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By Joseph W. Leonard

Seven formulas commonly used to evaluate industrial screening efficiency are investigated to determine if they are suitable for calculating the efficiency of rectangular-hole screens. Six formulas were found to be limited in application to square-hole screens. The seventh, although acceptable for evaluating rectangular-hole as well as square-hole screening efficiency, was found to be unwieldy. A new formula is developed based on the concept of misplaced sizes. This proposed formula permits the single step determination of efficiency and is applicable to all types of screening applications.

Jan 1, 1975

In preparation for the 118th meeting, New York, Feb. 17 to 20, 1919, the following committees have been appointed: Committee on Arrangements ALLEN H. ROGERS, Chairman. W. S. Dickson, Secretary. J. E. JOHNSON, JR. F. T. RUBIDGE. P. G. SPILSBURY. H. C. PARMELEE. FOREST RUTHERFORD. Committee on Annual Dinner Committee on Luncheon F. T. RUBIDGE. FOREST RUTHERFORD, Chairman. E. B. STURGIS. E. MALTBY SHIPP. Committee on Patriotic Meeting H. C. PARMELEE, Chairman

Jan 10, 1918

By I. C. Runge

This paper outlines in a step-by-step approach all of the major tasks to be undertaken for the design of a complex multi-seam open pit coal mine. Examples are drawn from three such projects in the Hunter Valley of New South Wales, Australia, where computer techniques for equipment production rate estimation, mining block layout, and mine scheduling were used extensively. The paper is divided into two sections - Conceptual Planning and Detailed Planning; and the various tasks associated with these sections are discussed in detail, with examples of typical problems to be overcome.

Jan 1, 1983

By L. L. McDaniel

DURING the past few years a number of improvements in smelting and power equipment have been made at the Douglas smelter of the FIG. 1.-GENERAL PLAN OF SMELTER. Phelps Dodge Corporation at Douglas, Ariz. In the summer of 1935 work was started on the first unit of a new reverberatory waste-heat boiler plant which ultimately was to furnish steam for a modern high-pressure power plant. A second reverberatory waste-heat boiler unit

Jan 1, 1939

By B. C. Craft

The outstanding event of the year 1932 in this area was the intensive drilling activity in the Zwolle field of Sabine Parish, Louisiana. More new development work was undertaken and completed than during the previous year. This was due in part to the increased price of oil and in a Includes 19 parishes: Beauregard, Bienville, Bossier, Caddo, Caldwell, Catn-houla, Claiborne, Concordia, DeSoto, Grant, Lincoln, Morehouse, Natchitoches, Ouachita, Red River, Richland, Sabine, Union, Webster. B H. K. Shearer: Oil and Gas Development in South Arkansas, North Louisiana and Mississippi in 1931. Trans. A. I. M. E. (1932) 98, 159. a Includes 14 counties: Ashley, Columbia, Dallas, Drew, Hot Springs, Lincoln, LnFayette, Little River, Miller, Ouachita, Pike, Sevier, Scott and Union. * H. K. Shearer: Oil and Gas Development in South Arkansas, North Louisiana and Mississippi in 1931. Trans. A. I. M. E. (1932) 98, 159. part to the fact that production is below local market demands. Exploration during 1932 resulted in the discovery of a new oil field and a new gas

Jan 1, 1933

In preparation for the 119th meeting, New York, Feb. 17 to 20, 1919, the following committees have been appointed: Committee on Arrangements ALLEN H. ROGERS Chairman. NY. S. DICKSON, Secretary. J. E. JOHNSON, JR. F. T. RUBIDGE. P. G. SPILSBURY. H. C. PARMELEE. FOREST RUTHERFORD. Committee on Annual Dinner Committee on Luncheon F. T. RUBIDGE. FOREST RUTHERFORD, Chairman. E. B. STURGIS. E. MALTBY SHIPP Committee on Patriotic Meeting H. C. PARMELEE, Chairman.

