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By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

By H. F. Yancey, M. R. Geer, Franklin T. Davis

Coke with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning, An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. Previous Work Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,' and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.'

Jan 1, 1944

By M. R. Geer, Franklin T. Davis, H. F. Yancey

Coke with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning, An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. Previous Work Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,' and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.'

Jan 1, 1944

By J. T. Ryan

SiR Humphry Davy's epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demonstrated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the workmen's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines had demonstrated some dangers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Consequently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Two Groups of Dangerous Coal Mine Gases Dangerous coal mine gases may be placed in two groups: (I) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CH4) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture. The explosive range of methane-air mixtures is well defined. The low limit is 5 per cent., the high limit 15 per cent., and the most explosive

Jan 1, 1927

By E. P. Mathewson

The experiments described in this paper were made at the Washoe Reduction Works, Anaconda, Mont., for the purpose of determining the relative speed of elimination of the iron, sulphur and arsenic during the process of bessemerizing copper-mattes. The samples were taken from a horizontal a barrel" converter, 8 ft. in diameter and 12 ft. 6 in. long, having an average charge of 9 tons of matte, and blown with a 16-lb. air-pressure. All samples were taken with the blast on, turning the converter from its normal blowing-position to nearly vertical, so that a conical mold, with a long handle attached to a horizontal rod, could be introduced from a platform above the converter into the mouth of the converter and a sample taken. The difficulties of taking a sample with the blast on are apparent, and the irregularities of' the lines in Figs. 1, 2 and 3 can be readily accounted for by the amount of slag in the samples. On the whole, the plotting of the results gives comparatively uniform lines, considering the conditions. The samples were taken by the regular sampling-force of the works at 10-min. intervals, as shown in Tables I., 11. and III., which also give the chemical analysis of the samples so taken. The test shown in Table I. was made with a new converter; that of Table 11. with a converter that had made three charges and had been cleaned out; that of Table 111. with a converter that had blown one charge to white metal, and had then been " washed " out and used for the test. In plotting these results, it was necessary to take, as a basis, the percentage of copper in the samples. This basis does not exactly represent the true condition, since the volume is constantly decreasing and a certain quantity of copper passes into the slag, but it is as near as can be obtained in practice. Take, for instance, in Table I., the sample No. 5, which shows: Cu, 59.9;

Jan 1, 1908

By A. Bar-Or, G. Hirsch, P. Wynblatt

The rates of nucleation and growth at various temperatures in U-0.45, 1.1, and 1.35 at. pet Cr alloys were determined, providing a qliantitative proo-f that the transformation under study is controlled by nucleation and diffusional growth. The linear relationship, log NV US 1/T2, suggests that the nucleation of the alloys is probably controlled by the classical law of nuclei formation. The established linear relationship, log G us 1/T, in the three alloys suggests that growth in each alloy is controlled by bidimensional nuclei formation. It was established that both the rate of growth and the rale of nucleation are retarded by chromium. Using classical formulae, sApN and sApG (the ß/a apparent interphase energies) were calculated from the nucleation and growth results, respectively. It was found that their values are of the same order of magnitude. However, why sApN is unaffected by the addition of chromium, while sApG increases with it, needs further clarification. In the last few years, an appreciable amount of research has been conducted into the mechanism of the ß —a transformation in uranium and uranium alloys. Recently, Burke1 reviewed the published work concerned with this transformation. He concluded that in dilute uranium alloys it is firmly established that, at high temperatures in the a range, ß decomposes by a diffusional process. However, he based his conclusion either on experiments dealing with the over-all transformation,2 or on qualitative results.3 It was felt that a better insight into the mechanism of transformation could be gained from the quantitative measurements of growth and nucleation rates, which we aimed to carry out in the present work. In a previous work,4 we have shown that a rim of a grains is formed during isothermal transformation at the high a range. The thickening of this rim with time was used for measuring the rate of growth in U-0.45 at. pet Cr.5 This method was also used in the present work for two more alloys. For meas- uring the rate of nucleation, a method of quenching and macroetching was developed to allow differentiation between a grains formed during isothermal transformation at the upper a range and those formed after quenching, Fig. 1. EXPERIMENTAL WORK AND RESULTS The Rate of Nucleation. The measurement of the rate of nucleation was effected by counting the num-

Jan 1, 1965

By John J. Egan

THE present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire Submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all Substances that occur or that may be in any way associated with steelmaking operations, Such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee's earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. SPECIFIC HEATS, HEATS OF FORMATION, ENTROPIES AND FREE ENERGIES OF VARIOUS PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES. I . Determination of specific heats and entropies of oxides, sulphides, nitrides, etc. over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc. over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineralogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By W. Irwin Moyer

