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By R. E. Hobart

The development of the Hauto power plant and the claims made by various engineers that electricity was more economical than steam for power purposes in and about the mines, led the Lehigh Coal and Navigation Co., in 1911, to conduct a test to ascertain the consumption of power used by a large steam hoisting engine. The question being one on which no reliable information could be found, and the opinion of various engineers differing to such an extent, it was decided that a test under actual operating conditions was necessary. This was arranged for at one of the collieries. The engine selected was 2 30 by 60-in. (76.2 by 152.4-cm.) piston-valve engine of modern type, and comparatively new. The boiler plant from which the hoist received its power was about 600 ft. (182 m.) from the engine, the latter being fed by a 10-in. (25.4-cm.) steam line insulated with magnesia pipe covering. Two batteries of the boiler plant, aggregating 1200 hp., were cut off and fed into a separate steam line leading direct to the hoist engine. Steam auxiliaries, consisting of feed-water pump and blowers, were fed by the boilers in test, and their consumption charged against the hoist. A barrel weighing device was installed, as it was felt that this would be the most accurate way of determining the consumption of water. The fuel, No. 3 buckwheat, was carefully weighed, and every precaution was taken to make the test accurate in every particular. The test was run for 1 week, or a total of 168 hr. A record was kept of the number of trips hoisted or lowered, and continuous indicator cards were taken. One particular set of cards was taken with the hoist operating balanced, and also with the hoist operating with no counterweight other than the empty cage, the coal in the car being weighed. The speed of the hoist was taken by means of a graphic recording instrument which registered the number of revolutions every 5 sec. From this record, speed-time curves were plotted.

Jan 1, 1918

By J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By C. Dinis da Gama

Because of the growing importance of back analysis for the interpretation of rock slope failures, particularly in open pit mines, it is suggested a methodologic sequence of activities for dealing with those problems. The principal mathematical tools for the interpretation of the most common mechanisms of slope failures are reviewed, including methods of stress and strain analysis, which seem to be more powerful for parametrization studies, and for developing more realistic explanations of slope behaviour, such as the measurement of displacements. An application of those methods is described, using slope failures detected in a Brazilian uranium mine (Cercado), thus providing reliable shearing strength parameters for the rock mass discontinuites, which were used in the final pit design. The concept of using backanalysis results to supply input data for pit design was implemented by means of the excavation of an experimental trench within mine limits, where specific instruments were installed, and several slope failures were monitored and backanalysed, in order to yield information about sliding mechanisms in the future open pit.

Jan 1, 1983

By R. R. Bryan

SINCE the first applications of cyanidation to silver ores about 1906, treatment of ores in the Pachuca district has been entirely by straight cyanidation. Until about the year 1921, Real del Monte removed a sulphide concentrate (largely pyrite) by tabling in the cyanidation grinding circuit. The ores milled prior to the year 1935 were dry ores, ideal for cyanidation, and yielded 90 pct of the silver and 92 pct of the gold. Since 1934 there has been a notable increase in the refractivity to cyanidation of the average ores received by the mill. Tonnages of the former amenable ores have gradually been replaced by tonnages of more refractory ones, so that present average recoveries have fallen to 83 pct of the silver and 90 pct of the gold. During this period there has also been an increase in the content of base metal sulphides' in many of the ores although this increase is not always directly related to the increased refractivity. Since March 1950, the Cia. de Real del Monte has been developing a flotation treatment for some-of its ores before cyanidation. Suitability for flotation is judged not only by the base metal content, but also by the amount of additional recovery of silver and gold made possible by the combined treatment. Selection and segregation of ores most suitable for flotation before cyanidation is a difficult problem for the mines, and the best that can be done is a compromise that leaves much to be desired. Development of Pre-cyanidation Flotation at Real del Monte Much laboratory work has been done on flotation of ores from the Pachuca district, however, the data could not supply reliable information on the many factors connected with the economics of low-base metal-high silver ores. Pilot plant operations would be required. Pilot plant facilities were made available in March 1950, when it became necessary to close down Loreto's 100 ton per day selective flotation plant because of exhausted ore supply. The results of the 100-ton pilot plant tests indicated that a large part of our tonnage of cyanidation ores could be profitably treated by flotation, and a tonnage of 1100 tons per day was selected as the maximum tonnage of ore that the mines were likely to deliver, and because this tonnage fitted with the grinding capacity of this circuit. Equipment was ordered for the production of a single flotation concentrate. The conception of flotation before cyanidation, at that time, was the production of a single concentrate to be shipped to the lead smelter. The 100-ton pilot plant was immediately increased to 350 tons by installing additional flotation cells.. This. plant was operated continuously until the 1100ton plant was put in operation in January 1951. In July 1950, an increase in the quotation for zinc called for an investigation- of the possibilities of producing a zinc concentrate, and laboratory tests on the tailings from the 350-ton plant indicated that a

