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By R. G. Burdick, W. R. Peters

Shallow underground voids resulting from early coal mining and other resource recovery activities over the past several decades are now being recognized as a significant cause of ground subsidence problems. Uncertain knowledge of abondoned coal mines also imposes potential hazards in current underground mining operations, since water inundation or the release of methane gas is a serious hazard when mine excavation operations break into an abandoned mine. Requirements for detecting and mapping subversive manmade tunnels in previous work has led to the development of a surface-operated automatic earth resistivity survey system and associated computer data reduction process for military applications. Field demonstration tests of this system have resulted in successful detection of tunnels at depth-to-diameter ratios greater than 10 to one. Under the sponsorship of the Bureau of Mines, a similar high-resolution earth resistivity system was designed and constructed for use as a potential means of detecting abandoned coal mine workings. The hardware and software aspects of third new system are described together with applications of the method for surveying and mapping abandoned coal mine workings. Field tests are presented to illustrate the detection of both air-filled and water-filled mine workings.

Jan 1, 1984

Jan 1, 1967

By A. C. Fieldner, W. A. Selvig

For purposes of coal classification it is desirable to know the composition and calorific value of the pure coal substance; that is, of the coal free from its ash-forming minerals. Two methods suggest themselves: (1) To free the coal from most of the ash-forming material previous to the analysis; and (2) to analyze the coal as received and calculate the analysis, with certain more or less arbitrary corrections, to the pure-coal basis. Calculation methods are obviously more apt to give correct results with low-ash than high-ash coals. With coals of unusually high ash it would appear preferable to remove, previous to the analysis, as much of the inorganic matter as possible, by float-and-sink or acid-treating methods. Effect of Ignition on Inorganic Constituents of Coal The need of corrections in calculating analysis to the pure-coal basis is due to the fact that the ash, as determined by ignition, is not the same, in either weight or composition, as the inorganic mineral matter in the coal. On ignition a number of changes occur in the coal such as loss of water of hydration of the shaly material, conversion of pyrite (FeS2) to ferric oxide (Fe203) with evolution of the sulfur as sulfur dioxide or possible fixation of more or less of the sulfur in the ash as calcium sulfate (CaSO4), and decomposition of calcite (CaC03) to calcium oxide (CaO). The amount of sulfur from pyrite which remains in the ash as calcium sulfate depends on the amount of calcite and pyrite in the coal. Certain coals high in both calcite and pyrite show relatively large amounts of sulfate sulfur in the coal ash. The determination of total carbon and hydrogen in coal includes, besides the organic carbon and hydrogen, the carbon of inorganic carbonates such as calcite, and the hydrogen of the water of composition of some of the ash-forming minerals. For detailed discussion of corrections proposed for calculations of coal analyses to the " pure "

Jan 1, 1930

By Fred D. Wright, Philip B. Bucky

FOREWORD By E. D. Gardner[$] THE present known petroleum reserves are limited, and unless important new fields are discovered the Nation will be dependent, in the not too distant future, upon imports or upon synthetic liquid fuels to supplement domestic petroleum supplies. As a national defense measure, it would appear desirable to develop a substitute source of liquid fuels within the borders of the country if new discoveries of petroleum should prove disappointing. Congress undoubtedly had this in mind when it passed the Synthetic Liquid Fuels Act (78th Congress, approved April 5, 1944). The act directed the Bureau of Mines to construct and operate demonstration plants for producing synthetic liquid fuels from coal and oil shale, and from forestry and agricultural products. As a part of this program, the Bureau of Mines has built a demonstration plant at Anvil Points, near Rifle, Colo., for retorting the oil shale, and has developed a mine to supply the plant with oil shale. At the beginning of mining operations, the physical qualities of the oil shale, which would have a bearing upon the selection of mining methods and practices for exploiting the deposits, were largely unknown. A comprehensive mining-research program has been set up to determine the best methods and practices to follow to obtain the lowest overall practicable mining cost for producing the oil shale on a large scale. Unusually low mining costs will be necessary for shale oil to be produced commercially. Consideration now is being given to exploiting a series of flat-lying beds 70 ft thick by a room-and-pillar method of three benches with the advance heading at the top. This report is one of a series giving the results obtained in research on mining problems. INTRODUCTION The structure and physical qualities of the oil shale indicate that the 70-ft interval of the oil-shale measure can be safely mined in open stopes; studies indicate that this method would be the most economical one to use.1 As labor will be a major item of expense, the largest equipment that could be operated efficiently in the workings would be required to obtain the lowest practicable mining cost. It was therefore desirable to know the maximum safe span of unsupported rooms and the size of pillars necessary to support the overburden. This paper describes the work done at the Columbia School of Mines Barodynamic Laboratory in determining the maximum safe unsupported roof spans and the minimum safe pillar dimensions for the oil-shale mine at Rifle, Colo.

