the skim-line level; average width, 18 ft., 10 in. at the skim-line level. The roof is 7 ft. above the skim-line level at the firing end. The average area in the uptake flue is 36 sq. ft., and the area above the skim line under the vulcatory arch is 24.3 sq. ft. Fig. 1 shows a diagrammatic plan and sectional elevation of this furnace. The furnace is equipped with two 400-b.h.p. Stirling waste-heat boilers set in parallel. California crude petroleum is used for fuel and has a specific gravity of 16.5" B., flashing in open test at 199" F. The oil is heated to about 200" F. in a steam heater before going to the burners, requiring about 9 b.h.p. per furnace day to heat it from the line temperature to the burning temperature. Measurement is made by oil meter, checked daily by reservoir readings. The oil is fed by gravity (34 Ib. static pressure) to seven low-pressure blast burners of the Steptoe type (Fig. 2). The blast for these burners is supplied at about 40-08. pressure by a motor-driven Connersville blower of 42 cu. ft. capacity per revolution. The air supplied by the blower through the burners for atomizing the oil amounts to about 10 per cent. of the theoretical air necessary for complete combustion of the oil. The remainder of the necessary air enters the furnace through the burner openings in the firing wall. No checker holes are provided, and the charge holes in the roof are equipped with slide gates and " dog houses" to minimize air leakages. The combustion of the fuel, as shown by gas analysis at the front of the furnace, is practically complete, the carbon monoxide in the gases being less than 0.5 per cent. The draft at the firing end of the furnace is 0.18 in. of water. At the throat or in the uptake above the "verb" the draft is about 1 in.

Jan 1, 1915

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By Hobart M. Kraner

THE mineralogy of blast furnace sinter is of interest because its mineral content is one of the important factors contributing to its character. There are so many other factors affecting the properties of the sinter, however, that it is well to mention them here. The proportion and character of the raw materials, that is, raw ores, concentrates, returns, and fuel, as well as the mixing and the water content, all have a marked effect on the physical properties of the product and the degree to which sintering action can be carried on. The process of sintering is a relatively fast operation. In as much as appreciable time is required to carry on processes of fusion in such masses of low thermal conductivity, large lumps of hematite ore frequently remain unfused and partly unchanged in state of oxidation in the sintering process. The kind, the grain size, and the amount of fuel used affect both the completeness of the fluxing reaction and the prevailing atmosphere. The rate of reduction in laboratory tests is not only dependent upon the state of oxidation of the sinter but also upon the sizing and porosity. Atmosphere and temperature affect the state of oxidation of the iron oxide, and the atmosphere alone may determine the ferrous minerals that finally develop. The rate and extent of cooling, the type of coolant, the subsequent handling, and screening all have serious effects upon the type of sinter that eventually enters blast furnace bins. The degree to which actual fusion or fluxing takes place in the sintering operation has a marked effect upon density. A sinter which has been extensively fused by high content of fuel in the batch will no doubt have a higher weight on the bulk basis than one which had a lower fuel content. As high temperatures are required to do this job, the iron oxide under these conditions will be largely magnetite. Sintering at low temperatures to produce larger proportions of hematite means a decrease in the amount of liquid formed and a much more sensitive bonding process. In this case the liquid must be distributed more uniformly and thereby used more efficiently than would be the case where higher temperatures were permitted to prevail more or less indiscriminately. Where coarse ore particles are used in a sinter mix it is not expected that any particles coarser than 1/4-in. can be fused and incorporated in the system to such an extent that the gangue contained within these lumps will have been converted or fused by the sintering process. It is for this reason that coarse ore, returns, or both, in a sinter usually result in a sinter which breaks easily and at the same time may contain some of the original minerals of the lump, such as quartz and hematite. In examination of sinters at Bethlehem Steel Co. minerals such as quartz and corundum have been found, none of which are considered normal associ- ates of wustite or magnetite. Some degree of heterogeneity or lack of equilibrium is not unusual in the sintering process. The differences in specific gravity between hematite and magnetite might be ample reason for poor strength in a not very well sintered mass containing coarse particles of. ore or returns. The shrinkage taking place in a lump of hematite in its conversion to magnetite by temperature and/or atmosphere is appreciable. Sintering of ores as it is carried out is crude chemistry, for the grain size is relatively coarse, the application of heat is certainly not uniform, and the time factor is inadequate for other than partial completion of reactions. Coarse lumps of coke or coal cause local heating around these centers, and fuel which is too fine may result in such slow burning that sufficiently high temperatures are not always obtained. High temperatures are essential to the work required. The Swedish practice of sintering is established on the basis of producing an easily reducible product high in hematite. This is achieved through uniformity of grain size in the sinter mix and close control of the temperature through careful regulation of fuel and sintering rates. This produces a sinter which is very tough in character and which has a high degree of porosity. Although the hematite content is not produced upon cooling by drawing air through the mass, there would be greater possibility of accomplishing this reaction with this type of sinter than is the case in American practice. In the latter, the temperatures are so high that temperature alone converts most of the mass to magnetite. The grains are so coarse in the final product that together with the fluxed condition it would be difficult to reoxidize them to hematite upon cooling. An examination of the iron-oxygen diagram' shows that hematite does not exist above 2651°F. It also shows that there is no liquid in the pure magnetite-hematite system until 2881°F is reached. On the other hand, in the system magnetite-wustite liquids exist at considerably lower temperatures than this. It will be seen, therefore, considering only the iron oxides, that the bonding action obtained in America in sinters comes about through considerable temperature and/or reducing conditions that produce compositions containing even less oxygen than is contained in magnetite or than results from the fusion of silicates. The bonding obtained from the iron oxides is encouraged by the reducing conditions that prevail in the vicinity of the fuel particles in a mass of this sort, where temperatures are above 2600°F. As magnetite and wustite are opaque, they do not lend themselves to petrographic study by transmitted polarized light. The silicates found in sinter and the glass that has not crystallized transmit light and can be studied by these methods in which indices of refraction and other optical properties of anisotropic crystals lead to their definite identification. The index of refraction is the only property that can be measured in glass under the microscope, and this is a clue to its probable approximate composition.