Jan 1, 1952

By Frank Marotta, Louis B. Lesem, Frank Greytok, John J. McKetta

Although one of the primary variables in the calculation of the flowing bottom-hole pressure in gas wells from surface measurements is the temperature at any point and its distribution in the flow-string, only few experimental data are available in the literature and little attention has been given to analysis of the problem. Virtually all of the recently published methods of calculating flowing bottom-hole pressures depend on the assumption that either the temperature is constant at some average value or that the variation is linear with depth. The purposes of this work are to analyze the problem theoretically and to verify the analysis by comparison with experimental data so that practical problems in the analysis of the behavior of gas wells can be solved with greater accuracy, reliability, and ease. MATHEMATICAL OUTLINE OF PROBLEM Assuming that: 1. The mass velocity and chemical composition of the gas stream are constant and in normal gas well operations, the change in linear velocity in the entire flow-string is trivial, 2. The product of the density and heat capacity of the gas is constant, 3. No horizontal temperature gradient exists in the gas stream, 4. Net flow of heat by conduction within the formation and in the gas stream in the vertical direction is trivial in magnitude and can be neglected, 5. The regional vertical geothermal gradient is constant, and 6. The temperature of the gas entering the borehole is constant, and equal to that of the reservoir, a set of two simultaneous, linear partial differential equations with appropriate boundary conditions was derived to describe the temperature distribution in the gas stream and the surrounding formation. These equations were solved by operational techniques for the distribution of temperature in the gas stream. The resulting integrals were evaluated numerically on an IBM 604 at the Machine Accounting Div. of the Railroad Commission of Texas. DERIVATION OF FUNCTIONS FOR THE DISTRIBUTION OF TEMPERATURE The physical system is a circular hole of radius a in an infinite medium with thermal conductivity K, density p8, and heat capacity c,. Under shut-in conditions the well is in thermal equilibrium with the surroundings and the increment in temperature is given by - ?T3/L x. Gas of density pg and heat capacity c.. flows upwardly through this hole in the direction of increasing x with a linear velocity W. Writing a heat balance on an element of gas ?x in thickness, convective heat transfer + conductive heat transfer + energy required to lift a unit mass of fluid = change in energy content. pa2W po Co To - pa2Wpo Co To x+xx - 2apK?x ?T8/?r r=a - Wpa2 po?x/778 = CoPopa2?x?To/?t... Dividing by (copopa2?x) and taking the limit as ?x tends to zero, -W (?To/?x + 1/778Co) + 2 K/a Po Co ?T3/?r r=u = ?To/?t

Jan 1, 1958

By S. F. Urban, G. Derge

AT the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for a large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions [f] operation. The most important general conclusion reached was that the time a heat is held under a reducing slag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. PROCEDURE The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. Companion slag and metal samples were taken just prior to slag-off and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional 13 heats. Slag sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from tie furnace in a well-slagged carbometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace heats. The Big Wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness, and was finally adopted as the most satisfactory design. The Long Wedge Mold (b) was a 2 by 2 by 5 ¼ -in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 2 ¾ in. long, and ¼ in. maximum thickness. The Small Wedge Mold (c) was 2 by 2 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness.