Jan 1, 1947

By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By Charles De Witt

The ore treated at the reduction plant (called Yangdei) of the Chiksan -Mining Co., Korea, is brought from four of the company mines, and from the small tribute mines. The largest shipments conic from Sajunkohl mule, situated about a mile and a half from the mill (Fig. 1). The ore is quartz of medium hardness. The overage assay value in gold is $6.95 per ton. At the mine the ore is put into bin,, and is Mien trammed over an 8 per cent. grade to the tipple bins above the mill, where the ore is drawn through the hull holes as desired. The capacity of the tipple bins is about 3,500 tons. On, from Moonsukohl, Chung Tarrie, Yang Chun, and the tribute mines is brought in by bulls and bull wagons. The bulls carry from 350 to 800 lb.; the average wagon load is about 1,200 lb. (Fig. 2). One shovelful of ore out of every ten is taken as a sample. Considerable ore

Jan 5, 1915

By A. R. Denison

The area discussed in this report comprises a group of 38 counties lying in the northeast corner of Texas. It covers all, and extends beyond, the borders of what is commonly described as the East Texas Basin. It includes two major oil fields, Van and East Texas; two major gas fields, Bethany and Waskom; and a number of fields, both oil and gas, of lesser importance. All commercial oil production comes from beds of Upper Cretaceous age and almost exclusively from the basal member, the Woodbine sand. Gas is produced from both Upper and Lower Cretaceous beds with the newer production from the older beds. East Texas Field This field continued as in 1932 and 1933 to dominate the drilling and production situation throughout the oil business. A total of 3681 producing wells was completed in this field during 1934. This is an increase of 1215 over the 2466 producers completed during 1933. Total wells

Jan 1, 1935

By Helmut Thielsch

In recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsifi-cation and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.' In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously. From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time—i.e., improving the plant efficiency— great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. Apparatus The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2½ in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1947

By Helmut Thielsch

In recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsifi-cation and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.' In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously. From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time—i.e., improving the plant efficiency— great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. Apparatus The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2½ in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1947

