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By C. H. Loux

This paper deals primarily with the advantages realized from the adoption of methods more suitable than those previously used. The improvements noted include: (1) modification of practice in shrinkage stoping, (2) use of sublevel caving over grizzlies, (3) improved haulage and loading, (4) use of contract wages wherever possible. The Washington mine is on Jonestown Hill, one mile south of Oxford, in northwestern New Jersey. It is producing 16,000 tons of concentrates a month, which are being shipped to the Alan Wood Steel Company's furnaces at Swedeland, Pennsylvania. History The first settlement in this region is reported to have been in 1735, and the magnetite ores were recognized immediately. The first furnace, built in 1741, began operation in 1743. During the Revolutionary War the output was chiefly used for making cannon balls, which, owing to the sympathies of the community, without doubt found their way into the hands of the British. This old furnace is still standing. Several important veins were soon developed, including the Martin, Strayley, McKinley, Adelaide, Welsh and Lanning. Mining was carried to a depth corresponding to the capacity of the pumps available. When these became inadequate, the workings were abandoned, and another vein was opened up. The Washington vein was probably discovered about 1850, and the first shaft started in 1854. In 1879, William H. Scranton made the first complete magnetic survey of the district and serious exploration of the deposit was begun. Rather indifferent success attended the earlier efforts of the many companies that attempted to mine and smelt the ore. In 1929 the property was leased by the Warren Foundry and Pipe Co. to the present operators, and the modification of practice then inaugurated is described in this paper. Geology These veins, like most eastern deposits of magnetite, are formed from, or are contemporaneous with, pegmatite intrusions into a gneissic country rock. The ore therefore follows the banded structure of the gneiss,

Jan 1, 1934

By Olav Dalen

A HUNDRED years have passed since Wöhler made the first few particles of aluminum by decompos-ing aluminum chloride with potassium. In 1854 Deville used sodium to decompose the double chloride of aluminum and sodium, but even various subsequent improvements of the process, especially by Castner, did not sufficiently decrease the cost of the metal to bring it into general use. In 1862 Monckton proposed to reduce Al O? with carbon by the aid of the electric current, but the efforts of the Cowles brothers to do so were not successful and in 1884 they turned to making aluminum alloys by electrolysis. At about the same time Hall in America and Heroult in France success-fully worked out the technology of dissolving A12O3 in fused cryolite and electrolyzing the bath. It is hard to realize that forty years ago the annual production of aluminum was only 30 to 40 tons per year and the price of the metal thirty times what it is today. Great strides in decreasing the cost of production, improving the quality of the metal, and increasing the output have been made in the lifetime of middle-aged men. The large consumption of electrical energy in the form of direct current makes it necessary to locate aluminum-producing plants near waterfalls, to avoid transmission losses. Norway with its abundant water-falls is therefore a logical place for the development of aluminum production, even though it is necessary to import the bauxite, which is the raw material of the process. It was foreigners who first started the aluminum in-dustry of Norway and the first two plants were built by the British Aluminium Co. in 1906 to 1908; one at Vigeland near Kristiansand, and the other at Stavan-gerfjord in Nordfjord. These two plants are still oper-ating and producing over 3000 tons a year. When the plant at Vigeland is enlarged the production of the company will be more than 4000 tons a year.

Jan 11, 1927

By James D. Sisler

Among the various studies made by the Coal Fact Finding Commission, appointed by President Warren G. Harding in 1922 to investigate all phases of the coal-mining industry in the United States and to report to Congress, was one concerning the amount and nature of losses in mining bituminous coal in the eastern part of the United States. This study was carried on under the direction of the U. S. Bureau of Mines. The writer was appointed field engineer to investigate the problem in Ohio, Pennsylvania and West Virginia. Some 400 mines were studied in these three states and conclusions were drawn from many sources of data. The summary report written by George S. Rice and J. W. Paul states that "the field reports indicate that the recovery in Ohio will remain about as at present, except in the Belmont district; whereas in Pennsylvania it will gradually improve, and in West Virginia it will improve rapidly." Since 1922, the writer has been interested in gathering material to substantiate or contradict these prophecies. Nature of Coal Losses There are six general causes of losses of coal in mining: (1) coal left on the roof and bottom; (2) coal lost in room, entry and panel pillars; (3) coal lost in oil-well or gas-well pillars; (4) coal lost under buildings, railroads and boundaries; (5) coal lost in handling and prepayation, underground and surface; (6) coal lost by rolls, thin or dirty areas and under streams. Local economic aspects that dominate the type of mining conditions determine to some extent whether certain losses are avoidable or unavoidable. In general, however, unavoidable losses include coal lost in the protection of buildings, streams, railroads, restricted properties and around oil and gas wells. Barrier pillars and other safety pillars are unavoidable losses as long as their size does not exceed the minimum for adequate safety. Natural physical conditions beyond human control, such as rock faults, clay veins, partings and binders, bad top and bottom, rolls and horsebacks, cause unavoidable losses. Unavoidable losses