Two methods for the rapid valuation of oil properties are in common use. The one best known and most widely used is the "per barrel" value, based on the present daily production of the well, without regard to its past performance or the history of the sand or pool from which it produces. The second method is the "time to pay out," or the lengt of time required for a well to place itself upon the credit side of the ledger, from which time the returns from its production (less the operating expenses) will be clear profit. The time basis for valuation is also commonly used in the appraisal of an undeveloped lease. In most oil fields, it is not thought good business to invest in production that will not pay out in at least 4 to 5 years. Nearly all buyers (except in certain regions of very persistent production like the deep-sand territory of the Appalachian field) expect wells to pay out in considerably less time than this. Like the barrel-per-day price, the time necessary for a well to pay out has been determined for each field, so that one frequently hears a field or district referred to as having a certain time to pay out. This is considered the norm for that field or district and the buyer and seller base their value, to greater or less extent, on their belief in the accuracy of this time. The writer long ago became convinced of the inaccuracy of the barrel-per-day method, except when greatly modified for local conditions, such as the age of the wells, their economic limit, operating conditions in the field, the future price of oil, and the persistence of the sand as a producer. When so modified, this method becomes more of an analytic or predicted probable-yield valuation. While the appraiser may not go through each step in a valuation based on future returnable revenue, his knowledge of the field and the local conditions surrounding his leases make it possible for him to estimate a fair sales value that, in many cases, will be a close approximation to the truth. This is quite different from she commonly understood barrel-per-day value, in that the conditions turrounding the sale of one lease or property at a fair market value may

Jan 1, 1923

By W. Irwin Moyer

Two methods for the rapid valuation of oil properties are in common use. The one best known and most widely used is the "per barrel" value, based on the present daily production of the well, without regard to its past performance or the history of the sand or pool from which it produces. The second method is the "time to pay out," or the lengt of time required for a well to place itself upon the credit side of the ledger, from which time the returns from its production (less the operating expenses) will be clear profit. The time basis for valuation is also commonly used in the appraisal of an undeveloped lease. In most oil fields, it is not thought good business to invest in production that will not pay out in at least 4 to 5 years. Nearly all buyers (except in certain regions of very persistent production like the deep-sand territory of the Appalachian field) expect wells to pay out in considerably less time than this. Like the barrel-per-day price, the time necessary for a well to pay out has been determined for each field, so that one frequently hears a field or district referred to as having a certain time to pay out. This is considered the norm for that field or district and the buyer and seller base their value, to greater or less extent, on their belief in the accuracy of this time. The writer long ago became convinced of the inaccuracy of the barrel-per-day method, except when greatly modified for local conditions, such as the age of the wells, their economic limit, operating conditions in the field, the future price of oil, and the persistence of the sand as a producer. When so modified, this method becomes more of an analytic or predicted probable-yield valuation. While the appraiser may not go through each step in a valuation based on future returnable revenue, his knowledge of the field and the local conditions surrounding his leases make it possible for him to estimate a fair sales value that, in many cases, will be a close approximation to the truth. This is quite different from she commonly understood barrel-per-day value, in that the conditions turrounding the sale of one lease or property at a fair market value may

Jan 1, 1923

By W. L. Zeigler

THE tailing from the gravity concentration plant of the Hecla Mining Co., Gem, Idaho, was former-ly loaded into railroad cars to be used for ballast, highway surfacing material, or concrete work, or dis-posed of by an aerial tramway, which dumped it into another gulch. The tailing averages about 1.2 per cent lead and 0.8 oz. silver to the ton. Further treatment for the recovery of the valuable metals had been investigat-ed several times with results that did not warrant the construction of a retreatment plant; but early in 1925 experimental work was again started with small tests, and later with a 10 tons per day flotation test plant. This showed that the tailing could be ground and treat-ed by flotation at a profit. It was decided to make the new flotation plant an addition to, rather than incor-porate it in the old concentrator, the original capacity of which had been increased many times, the present arrangement being by no means ideal. The old mill buildings were of timber and board contruction, creat-ing more or less fire hazard, so all new construction was made fireproof. Construction work on the new plant was started in the middle of July, 1925, and the plant was placed in operation early in December. The building is of concrete and steel with hollow tile walls, steel sash and corrugated asbestos roofing. The ball-mill floor has for its foundation a cellular reinforced concrete block about 14 ft. deep, extending to cemented river gravel, and the cells filled with tailing to give weight to the block. Overhead, built into the steel frame, is a 5-ton hand-operated traveling crane. With both ball-mills running fully loaded, there is not the slightest trace of vibra-tion in the foundation or building. The flotation floor is of reinforced concrete beam construction and spans Canyon Creek. Adjustable plunger feeders are arranged under the the tailing-bin, which feed by gravity to a 14-in. eleva-tor, discharging to a short 18-in. conveyor. From the conveyor the tailing is discharged into a dividing hop-per, from which point the plant is arranged in three separate units. Each unit consists of a ball-mill in closed circuit with a classifier, and an 8-cell flotation machine and has an approximate capacity of 300 tons per 24 hours.