Jan 1, 1954

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By NEWTON B. KNOX

THE war has forced the principal industrial nations of the' world into the strait jacket of a closely controlled economy; taxes have been heaped upon all enterprises in order to maintain the armed forces and to deprive the people of the ability to bid for goods now unavailable. These restrictions, controls, and taxes are unlikely to disappear entirely after the war has been won, for debts will remain to be paid with a long period of difficult readjustment. Although the new economy will doubtless offer plentiful opportunities for the advantageous use of capital, no investor can ignore the favorable conditions offered by industry in Latin America, where taxes are relatively low and the restrictions on free enterprise comparatively mild. In mining in South America, the great international corporations have

Jan 1, 1944

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By K. Thirumalai

Rock response to heating depends on properties of rock material and varies widely between different rock types. By dissipating energy, surface melting limits rapid heating and fragmentation of rocks achieved by surface heating methods. This study advances a concept of rock fragmentation by rapid internal heating of a localized inner volume of rock. The working of the method to achieve fragmentation of rocks (Charcoal granite and Dresser basalt) having poor response to surface heating is analyzed. Experimental data on elevated temperature rock properties required for the study are presented. Based on the properties of test rocks, a high frequency (50 MHz) dielectric heating method of generating localized internal heating was selected for experimental study. The test rocks were fragmented without melting under localized heating below 600ºC. The heated volume required for fragmentation was observed to be less than 2 percent of the test block volume. A practical application of the method for in situ fragmentation of rocks is suggested.

Jan 1, 1971

By AIME AIME

IN many countries the lack of liquid petroleum supplies has centered interest upon the hydrogenation of coal and coal tars for the preparation of motor fuel. In the United States, hydrogenation has been of greater interest for grading up low-value petroleum fractions to the more valuable volatile fuels and for the preparation of a variety of premium products, including aviation gasolines, solvents, Diesel fuels, and lubricating oils. Chemically, the basic reason for this process is that, as shown in Table 1, the ratio of hydrogen to carbon (H/C ratio) in available raw materials is quite different from that characterizing the products sought.