Jan 1, 1931

By John P. Harmon

This paper was written with two objects in view: (1) To describe in detail what has been done toward the ventilation of the main unit of the Portovelo mines and the results; (2) to give information that may be useful to anyone who may have to make a preliminary mine ventilation survey, with recommendations for the improvement of the existing system and finally the maintenance of the improved system. General Description The mining operations of the South American Development Co. at Portovelo, Province of El oro, Ecuador, are described here only briefly, as a full discussion does not fall within the scope of this paper. The orebodies are of the steeply dipping, gold quartz vein type, averaging about 2.0 meters wide. As shown in Fig. 1, the ore chutes are relatively far apart, making considerable development work necessary before connecting raises can be driven between the levels. Faulting' on a large scale and a parallel vein system have made long dead-end drifts and many crosscuts necessary in the exploration of veins. The ventilation of these dead ends is described under Auxiliary Ventilation. The method of mining2 is the filled rill stope method, similar to the method that is largely employed at the Butte mines. The main shaft of the mine is in the Amarillo Valley, on either side of which mountains rise abruptly to a height of several hundred feet above the collar of the shaft. Entrance is made to the mine: (1) Through the American shaft, which extends vertically from the surface to a depth of 1100 ft., of which only the first 700 ft. are in active use at the present time; (2) levels are driven from the American shaft at intervals of 30 m. (100 ft.), of which only the third, fifth and seventh levels need be considered in the ventilation problem; (3) adits at intervals of 30 m. (100 ft.), with a few exceptions, above the collar of the American shaft.

Jan 1, 1931

By Alexander L. Holley

THE Pernot system of rotating and withdrawing the hearth of a Siemens regenerative gas furnace for the production of Martin or open-hearth steel, is, perhaps, the most conspicuous of the several improvements which have lately been made in the steel manufacture. These several improvements in the open-hearth plant are not combined in any existing works, but most of them will be combined in not less than three works now erecting in the United States; and it seems probable that their joint result will not only reduce the cost of products of ordinary grades to Bessemer rates, but that it will produce new and better grades of products. The open-hearth steel furnace and its operation are so generally understood that but a few words of general description are necessary. The ordinary furnace is not unlike the common reverberatory puddling furnace, except that an intense, uniform, and controllable temperature is maintained by the Siemens gas regenerative system. The materials. employed are various : melted or unmelted pig with ore, and with or without scrap; pig iron purified from silicon and phosphorus, with or without scrap; pig iron and scrap, melted together in a cupola, or charged hot or cold, together or separately, into the steel furnace; a pig-iron bath, and hot or cold steel or iron scrap, direct sponge or Catalan or puddled blooms charged into the bath. The operation is, to a greater or less extent, according to the nature of the materials used, a desiliconization and decarburization of the pig or other crude iron, and its dilution by already purified materials. Manganese is employed at the end of the operation to remove oxide of iron and silica, a regulated amount of manganese remaining in the product. Figs. 2 and 3, Plate IV, represent the hearth and roof of the Pernot furnace; Fig. 1 shows, in cross section, the general arrangeent of open-hearth plant with Pernot furnaces, as generally designed by the author, and now building at two works. The engrav-