Jan 8, 1927

By W. Irwin Moyer

Two methods for the rapid valuation of oil properties are in common use. The one best known and most widely used is the "per barrel" value, based on the present daily production of the well, without regard to its past performance or the history of the sand or pool from which it produces. The second method is the "time to pay out," or the length of time required for a well to place itself upon the credit side of the ledger, from which time the returns from its production (less the operating expenses) will be clear profit. The time basis for valuation is also commonly used in the appraisal of an undeveloped lease. In most oil fields, it is not thought good business to invest in production that will not pay out in at least 4 to 5 years. Nearly all buyers (except in certain regions of very persistent production like the deep-sand territory of the Appalachian field) expect wells to pay out in considerably less time than this. Like the barrel per day price, the time necessary for a well to pay out has been determined for each field, so that one frequently hears a field or district referred to as having a certain time to pay out. This is considered the norm for that field or district and the buyer and seller base their value, to greater or less extent, on their belief in the accuracy of this time. The writer long ago became convinced of the inaccuracy of the barrel per day method, except when greatly modified for local conditions, such as the age of the wells, their economic limit, operating conditions in the field, the future price of oil, and the persistence of the sand as a producer. When so modified, this method becomes more of an analytic or predicted probable yield valuation. While the appraiser may not go through each step in a valuation based on future returnable revenue, his knowledge of the field and the local conditions surrounding his leases make it possible for him to estimate a fair sales value that, in many cases, will be a close approximation to the truth. This is quite different from the commonly understood barrel per day value, in that the conditions surrounding the sale of one lease or property at a fair market value may

Jan 1, 1922

By H. J. Struth

Conditions in the gasoline market undoubtedly influence the oil industry's general economic situation to a greater degree than perhaps any other single factor. No matter how efficiently the oil industry manages to conduct its producing operations, a drop in the price of gasoline exerts definite pressure upon the posted price of crude oil in the field. Efforts of the recent past have shown that profits from the producing division of the industry are closely tied in with the course of the gasoline market. When refinery gasoline prices are depressed, as they have been during recent months, it is utterly impossible for purchasers to maintain a crude market that is commensurate with the cost of production, regardless of how well balanced the producing situation may be. In fact, the producer can no longer regard his operations in the light of an independent unit of the oil industry, since his financial well-being is directly dependent upon the well-being of the refiner. Because gasoline is the principal constituent of crude oil, it is obvious that profitable refining operations can only be maintained through profitable gasoline markets. Likewise, when the price of gasoline influences a profit for the refinery it also influences the prosperity of the producer, through the advent of higher and more profitable posted prices for crude oil in the field. Financial results for 1932 showed material improvement over the preceding year, primarily because the price of gasoline was maintained at levels somewhat above those of 1931. Consequently, the producer was able to record improvement in the crude market, through a somewhat higher level of posted prices. While effective methods of prora-t,ion of crude production are given credit for the advance recorded in the crude market last year, it is also a fact that the advent of higher prices for gasoline had a direct influence upon the posted prices of crude oil. For example, when gasoline was sold in Group 3 at 2 3/4 a gallon in June and July, 1931, the price of 36-gravity Mid-Continent crude was down to its lowest point of only 18c a barrel. As refinery prices advanced, however, there was a corresponding advance in posted prices of crude oil. Thus, when Group 3 gasoline commanded a price of 5c a gallon