Jan 11, 1918

Andes Copper has an old camp and a new camp, both isolated until recent road improvements. The old camp is at Potrerillos and the new one at El Salvador, 25 road ,miles away. The company was incorporated in 1916 and the first mine, concentrator, leaching plant, smelter and town were built in the succeeding twelve years. The first blister copper was poured on January 24, 1927. Economic conditions determined the long development period but the end result was the design and construction of a mining complex that was all of a piece, unlike the piecemeal additions to El Teniente and Chuqui. The mining episode at Potrerillos came to an end in 1960 when the ore at La Mina became exhausted and the new mine, El Salvador was brought in. Both of these ore deposits come within four hpundred feet of the surface and had they been developed within the last five years might reasonably have been brought in as open pit mines. However, that is conjecture, and as it stands the operation at La Mina was so ideal for the mining method selected, blockcaving, it became a classic for the textbooks. On the other hand, El Salvador has turned out to be a blockcaving mine to test an engineer's skill. In mining the copper deposit at Indio Muerto mountain, there are ground conditions of every conceivable type. Tunneling in one section, the back can cave like sized pea gravel and only spiling can hold it; in another heading only the lifters are shot but often the rest of the round will sit down in one piece; elsewhere the bottom squeezes up and closes the drifts; and contrary to all other locations, there are sections where the block can be undercut without support. Today the scope of operations at Andes extends from mining to electrolytic copper. Ore is mined at El Salvador and the concentrator is also situated there. Concentrates pipelined 14 miles to Llanth, the water decanted, and then it is hauled by rail 40 miles and 5500 ft higher to the Potrerillos smelter and refinery. Potrerillos and El Salvador are respectively 90 and 70 miles from the port of

Jan 11, 1969

By Fred H. Klaer

Water supplies dependent upon induced infiltration can be developed by vertical wells, by infiltration galleries, or by horizontal water collectors. Each method is described and the advantages of water obtained by induced infiltration with respect to cost, chemical quality, and temperature are shown by specific water supplies. THE subject of ground water in industry is assuming increasing importance as new processes and new industries are developed. Industrial specifications of chemical quality and temperature for process water and for cooling purposes are becoming more rigid, and water must now have many properties to meet these requirements. As ground water is usually more constant in quality and temperature, many industries are turning to ground-water supplies to satisfy their growing need. As many published articles have stated during the past several years, the ever increasing demands have caused shortages of water supply in many localities throughout the United States. Although such shortages are generally of a local nature, they have given rise to many attendant problems, such as increased pumping costs, salt water encroachment, and rising ground-water temperatures. One partial solution to the problems of overdevelopment of the ground-water reservoirs in many areas can be accomplished by developing ground-water supplies that are dependent upon induced infiltration and by planning the use of underground reservoirs. These reservoirs can be filled during periods of excess precipitation and stream flow and can be emptied during periods of drought, in a manner similar to the use of surface reservoirs. In this way water that otherwise would be wasted into the oceans is salvaged during periods of excess. The development of water supplies dependent on induced infiltration is a relatively new concept and should be defined. When a well is pumped, the water level around the well is lowered in the shape of an inverted cone or cone of depression. As pumping is continued, the cone of depression will continue to expand, horizontally and vertically, until the quantity of water crossing the perimeter of the cone plus the recharge within the area of the cone is equal to the quantity of water being pumped.

Jan 1, 1954

By G. S. Hume

In Alberta, an oil well with an estimated capacity of 60 to 100 bbl. was "brought in" at Wainwright, the oil being derived from the Colorado group of rocks. In the Norman fields, Mackenzie River area, two new holes completed showed no oil in commercial quantities whereas the "Discovery" well has now an increased flow amounting to about 100 bbl. In Kent Co., Ontario, a well from low down in the Trenton formation gave an initial flow estimated at 200 bbl. This opens up new possibilities for the Ontario fields as this is the first oil from this depth in the Trenton. ACTIVE drilling operations for oil were carried on during the summer of 1923 in various parts of western Canada, particularly in Alberta. During the early part of the summer, interest centered in southern Alberta, in the Coutts area, just north of the producing Kevin-Sunburst field of Montana; but on Nov. 14 a strike of oil by British Petroleums Ltd. at its well near Wainwright, 120 mi. east of Edmonton, diverted public attention to a new field. According to present estimates, this well has a possible production of from 60 to 100 bbl. a day; the oil is 15° Bé. with an asphaltic base and is obtained from a sand at the depth of 2019-2036 ft. The oil stands at 1700 ft. in the casing and there is sufficient gas pressure to cause it to flow when the well is opened. The oil horizon is in a sandstone in rocks of Colorado age. It is known that there is a terrace structure of which the western edge extends in a northwesterly direction from the vicinity of Hardisty to Viking, where it probably swings more to the north. At Viking a small dome-like structure on this terrace gives rise to an important gas field. Wainwright lies directly northeast of Hardisty. The exact structure in the Wainwright field is unknown. At Fabyan, 6 mi. northwest of Wainwright, the Imperial Oil Co.1 last year brought in a large gas well estimated at 14,000,000 cu. ft.; the escaping gas sprayed a small amount of heavy black oil over the derrick. The gas was obtained at a depth of