Jan 1, 1879

By Robert Archer

Two new alloys of the "strong alloy" class having improved fabricating qualities are described; also methods of producing alloys of the duralumin type with greater strength and hardness than previously obtained, are given. IT is about fifteen years since the development in Germany, largely by Alfred Wilm, of the aluminum alloy called duralumin. In this alloy, combining as it does the tensile strength of mild steel with the lightness and corrosion resistance of aluminum, a distinctly new material was presented to the engineering world. Despite the evident usefulness of this material, however, its commercial development has been slow, due in part to the difficulties involved in its fabrication. In view of the potentially great utility of strong aluminum alloys, it seemed desirable to find means of producing such alloys with better fabricating properties, and work was undertaken with this object in the laboratories of the Aluminum Company of America several years ago. This work has resulted in the production of two new types of aluminum alloy of the "strong alloy" class, having distinctly improved fabricating qualities. The knowledge gained has also made it possible to produce alloys of the duralumin type with greater strength and hardness than previously obtained. There have thus been made available some new engineering materials which it is the object of this paper to describe. These alloys, including duralumin, are fundamentally wrought alloys. Castings of the same compositions, heat-treated in the same manner give inferior physical properties, particularly as to ductility. The statements made subsequently concerning properties and heat treatment apply to material that has received sufficient working to thoroughly break down the cast structure. The material referred to has; in general, undergone a reduction in section of at least 80 per cent. by mechanical working. It may be mentioned in passing that other compositions have been found that are suitable for the production of the maximum physical properties in heat-treated castings.

Jan 2, 1925

By Vsevolod Krivobok

IT is generally recognized that "low temperatures" have a definite effect on the properties of metals and alloys. Furthermore, it is also generally understood that the effect is decidedly adverse. The possibility that the same low-temperature treatment might be employed for the purpose of improving certain properties of the .alloys has received less attention until recently, and the experimental and theoretical knowledge consequently is meager. The effect of low temperatures may be studied in two ways: by studying such properties as tensile strength, hardness, impact resistance, etc., at low temperature, and by studying the properties of alloys at room temperature after these alloys have been subjected to a low-temperature treatment. Even in the latter case, certain properties will differ materially from the same properties obtained on identical material but without cold treatment. In other words, subjecting alloys to cold treatment results in an irreversible change in mechanical properties. Changes of this character are usually indications of the appearance of a new phase or phases, and would be likely to occur in alloys which, either by virtue of their composition or by heat treatment, are retained at room temperature in a metastable condition. Consequently, studies of the effect of low temperatures logically should be conducted from the physicochemical point of view, since the results of such studies not only would furnish metallurgists with interesting theoretical data but would clearly indicate the classes of alloys that would hold promise of improvement, and, possibly, of new applications. As the present investigation deals with chromium and chromium-nickel alloys of iron of the stainless variety, it has been thought desirable to present the data concerning low-temperature properties of these alloys, available from the most recent and most comprehensive work of H: S. Russell.' A summary, of these data is given in Table 1. The data are confined to a limited number of alloys of the type dealt with in the present

Jan 1, 1931

By Maxwell Gensamer, Vsevolod N. Krivobok

It is generally recognized that "low temperatures" have a definite effect on the properties of metals and alloys. Furthermore, it is also generally understood that the effect is decidedly adverse. The possibility that the same low-temperature treatment might be employed for the purpose of improving certain properties of the alloys has received less attention until recently, and the experimental and theoretical knowledge consequently is meager. The effect of low temperatures may be studied in two ways: by studying such properties as tensile strength, hardpess, impact resistance, etc., at low temperature, and by studying the properties of alloys at room temperature after these alloys have been subjected to a low-temperature treatment. Even in the latter case, certain properties will differ materially from the same properties obtained on identical material but without cold treatment. In other words, subjecting alloys to cold treatment results in an irreversible change in mechanical properties. Changes of this character are usually indications of the appearance of a new phase or phases, and would be likely to occur in alloys which, either by virtue of their composition or by heat treatment, are retained at room temperature in a metastable condition. Consequently, studies of the effect of low temperatures logically should be conducted from the physicochemical point of view, since the results of such studies not only would furnish metallurgists with interesting theoretical data but would clearly indicate the classes of alloys that would hold promise of improvement, and, possibly, of new applications. As the present investmigation deals with chromium and chromium-nickel alloys of iron of the stainless variety, it has been thought desirable to present the data concerning low-temperature properties of these alloys, available from the most recent and most comprehensive work of H. S. Russell.l A summary of these data is given in Table 1. The data are confined to a limited number of alloys of the type dealt with in the present

Jan 1, 1931

By Hisaaki Takada, Atsushi Yoshida, Kazuo Satoh, Norikazu Nanko, Naoshichi Higashi