Jan 1, 1936

By E. A. Rychkun

The transition from Larger word type computers to the small byte oriented micro-computers has allowed specialized software to be placed directly under the control of the people requiring solutions. In addition, with the advent of interactive graphics, many complex geological and mining engineering problems can be solved graphically, thereby further forcing obsolescence on larger computers. Although the industry has not yet caught on or taken full advantage of this fact, some companies have begun to move in this direction. One such case is the Coal Evaluation System presently in use at Manalta Coal Ltd. in Calgary, Alberta. This system, designed to allow interactive analysis of simple to complex coal deposits, leads one from geophysical/core log data, to geological modelling, strip or open pit design, equipment selection, cost estimation, and cash flow analysis. The micro-computer system used is portable, stands alone, and costs less than $120,000. It is the purpose of this paper to present the coal evaluation system and its development methodology which maximizes the use of the newest computer technology. Further, in order to illustrate the practical application of the system, an example application based upon a large operating coal mine will be discussed.

Jan 1, 1983

T. M. Drown, South Bethlehem, Pa.: Mr. Thackray's paper shows in a striking way the high degree of rapidity and ac curacy exhibited by the chemists of our steel-works in ordinary everyday practice. That determinations made in an hour should present only slight differences in the third place of deci male is certainly matter for surprise and congratulation. This remarkable result has been due, perhaps, in part, to a remark able cause. The managers of works, ignorant of all the diffi culties of the laboratory, have demanded "the impossible " of their chemists—and the chemists have done it! Andrew A. Blair, Philadelphia, Pa.: Mr. Thackray's paper is extremely interesting, especially in its bearing on the question of a standard method for the rapid determination of phosphorus in the laboratories of steel-works. Before discussing the re sults in general, I desire to explain the results obtained by me under method A'. This is the method which I have used in the work of the sub-committee on Methods of the Interna tional Steel Standards Committee. It may be described briefly as follows: Solution in nitric acid; oxidation of carbonaceous matter by permanganate; precipitation of phosphoric acid by molybdate solution; reduction of molybdic acid in the reductor, and titra tion by permanganate. This method was used apparently by only three chemists, Dr. Dudley, Mr. Crowell, and myself. In determining phosphorus by this method, among the most essential points to be considered are the ratio of iron to molyb dic acid, or the reducing action of zinc on molybdic acid as compared to its reducing action on iron, and the ratio of molyb dic acid to phosphorus in the ammonium phospho-molybdate obtained by precipitation from the solution of the steel. In regard to the first point, the usually accepted ratio is 1 to 0.90756, or, as it is roughly stated, 0.9076, which is based on the assumed reduction of the molybdic acid to Mo12019,. This

Jan 1, 1896

By W. A. Anderson, R. F. Mehl

RECRYSTALLIZATION of cold-worked metals has long been known to proceed by a process of nucleation and growth.1 When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.' Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrystallization is thus analyzed into its two component rates.2 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;* values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of N and G over appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By Benjamin F. Tillson

THE past seven years, and 1937 in particular, have witnessed the return of New Jersey iron mining to a place of importance. Following the World War period, little mining was done for several reasons. The properties were operated by small merchant furnaces whose demand was not sufficiently large to warrant large-scale methods with their attendant low operating costs. Under those conditions, the ore produced could not compete with that from the Great Lakes. However, when on Nov. 1, 1.929, the Alan Wood Steel Co., of Conshohocken, Pa., leased the Scrub Oak and Washington properties at Mine Hill and Oxford respectively, they made radical changes in the mining and milling processes which greatly reduced the cost of production and pointed the way to a renewed interest in mining in New Jersey. The following factors have been advanced as influencing the reopening of New Jersey mines:

Jan 1, 1938

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

By AIME AIME

MANY interesting papers, opportunity of seeing o1d friends, and an exposition showing all that is latest in equipment, all were factors in bringing a large crowd to Detroit during "Metal Week," October 2-6. The Institute's Iron and Steel and Institute of Metals Divisions held technical sessions at the Statler Hotel on October 4 and 5, and that hotel was also headquarters for the American Society for Steel Treating and the American Society of Mechanical Engineers, both of which also had technical sessions. The American Welding Society and the Wire Association met at the Book-Cadillac Hotel, and the exposition was staged at Convention Hall, out Woodward Avenue. All in all it was a big week for men interested in metal working. One of them stated to your reporter on the train en route to Detroit that this was the one convention that he never missed, and doubtless others felt the same way about it.

Jan 1, 1933