Jan 2, 1924

By William Metcalf

IT is the object of this paper to oppose unnecessary changes, and the introduction of new and confusing terms. From the earliest times of which we have any record on the subject, iron has been divided into general classes. Whether iron was first known in the form of wrought iron or of steel, is a matter of no importance; but at the time when cast iron first became a prominent article of commerce, wrought iron and steel were old products¬steel, at that time, being generally made from wrought iron by the process of cementation. As steel was then properly defined as iron containing more carbon than wrought iron, so cast iron was appropriately defined as iron containing more carbon than steel. Until the year 1776, when Huntsman first began the manufacture of a new kind of iron by melting wrought iron and steel in crucibles, the above definitions were all that could be desired. At first, probably, owing to imperfect appliances, only a highly carburized iron was melted in crucibles, and this led to its being called cast steel. If our ancestors had found a name for this material not involving the use of the word steel, we would have been saved the trouble of the present discussion. As the arts developed, new uses were found for steel, and the products of the crucible were varied, until at the present day it is quite common to find steel containing no more carbon than average wrought iron, and other steel containing nearly or quite as much carbon as some cast iron. All of these various products of the crucible have retained, or received, the name cast steel, usually abbreviated to the simple word steel, without causing any confusion among producers or consumers in regard to terms or their meaning. In 1855, twenty-one years ago, the Bessemer process was introduced ; this was followed in a few years by the Siemens-Martin process, and the products of both were at once, and have ever since been, called steel, from the fact that they were identical in chemical and physical properties with crucible cast steel. At the present time, then, we have three subdivisions of cast steel, viz.: Crucible cast steel, Bessemer cast steel, and Siemens-Martin,

Jan 1, 1877

By W. L. Austin

AT the Steptoe metallurgical plant, where ore of the Nevada Consolidated Copper Co. is beneficiated, a small copper-leaching annex has been in operation treating flue dust from roasting-furnace dust chambers, together with a siliceous oxidized ore. This leaching plant was designed to obviate smelting low-grade siliceous flue dust, which interfered with the operation of the reverberatories by forming a blanket on the charge The major portion of the copper content of the flue dust accumulating in the upper chambers of the. roaster flue, and at the stack, is water soluble, and also contains much free sulphuric acid and soluble sulphate It was found that sufficient acid could be obtained by mixing this material with water to provide a lixiviant for leaching the siliceous copper o mentioned. This was the sole source of the lixiviant used in the operatic to be described. An analysis of the flue dust showed it to be composed as follows: Per Cent. Copper 3.00 SiO2 23.41 Fe : 4.08 CaO + MgO : 2:72 Al203 6.07 Free H2SO4 19.94 S03 combined as sulphate 25.10 H2O combined With the sulphates 10.67 0 2.50 Total 97.49 Copper soluble in dilute H2SO4 2,56

Jan 7, 1914

By W. L. Austin

At the Steptoe metallurgical plant, where ore of the Nevada Consolidated Copper Co. is beneficiated, a small copper-leaching annex has been in operation treating flue dust from roasting-furnace dust chambers, together with a siliceous oxidized ore. This leaching plant was designed to obviate smelting low-grade siliceous flue dust, which interfered with the operation of the reverberatories by forming a blanket on the charge. The major portion of the copper content of the flue dust accumulating in the upper chambers of the roaster flue, and at the stack, is water soluble, and also contains much free sulphuric acid and soluble sulphates. It was found that sufficient acid could be obtained by mixing this material with water to provide a lixiviant for leaching the siliceous copper ore mentioned. This was the sole source of the lixiviant used in the operation to be described. An analysis of the flue dust showed it to be composed as follows : Per Cent. Copper.............................................. 3.00 siO2................................................. 23.41 Fe................................................... 4.08 CaO + MgO......................................... 2.72 Al203................................................ 0.07 Free H2S04........................................... 19.94 SO3 combined as sulphate.............................. 25.10 H2O combined with the sulphates....................... 10.67 0................................................... 2.50 Total................................... 97.49 Copper soluble in dilute H2SO4.......................... 2.56 The oxidized ore, locally known as carbonate, has the following composition:

Jan 1, 1915

By AIME AIME

AT a recent meeting of the Utah Section. A.I.M.E., P. D. Nielson, general plant superintendent of the new Geneva steel plant at Provo, Utah, spoke on "General Operations of the Geneva Plant." Mr. Nielson explained that the plant was located at Provo, Utah, on account of railroad facilities, the proximity of coal, iron, and limestone, and the nearness of water for operating the plant. Water probably was the most important item in making the decision.