By J. R. Stone, J. T. Roy

ASARC09s continuous tapper for lead blast furnace is described. Its use throughout the company's plants has resulted in higher production rates, lower labor costs, and better working conditions. It has also permitted wide latitude in blast pressures, as well as in charge and slag compositions. The practice of tapping a lead blast furnace has remained essentially unchanged for many years. In principle, it is a batch operation discharging the products from the continuous smelting of lead-bearing materials. As such, it imposes certain restrictions on the proper functioning of the smelting operation. First, it calls for a highly developed sense of timing, and a considerable amount of physical effort on the part of the operator. Dirty and hot working conditions, as well as the hazards of flying metal and slag, usually prevail. These conditions have resulted in higher labor costs, both in rate and in amount. Labor turnover has also been high. Secondly, rigid control of mechanical and metallurgical factors must be maintained. Frequent oxygen lancing of the tap hole is needed to permit tapping, thereby increasing operating costs. Rapid increases in smelting rate, plugged tap holes, or forgetfulness on the part of the operator may permit the molten material to rise above the tuyeies and freeze the furnace. Also, the operator will often blow out the tap hole after draining, filling the area with fume. Composition of charge also vitally affects the tapping. The type of lead-bearing material being smelted will naturally affect the smelting rate, and thus the frequency of tapping. The amounts and types of fluxing materials, which determine the ultimate fluidity of the slag, must be regidly controlled. Finally, the batch tapping of a continuous smelting operation of this type appears to be wrong in principle. The molten material drains into the crucible at the bottom of the furnace where it starts cooling immediately and continues to cool until tapped out. While keeping the lead molten is no particular problem, maintaining a fluid slag at all times is often difficult, and sometimes impossible. These factors all point to the desirability of a method for the continuous tapping of a lead blast furnace. The expected advantages would be more desirable working conditions, lower labor costs, increased production, and a much wider latitude in both blast pressure and charge composition. CONTINUOUS TAPPING Historical. A number of devices, e.g., mechanical tappers, siphons, and lead wells, have been tried in the past in attempting to effect continuous tapping. None proved to be entirely satisfactory for tapping lead and slag simultaneously. It was not until 1955, however, that ASARCO designed and put into operation a successful tapping unit at its East Helena, Mont. lead smelter. This unit is described in detail in U.S. Patent NO. 2,890,951. Continuous Tapping Unit—See Figs. 1 and 2. Fig. 1 is a schematic drawing of the unit in place, showing front and side views. The component parts are identified in the caption. Fig. 2 is an actual photograph, front view, of the tapping unit attached to the base of the blast furnace. Operation. The operation of the tapping unit is quite simple. Essentially it consists of a narrow tapping bay surrounding the furnace tap hole, with a deep notch in the front wall. When the blast furnace is started this notch is open down to the level of the tap hole. Starting the furnace may be accomplished in several ways but the most satisfactory method is to plug the tap hole with clay, permitting metal and slag to build up inside the furnace. Before the liquid reaches the tuyeres, the plug is removed and the furnace is drained to the settler. The blast is then stopped momentarily while the notch in the front wall of the tapping bay is dammed with chrome brick and plastic chrome ore. The blast is again started, and the height of the dam is adjusted so that the liquid in the bay will counterbalance the internal pressure of the furnace. When the desired level is reached the slag and metal will overflow to the settler. It should be noted that the molten material ,is not siphoned from the furnace and that the metal 'acts as a liquid valve controlling the flow of slag through the tap hole. During normal operations the tapping bay is filled primarily with lead, covered with a thin layer of slag. Thus, the heavier lead plays the major role in compensating for variations in furnace pressures. Due to the high specific gravity of lead, changes in the liquid level in the tapping bay will never exceed a few inches. For this reason it is seldom necessary to change the height of the dam due to minor variations in operating conditions. Some turbulence of the liquid in the bay is essential at all times. This indicates that the level of the

Jan 1, 1963

Jan 1, 1970

THE transformation, in a sample of levitation melted iodide titanium, has been studied with a Leitz hot-stage microscope. The specimen was etched in HF:HNO3: glycerine, (1:1:2) giving a structure shown in Fig. 1, and was then heated at approximately 5OC per min. At 870°C (±5OC) the etching product disappeared, the a-grain boundaries showed in relief, and some new grain boundaries (presumably of ß) appeared (Fig. 2, see arrow). Some evidence of ß-grain growth is indicated by the apparent longitudinal movement of a ß-grain boundary shown in Figs. 2 and 3 (see arrows). The specimen was later heated to 1000°C and then cooled at 2°C per min. At 845°C rumpling of the surface was first noticed, Fig. 4, and continued at constant temperature. The photomicrograph reproduced in Fig. 5 was taken 6 sec after Fig. 4, at 845°C. Fig. 6 shows the structure after cooling to room temperature. The room-temperature structure, showing a rumpled surface has been observed by previous investigators.' These structures presumably indicate a sheer transformation ß - a, athermally nucleated, but capable of isothermal progression.