Jan 1, 1933

The Diamond mechanical soot blower system, manufactured by the Power Specialty Co., Detroit, Mich., consists of a permanent installation of units arranged in groups to fit the design of the various boilers to which they are attached. The units are so arranged as to effect the cleaning of the fire surfaces of the boiler, particularly the tubes, by means of steam jets. When this steam is released among the tubes at a velocity of approximately 2700 ft. per sec. (assuming a pressure of 150 lb.), a perfect whirlwind of currents is created, reaching all the nooks and crannies of the boiler, and thoroughly removing the particles of soot and fine-ash accumulation. This operation requires but a moment's time-from 20 to 50 sec. per unit¬and is performed from two to four times a day, while the boiler is under full load, using a greatly decreased amount of steam and labor as compared with the hand hose or any other system of blowing. Moreover, this cleaning is effected without admitting air, with its cooling effects, to the boiler setting. The Diamond model "G" blower consists of five principal elements as follows: 1. A head through which the steam passes from the main supply line when the valve is opened. The head is the foundation element to which the other elements are attached. 2. A wall box which is bricked into the setting. The box supports the unit, and is so constructed that the blower can be turned freely without admitting air to the inside of the setting. 3. A blower element running cross-wise of the bank of tubes, and consisting of a small header with nozzles so placed as to discharge steam between the boiler tubes. 4. A sheave or hand wheel by means of which the blower element is rotated. 5. Bearings attached to the boiler tubes which support the blower element and permit it to revolve freely. The nozzles from which the steam issues are designed on the principle of the Venturi tube, and vary in design for different pressures. The expanding walls of the Venturi nozzle increase the velocity of the steam over 200 per cent., as compared with a nozzle having a straight orifice. Thus, the velocity of the steam issuing from a straight nozzle at 150 lb. pressure is 912 ft. per sec., whereas, at this pressure the velocity of the steam issuing from a Diamond Venturi nozzle is 2795 ft. per second.

Jan 5, 1918

By Terkel Rosenqvist

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

Jan 1, 1952

By Arthur C. Simmons

Oil production and activity in northern and central Pennsylvania was slightly less in 1939 than in the previous year, but owing to higher average prices 1939 was undoubtedly a better business year. The last quarter showed markedly increased activities throughout all of the Pennsylvania fields. Production, Stocks and Price Storage of Pennsylvania crude oil at pipe lines and refineries totaled 5,413,000 bbl. on Dec. 31, 1938, and declined during the year 1,124,000 bbl. to a total of 4,319,000 bbl. at the end of 1939. The stocks of crude at the end of the year represent the lowest point reached in Pennsylvania-grade crude storage in recent years. Stocks increased slightly during April, May and June, but decreased during all other months of 1939. The Bradford field production within the state of Pennsylvania averaged 35,340 bbl. per day throughout 1939, which represents a decrease of 1419 bbl. a day from the 1938 average. The production in central and southern Pennsylvania increased 1176 bbl. per day, averaging 12,159 bbl. throughout 1939. Table 1 includes annual production for the part of Bradford field situated within the state of Pennsylvania, for central and southern Pennsylvania, and for the entire state of Pennsylvania. A definite segregation of production between the Bradford field and central and southern Pennsylvania is slightly ambiguous because a portion of the oil from the newly discovered Music Mountain pool is included statistically in each area. In all probability the entire increase and some small addition to the production from southern Pennsylvania can be attributed to oil produced from the Music Mountain pool. Within the Bradford field, six price changes occurred throughout the year. At the beginning of 1939 the price of Bradford crude oil was $1.80 per barrel, whereas by the end of the year it had risen to $2.50. The weighted average price for Bradford crude during 1939 was $2.059 per barrel.

Jan 1, 1940

By Arthur C. Simmons

Oil production and activity in northern and central Pennsylvania was slightly less in 1939 than in the previous year, but owing to higher average prices 1939 was undoubtedly a better business year. The last quarter showed markedly increased activities throughout all of the Pennsylvania fields. Production, Stocks and Price Storage of Pennsylvania crude oil at pipe lines and refineries totaled 5,413,000 bbl. on Dec. 31, 1938, and declined during the year 1,124,000 bbl. to a total of 4,319,000 bbl. at the end of 1939. The stocks of crude at the end of the year represent the lowest point reached in Pennsylvania-grade crude storage in recent years. Stocks increased slightly during April, May and June, but decreased during all other months of 1939. The Bradford field production within the state of Pennsylvania averaged 35,340 bbl. per day throughout 1939, which represents a decrease of 1419 bbl. a day from the 1938 average. The production in central and southern Pennsylvania increased 1176 bbl. per day, averaging 12,159 bbl. throughout 1939. Table 1 includes annual production for the part of Bradford field situated within the state of Pennsylvania, for central and southern Pennsylvania, and for the entire state of Pennsylvania. A definite segregation of production between the Bradford field and central and southern Pennsylvania is slightly ambiguous because a portion of the oil from the newly discovered Music Mountain pool is included statistically in each area. In all probability the entire increase and some small addition to the production from southern Pennsylvania can be attributed to oil produced from the Music Mountain pool. Within the Bradford field, six price changes occurred throughout the year. At the beginning of 1939 the price of Bradford crude oil was $1.80 per barrel, whereas by the end of the year it had risen to $2.50. The weighted average price for Bradford crude during 1939 was $2.059 per barrel.