Kamioka Mine of Mitsui Mining & Smelting Co., Ltd. is the largest lead-zinc mine in Japan and is composed of two mines, Tochibora Mine and Mozumi Mine, which have daily production rates of 5,200 metric tons and 1,800 metric tons of crude ore respectively. In the mines, there are many massive pyro-metasomatic deposits which have been derived from the replacement of limestone. The deposits are composed of skarn minerals which mainly contain hedenberite. The country rock is generally hard and fine-grained gneiss. These deposits have been mined by means of the sublevel stoping method, induced block caving method and sublevel caving method at Tochibora Mine and mainly by the cut and fill method at Mozumi Mine. Since the 19601s, the trackless mining system has been introduced successfully into both mines, and is still promoted to be applied over wider areas. The underground hauling system is simplified remark- ably and much improved by adopting trackless ramps to the existing vertical and horizontal underground framework. Moreover, through the combination of the trackless mining system with the mining methods stated above, a notable increase in efficiency has been achieved. This is due to the high performance of the introduced machinery, reductions in man power of miscellaneous jobs, and also has enabled a highly efficient performance through its mobility. In addition, as it becomes possible to realize a flexible development to meet the irregularly shaped deposits and also becomes much easier to recover the remaining pillars by secondary mining, the extraction rate of ore has been improved considerably. With the introduction of the trackless mining system, the development method has been changed, thus former hand-hold leg-drills are now mostly re- placed by jumbo-type drills. Repair shops for Load-Haul-Dump machines also have been provided with an established service system. Reinforcement and rearrangement of the ventilation system has been carried out.

Jan 1, 1977

By Alfred W. Gauger, George A. Burrell

The senior author of this paper, while in Colorado on other official business, made a trip to the Cripple Creek gold-mining district to get more data than are at present available regarding the composition of the gas that issues from the rock into the mines of the district. This was done at the suggestion of George S. Rice, Chief Mining Engineer of the Bureau of Mines. There are -many questions of interest and importance in connection with the ventilation of the mines in the Cripple Creek district, such as the menace to life and mining of a suffocating gas entering the mines from the rock, the danger due to powder smoke (from blasting operations), and danger of continued inhalation of rock dust by the miners. This report confines itself to the first problem, the gas from the rock, and principally to one phase of this question, the composition of the gas and its effects on men and lights. A more thorough study of this and other ventilation problems is planned. That the rock gas is a real menace is shown by the fact that miners (variously estimated from 25 to 50 by different persons interviewed) have been killed by it in the 25 years that mining has been vigorously carried on at Cripple Creek. Many men have had narrow escapes from death, some of them having been incapacitated for days. In addition, much loss of time results because at certain periods of the year or on certain days it is impossible to enter some workings. At a few mines, fans force air into the workings, thus supplementing the natural ventilation and much improving conditions, but the improvement is not entirely adequate at all times. Origin of the Gas Lindgren and Ransome1 think that the gas found in the rocks of the Cripple Creek mining district represents the last exhalations of the ex-

Jan 1, 1917

By Charles E. Reed

With the increasing importance of clay in drilling operations which demand more precise and exacting control over its behavior, there has come the realization that most of our present methods of control over many of its important properties still represent more of an art than a science. Such a situation with respect to a material of such industrial significance is unfortunate, and naturally many investigations have been conducted to improve our knowledge. In general, these investigations have revealed the complex nature of clay behavior and while sometimes they may not have seemed to contribute directly to a solution of the field operator's problems they have been of inestimable importance in bringing to light the broad fundamental scientific principles upon which must be based any effective working theory correlating the known facts of clay behavior and predicting profitable new lines of attack for its improvement. Major Facts Concerning Behavior of Clays In the study of clays, as in that of most other colloidal materials, it has been impossible to make progress by the study of isolated facts. On the other hand, analysis of large groups of facts, many of which seem at first completely unrelated, can lead to a deeper insight into the structure of clays and the mechanism of their behavior. It will be well to list the major facts on which the analysis here presented is based, starting with those that have emerged repeatedly from past investigations and which thereby constitute an impregnable foundation upon which must rest any comprehensive theory of clay behavior: 1. Clays consist of hydrated aluminosilicates of extremely fine and variable particle size. 2. Suspended in water, clays exhibit variable degrees of swelling, depending upon their origin and upon the chemical and colloidal nature of any other substances present. The magnitude of the swelling is a direct indication of the extent to which the clay has become dispersed.