Jan 1, 1944

By Anthony G. Reid

INTRODUCTION At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000". But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant in¬crease in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000", But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant increase in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would be the principal bridge to the bright future. The next decision involved the question of where to look for these vast new reserves. Chinese exploration teams had already looked at most of the onshore sedimentary basins and, while they were the first to admit that there was much yet to do, it was fairly clear to them that the potential for large new accumulations was confined to two areas: the little explored, remote, inhospitable regions of western China, principally Xinkiang Province and the equally unexplored offshore basins of the continental shelf and slope. In both cases China faced a very serious problem. The inhospitable environments were severely straining her petroleum industry's current technological ability to cope, particularly as the government needed rapid results. Thus the pragmatic and, to the foreign oil industry, unexpected decision to invite cooperation with the outside world. The reasons for the initial emphasis on the exploration of the offshore basins with the cooperation of foreign oil companies are again supposition on my part, but probably involved considerations of technical merit, ease of development and delivery to markets together with more sensitive issues such as controling the influence of foreign philosophies and values on the Chinese population by containing most foreign activity to the offshore. So within three years of the death of the great helmsman, China had developed a plan to involve foreign oil companies, both state and private, in a grand plan to rapidly increase the nations oil production. In fact, by this time, the first round of talks had been concluded and the first phase begun, and what a beginning. Some forty eight companies from thirteen countries had signed documents to participate formally in this world scale event. It was far easier to list those companies which did not participate than to list those which did. FOREIGN COMPANY INTEREST Why the rush by the world's oil industry to be involved in China? What was China offering which made everyone so anxious to join in? Again the answer is complex in detail, but principally involved a combination of factors which together caused this virtual stampede. Timing was a major element. Oil Companies, despite an ever increasing take by governments, were beginning to benefit. from the' rapid escalation of crude prices induced by OPEC and were looking for suitable areas to reinvest these funds. Producers

Jan 1, 1982

By Robert D. Coale, Reinhart P. Ehrlich, Terry L. Thompson

The copper concentrate slurry pipeline and pumping system of the Bougainville Copper Ltd. facilities on Bougainville Island in Papua New Guinea, is discussed. Development work necessary for the pipeline design is dealt with including a description of the 17-mile by 6-in. pipeline and pumping system as it was installed. The commissioning of the pipeline is reviewed as well as current operating performance, including data on corrosion, pump parts life, and manpower requirements.

Jan 1, 1977

By D. J. Spottiswood, C. N. Robinson, D. E. Spiller, E. G. Kelly

This paper describes the performance of a new design of spiral that is optimized for fine coal cleaning. Reduced Performance (Tromp) curves are presented to compare this spiral with the older design, as well as with other commonly used coal cleaning equipment. As an aid to equipment selection and circuit design, data are also presented to show how variables, such as flow rate, pulp density, and particle size, affect efficiency and the separation specific gravity.

Jan 1, 1985

By Edward T. Koch

A new concept involving the use of a crawler-mounted slurrifier for open-pit ore mining and overburden removal is dealt with. The design and application are discussed. Based on field experience, the area and type of operation where this machine would be effective is indicated. The slurrifier is also compared with draglines, shovels, and bucket wheel excavators. A number of the design concepts, as well as the mechanical and operational parameters, are discussed.