Jan 1, 1960

By B. N. Das, P. A. Beck

THE o phases have a complex tetragonal structure with Lo/ao = 0.52 and 30 atoms per unit cell.1 A large number of such phases are now known to occur in various binary systems of the transition elements and they exhibit the following typical features: 2,3 The composition of binary o phases is variable, ranging from approximately A4B to ABI. With only a few exceptions, in the o phases the A-ele-ment comes from the V- or Cr- group of the periodic table, while the B-elements are from the Mn-, Fe-, Co-, or Ni- group. In the first long period the corresponding o phases of the V- and Cr-series have approximately the same compositions. However, as the B-element changes from Mn to Fe to Co to Ni, the mean composition shifts monotonously toward higher A-contents.2-4 For example, if the mean compositions of the various o phases with vanadium are compared with each other, the composition shift mentioned above becomes plainly visible: V 30Mn0 80 Vo.45Feo..,, Vo .,Coo. 45 and Vo.5Nio.3. Similiar composition shifts, although not the same composition values, were observed in u phases formed by second and by third long-period transition elements.3'4 This behavior, very characteristic of o phases, is in rather sharp contrast to the usually quite well-behaved stoichi-ometry of the Laves phases. In the latter, the AB2 stoichiometry predominates, with A the large atom and B the small atom.= The p phase occurs in the four binary systems of Mo or W with Fe or Co. On the basis of their crystal structure determination, Arnfelt and westgren6 ascribed to the p phase in the Co-W system the ideal composition W,Co7. Since all four binary pphases have nearly the same composition, it would seem quite plausible that some definite stoichiometry such as A6B7, might be characteristic of this phase, as AB2 is of the Laves phases. On the other hand, it has been noted,7 that the phases occur at average electron concentrations near to those at which the various cr phases are found. Also, it has been pointed out by Shoemaker and associates8 that structurally the a phases and the p phases are somewhat related to each other; both of these structures may be described in terms of suitable stackings of quasi-hexagonal layers'of atoms. By studying a suitably chosen ter- nary phase diagram, one might expect to be able to find out which one of the two conditions, the analogy with the o phase or the constant ratio between the number of large atoms and the number of small atoms in effect governs the behavior of the p phase. Several isothermal sections of ternary systems containing o phases have been investigated. In all cases where two binary o phases occur, these were found to be connected b a more or less straight ternary o phase field.7' '10 Such elongated o phase fields were also found in ternary systems in which only one of the limiting binaries is known to contain o phase. In this manner a latent o forming tendency could be detected and the virtual composition of a "binary o phase", which does not actually occur as such was approximately determined by extrapolation. The behavior of the phases, including their composition shift, is analogous to that of the classical electron compounds, as described by Hume-Rothery.11 In order to decide whether the p phase is essentially a "size compound" like the Laves phases, where a fixed stoichiometric ratio is quite generally maintained between the "large atoms" and the "small atoms", or whether the p phase is typically an "electron compound" in the same sense as ois, it was decided to investigate an isothermal section of the Mo-Mn-Co system. The Mo-Co system12 and the Mo-Mn system13 each are known to have a binary o phase. It could be therefore expected that a ternary o phase field will connect these two binary cr-phase fields. The p phase is known to occur in the Mo-Co system. If the p phase should turn out to form an elongated phase field extending deep into the ternary system, the following considerations mighto apply. The atomic radius of manganese (1.314for C.N.12) is between the va,lues for Mo (1.40Afor C.N.12) and for Co (1.26Afor C.N.12). If it is assumed that p is a "size compound", and that Mn is substituting for the smaller Co atoms in the p-structure in the ternary system, the y-phase field might be expected to extend parallel to the Mn-Co binary line. If Mn is substituting for the large Mo atoms in the p-structure, the p-phase field may be expected to extend parallel to the Mn-Mo binary line. On the other hand, if the p-phase turns out to be an "electron compound" like o, the ternary p-phase field should extend parallel to the ternary o -phase field connecting (Mo,Mn)owith (Mo, Co) a

Jan 1, 1961

By Homer S. Frankhouser

Materials may be dredged, processed, stored and loaded for shipment at a single site in water depths ranging from 250 to 1200 ft. Solution mining may also be accomplished in deep sea situations. And, open air subsea mines with direct surface access may be developed and worked under the ocean floor. These concepts for deep sea mining are the results of extensive testing of individual components of the proposed systems by Dravo Ocean Structures, Inc., a subsidiary of Dravo Corp. A basic structure in these systems is the articulated platform. The platform consists of a gravity- type base and a buoyant cylindrical column which is constructed at an onshore location, towed to the offshore site and installed in a matter of days without use of heavy equipment. The base is also buoyant for towing purposes. This allows for gradual flooding to the point of negative buoyancy for positioning and anchoring to the ocean floor.

Jan 1, 1971

Jan 1, 1968

Jan 1, 1968

Executive SCOTT TURNER, Chairman FREDERICK M. BECKET JOHN A. MATHEWS H. A. GUESS WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL D. MERICA ROBERT E. TALLY Admissions JOHN M. LovEJOY, Chairman GEORGE D. BARRON ERLE V. DAVELER WILLIAM H. BASSETT W. D. B. MOTTER, JR. Alternates HENRY B. FERNALD F. JULIUS Polls AMOR F. KEENE

Jan 1, 1932

Jan 1, 1970

By J. B. Dyess

TARNISH films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper .2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen. sulphide in air to form the various oxide-sulphide films studied. The comparative resistances afforded by (1) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of T= MX10 8 2D X 96,494 X 103 (a) where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angström units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values2 of t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939