Jan 1, 1938

By R. R. Knuckey

HAVING been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout. the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. DESIGN OF SEPARATOR The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed paddle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the paddles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1943

By AIME AIME

AN entirely new type of classifier is being put on the market by The Dorr Co., following three years of development and the experimental use of thirty machines of the improvement design in various parts of the world. It is known as the Multizone classifier. Compared with the older type the lower or overflow end has been decked over and is surmounted by one or more circular overflow columns. Feed is introduced near the middle of the machine and passes downward and under a vertical baffle, then along the underside of the deck to the base of the overflow columns. Under the baffle there is a restricted turbulent zone of high pulp velocity which holds the fine and critical size particles in suspension, preventing

Jan 1, 1937

By Ralph H. Sweetser

MUCH progress in -blast-furnace construction and in the manufacture of firebrick for furnace linings has been made since the publication of Bulletin 130 of the U. S. Bureau of Mines on "Blast-Furnace Breakouts, Explosions and Slips, and Methods of Prevention," by F. H. Willcox in 1917. At the time of publishing this report comparatively little information was available to blast-furnace men as to the fundamental facts relating to the character of blast-furnace refractories. Some of the accepted theories of only a few years ago have been completely reversed. The mortality of blast-furnace linings used to be so great that nearly every furnace plant had one or more complete linings in the brick shed ready for use in case of a lining suddenly "going out"; it was generally accepted that a furnace could not "keep her lines" more than two or three years at best, and often a hot spot in the shell would develop, or a breakout occur in the hearth or bosh within a year or two after blowing in on a new lining. In some respects these frequent relinings were not so detrimental as to he a complete loss because they afforded opportunities to take advantage of advances in blast-furnace practice. At present the cost of relining has greatly increased, but the life of a lining has also increased. Anything less than five years on a lining is now considered a short blast.

Jan 1, 1932

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By E. Miller, J. M. Eldridge, K. L. Komarek

Activities of magnesium in liquid Mg-Sn alloys have been determined between 5 and 90 at. pct Sn and 990" and 1290°K by an improved isopiestic method wherein tin specimens, heated in a temperature gradient and contained in crucibles of special geometry, were equilibrated with magnesium vapor in a closed titanium system. The crucibles were designed so that the equilibrium compositions of the specimens were satisfactorily preserved on termination of the experimental runs by quenching. The activity values are in excellent agreement with those predicated on the phase diagram and allowed a delineation of the solidus curve of the compound Mg2Sn near its melting point. EQUATIONS have been recently derived relating the chemical potentials of the components to the liquidus and enthalpy data for binary systems exhibiting one congruently melting compound.' The liquidus curve of the Mg-Sn system between the eutectics was carefully redetermined and the thermodynamic properties thus calculated were in reasonably good agreement with values derived from electromotive-force measurements of an,' but differed greatly from the iso-piestically determined values of Ashtakala and Pid-geon.3 The present study was initiated: a) to resolve the discrepancies; b) to develop a method for measuring activities in systems having volatile (and possibly highly reactive) components; and c) to use the method in a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVb systems, i.e., Mg-Pb, Mg-Sn, Mg-Ge, and Mg-Si. This paper describes the results for the Mg-Sn system. An isopiestic technique, originally developed by Herasymenko 4 and adapted for alloys having a component of high reactivity and low volatility,5-8 was modified in this study by using crucibles designed to preserve the equilibrium composition of highly volatile liquid specimens on quenching from high temperatures. Tin specimens, contained in tightly covered graphite crucibles and heated in a temperature gradient, were equilibrated with magnesium vapor of fixed pressure from a magnesium reservoir kept at constant temperature in a previously evacuated and sealed titanium tube. During equilibration magne-

Jan 1, 1967

By ROBERT E. CROCKETT

MAGNETITE mining and milling in New York, New Jersey and Pennsylvania continued to remain comparatively inactive during 1933, owing to the low rate of output of the steel industry and also to unrestricted importation of foreign ores. However, some improvement over conditions existing in 1932 was noticeable, particularly in New Jersey, where one plant, that of the Washington mine of the Alan Wood Mining Co., at Oxford, went on full production in August. At Lyon Mountain, N. Y., the Chateaugay Ore and Iron Co. resumed mining and milling operations in October, on a reduced scale, principally to provide employment during the winter months. The Chateaugay company produces a special low-phosphorus pig iron. During the year they obtained a contract to supply their product for use in the manufacture of the suspension cables of the New. Golden Gate Bridge.

Jan 1, 1934

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970