Jan 1, 1976

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By A. Gemperle

Electron diffraction and transmission electron microscopy on foils at room temperature were used to investigate the ordering of Fe-Si alloys containing 10 to 23 at. pct Si. A certain degree of DO3 order was found in all alloys. With the exception of the lowest silicon concentration for which the antiphase domains could not be clearly resolved, the alloys have a domain structure of two-domain type with boundaries having 1/4a01<111> displacement vectors for less than 12.3 at. pct Si and with boundaries having 1/2 a0<100> displacement vectors for more than 12.3 at. pct Si. The alloys with 12.3 at. pct Si have a domain structure consisting of fine domains with 1/2a&apos;o<100> boundaries within much larger domains with 1/4a&apos;o<111> boundaries. The development of these structures can be explained by transition of the alloy from the disordered state into the B2-type order and then into the D03-type order by the mechanism proposed previously for the FeSAl alloys. The existence of the B2 structure in the lower part of the investigated concentration range reported in some articles can be explained by fine domains with 1/2a&apos;o<100> boundaries formed by several disordered planes within large domains with 1/4a&apos;o<111> boundaries. The ordered structure predicted by the theory —with practically no domain boundaries —is found in the alloys having 12.3 at. pct Si where it develops in the B2 structure region. ORDERING in Fe-Si alloys was first studied by phragmenl who found that beginning with 13 at. pct Si the DO3 (Fe3Si) superlattice reflections appear in the diffraction patterns. The equilibrium diagrams constructed later by corson2 and Haughton3 from various measurements proposed the existence of a homogeneous solid solution (a phase) in the range from 0 to 25 at. pct Si. Jette and Greiner4 and Farquhar et al.5 measured the relation between lattice parameter and composition and they considered the break in the curve at 9 to 10 at. pct Si to be caused by the ordered solution a"(Fe3Si). Glaser and Ivanick6 Determined critical ordering temperatures of the alloys containing from 10.9 to 27.9 at. pct Si from the measurement of the electric resistivity of quenched samples. In all cases the critical temperature was lower than the melting point and it was highest for 25 at. pct Si. Lihl and Ebel7 measured the lattice parameter curves at various temperatures up to 1000°C. The region between two breaks on these curves, corresponding to 10 to 12.5 at. pct Si at room temperature, was considered by them to be two-phase (a + a"). They concluded by extrapolation of the measured values that a" in the alloy having 25 at. pct Si is stable up to the melting point. Davies8 studied superlattice reflections in the X-ray diffraction patterns of an alloy containing 8.7 at. pct Si. He found the B2 structure and short-range order in the slowly cooled samples and the DO3 A. GEMPERLE is Research Scientist, Institute of PhysicS, Czechoslovak Academy of Sciences, Prague, Czechoslovakia. __Manuscript submitted January 2, 1968. IMD structure in the quenched and annealed samples. This investigation first reports the presence of the B2 structure, phase a&apos;: in Fe-Si alloys. Meinhardt and krisement9,10 also found its existence in Fe-Si alloys by neutron diffraction. No order was detected by them in the alloy containing 8 at. pct Si. The onset of B2 order was observed at a composition of 9.2 at. pct Si. They found almost perfect B2-type order with partial DO3-type order at room temperature in the 10 to 12.5 at. pct Si range and almost perfect DO3-type order in the 12.5 to 25 at. pct Si range. They established the critical temperatures Tc of both the structures through measurement at higher temperatures. The critical temperature for the B2 structure was found to be always higher than the critical temperature for the DO3 structure of the same alloy. They extrapolated the curves of the critical temperatures and concluded that the alloys with more than 17 at. pct Si have the B2 structure up to the melting point and the alloys with more than 23 at. pct Si have the DO3 structure up to the melting point. The results of Meinhardt and krisement9,10 were confirmed by Dokken&apos;s measurement" of the temperature dependence of the electrical resistivity in the 10.8 to 15 at. pct Si range. On the other hand chessin12 detected by X-ray diffraction a considerably lower degree of order in the 12.7 at. pct Si alloy. ANTIPHASE DOMAIN STRUCTURE IN ALLOYS WITH B2- AND DO$-TYPE ORDER The ordered structures B2 and DO3 can be described in terms of a subdivision of the bcc lattice into four fcc sublattices with a parameter double that of the bcc lattice. Following Marcinkowski13 we will label them I. 11, 111, IV. The B2 structure in the AB alloy is formed by placing A atoms on sublattices I and II and B atoms on sublattices III and IV. In a non-stoichiometric perfectly ordered alloy having concentration (A) > (B), A atoms occupy sublattices I and 11. and A and B atoms distributed at random occupy sublattices III and IV. The DO3 structure in an A3B alloy is formed by placing A atoms on sublattices I, 11, and 111, and B atoms on sublattice IV. In a nonstoichiometric, perfectly ordered alloy having concentration (A)/3 > (B), A atoms occupy sublattices I, 11, and 111, and A and B atoms distributed at random occupy sublattice IV. As further shown in Ref. 13, two types of domains are possible in the B2 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4 a&apos;o<ll1> only. Four types of domains are possible in the DO3 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4a&apos;o<111> and 1/2a&apos;o<l00>. Bethe14 suggested on the basis of theoretical considerations that in a structure with two sublattices at low temperatures only one domain should be present in the whole crystal at equilibrium. Similarly Bragg15 concluded that at low temperatures the domain struc-

Jan 1, 1969