Jan 1, 1940

By M. R. Geer, Franklin T. Davis, H. F. Yancey

COKE with low phosphorus content is required by some of the electrometallurgical and chemical plants recently attracted to the Pacific Northwest by the hydroelectric power available from Bonneville and Grand Coulee dams. Shipping such coke into the area from eastern points involves a high freight charge, and during wartime consumes precious rail and ship-bottom space, so it is highly desirable to produce coke from the coking coals of Washington to meet the requirements of these industries. Although coke has been made from Washington coals since 1884, little has been known about their phosphorus contents or about the extent to which phosphorus could be reduced by cleaning. An investigation was undertaken, therefore, to determine the manner in which phosphorus occurs in the coking coals of Washington and its amenability to removal by ordinary coal-washing methods. PREVIOUS WORK Phosphorus is a deleterious element in coke used for numerous metallurgical processes, including the production of pig iron, yet comparatively little published information is available on the occurrence and elimination of phosphorus in any of the coals of this country. A variation from 0.009 to 0.062 per cent phosphorus in various horizons of the Pittsburgh bed in the Connellsville region of Pennsylania has been reported,1 and a reduction in phosphorus content from 0.020 per cent in the raw coal to 0.018 per cent in the washed coal was obtained in washing coal from the same bed in the Pittsburgh area;2 the latter figures represent average analyses for a year's operation of the washery on about 800,000 tons of coal. A reduction in phosphorus content from 0.018 to 0.011 per cent in washing coal from the Pittsburgh bed at another washery was observed, and the same report provides data on the phosphorus reduction obtained by separating 10 other coals on a bath of 1.35 specific gravity.3 European investigators have been especially active in correlating phosphorus content with petrographic analysis; fusain and durain generally contain the highest percentage of phosphorus, but this relationship is not universal.4 Some of these investigators have found that phosphorus is removed in the coal-washing process,5 but others have observed that the clean coal contained as much or even more phosphorus than the raw coal.6

Jan 1, 1944

By C. W. Haworth, M. G. Hall

THE diffusion of copper in silver has been studied by Sawatzky and Jaumot1 and Cahoon and Youdelis.2 Sawatzky and Jaumot measured tracer diffusion in single crystal specimens but the 12.9 h half-life of CU64 limited the time of the diffusion anneal to about 50 hr, and in consequence the minimum temperature of the investigation was 716°C. Cahoon and Youdelis employed polycrystalline diffusion couples, and measured the interdiffusion coefficient over the range 0 to 2 at. pct Cu. These experiments were performed at temperatures down to 630°C and a discontinuity in the Arrhenius plot was observed at -700°C. The high D-values at lower temperatures were attributed to the effect of grain boundary diffusion. The present experiments were undertaken to investigate this anomaly and study the low temperature region of the diffusion of copper in silver. The method employed single crystal samples and a plated source of copper. Silver single crystals 2½ by 4 in. sq were grown from zone-refined silver bar (>99.99 pct Ag) by the Bridgeman technique, and $ in. thick slices were cut by spark machining. The specimens were electro-polished, and a 2 µm layer of copper was electroplated on to the planar surface at one end of each specimen using a potentiostatic voltage source. The following solution was used for plating: CuSO4 . 5H2O 125 gm H2SO4 (S.G. 1.8) 53 ml H2O 1000 ml The diffusion couples were sealed in capsules, in an argon atmosphere, and were annealed at either 701, 597, or 498°C. The temperature measurements were made to an accuracy of *l°C After the anneal, the penetration of copper into the silver was determined using an electron probe micro-analyzer. 100 sec scaler measurements of the intensity of Cu Ka! X-radiation were performed at 2 to 5 µm intervals along a line normal to the source, with a beam potential of 25 kv. Allowances were made for the background radiation, and the dead-time of the counting system in the normal way, and the intensity ratios were corrected to weight concentration by the method of Duncumb & de-Casa.3 For the analysis of the diffusion profiles, it was first observed that the copper layer did not completely dissolve in the host crystal for the specimens annealed at 498 and 591 whereas for the specimen annealed at 701°C, a single phase solid solution was formed. For the 498" and 597°C specimens, the concentration of copper in the silver at the interface was therefore constant throughout the anneal and the analysis for a

Jan 1, 1970

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,' for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.' They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952