Jan 1, 1947

By John E. Latz

QUICKSAND far below the surface, stopped two attempts by the Potash Co. of America to sink a third shaft to a potash bed that lies 1000 ft below the southern New Mexico desert. Virtually all methods of grouting were employed in the two failures without any indication of consolidation of the flowing sand. Sinking the South Shaft at the Carlsbad potash mine seemed an almost insurmountable task, until freezing was employed as a final resort. This process that proved to be the answer may be defined as "the sinking of a shaft by freezing, consists of the formation, in the water-bearing strata, of a large block of frozen ground in which it is possible to sink a shaft without danger of an influx of water, providing the ice-wall between the water outside and the shaft itself is strong enough to resist the hydrostatic pressure." Freezing Method Used Extensively in Europe Successful frozen ground shaft sinking projects had been completed in Europe, and Russel G. Haworth, resident manager of the Potash Co. of America, went abroad in search of the know-how needed for the New Mexico undertaking. The freezing process, with a history of two failures at the time, was first successfully employed by Poetsch in 1885 at the Houssu Collieries near Haine St. Pierre, Belgium. Poetsch contracted to sink the remaining 64 ft of an uncompleted shaft through water laden strata from a depth of 190 ft to a depth of 254 ft. This work was in progress until 1887. The freezing and sinking consumed more than two years. As a result of early failures, the process was not favorably received until soon after the turn of the century. The accurate prediction of success in a given application was made possible by the concerted effort and study of a group of European engineers. Means of accurate deviation measurement and control were devised, the nature and properties of frozen water laden soil (the ice wall) were investigated, a thorough and rational basis of refrigeration load calculation developed, and concurrently the efficiency and dependability of refrigeration machinery was greatly advanced. Numerous shafts in Germany, Belgium, France, and England today testify to the reliability and economical surety of the freezing method. Applied to the South Shaft, which is circular in cross-section and 15-ft diam, the freezing method consisted of drilling holes 350-ft deep, through the water bearing strata into impervious ground-the freeze hole pattern being concentric with the shaft and 31-ft diam. The holes were cased with pipe closed on the bottom end. Smaller tubes were placed inside these casings and connected to a header supplying chilled brine from a refrigeration plant. The brine descended in the tubing to the bottom of the hole and ascended through the annular space between the two pipes to the top of the casing; flowed into the return header and back to the refrigeration plant. Under these conditions, each of the freeze hole casings became surrounded by a cylinder of ice

Jan 1, 1952

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By D. R. Pratt, R. W. Hanks

The method of Caldwell and Babbitt for detennining Bingham plastic rheological constants from engineering pipe flow data has been erroneously used in many previous applications. A reanalysis of extensive pipe flow data from the literature is performed. Critical Reynolds numbers corresponding to the laminar-turbulent transition calculated from these data are found to agree with theoretically calculated values for the entire flow range studied. Similar agreement is found for the authors&apos; own data&apos; for flow of 10 slurries between parallel plates. The Bingham plastic model is shown to be a reliable representation of the flow of non-Newtonian slurries provided it is properly applied. If the Hedstrom number He = pD2 t0/?2 > 104, then the linear approximation method of Caldwell and Babbitt is invalid for pipe flow data obtained in systems of ordinary engineering interest, and the complete nonlinear form of the pipe flow Bingham plastic equation must be used in determining rheological parameters. INTRODUCTION Many materials of engineering interest must be handled and transported as slurries or suspensions of insoluble particulate matter in a Newtonian liquid. These suspensions frequently exhibit non-Newtonian rheological behavior which is reasonably well described by the simple Bingham plastic rheological equation1 Using this particular equation to describe the laminar flow characteristics of slurries was discussed at length by Caldwell and Babbitt2-4 who considered the flow of various clay slurries and sewage sludges. The model has since been used by many others.5-7 More recently the problem of predicting the laminar turbulent transition Reynolds number for Bingham plastic fluids has been treated8 for the case of flow in pipes. This paper points out errors which have existed in the analysis of Bingham plastic flow since the work of Caldwell and Babbitt2-4 and presents a reanalysis of the laminar turbulent transition calculatiod for Bingham plastic flow in pipes. In addition, new data obtained for flow of Bingham plastic slurries between parallel plates, both in laminar flow and in the laminar turbulent transition region, will be presented and compared with the theoretical analysis of laminar turbulent transition for flow between parallel plates. THEORETICAL ANALYSIS PIPE FLOW The mathematical analysisl-4 of laminar flow of a Bingham plastic fluid leads to the following equation. where q = <v>/R is a pseudoshear rate, rw is the wall shear stress Eo = r0/rw, r0 is the yield stress and 1 is the coefficient of rigidity or plastic viscosity from Eq. 1. Caldwell and Babbitt2-4 recognized that the quartic term in Eq. 2 was small compared to the other terms whenever 5, « 1, and that for large values of 7, a plot of Eq. 2 becomes linear. The slope of such a plot with rw as ordinate is 4? and the intercept is (4/3) ro. This approximation is illustrated schematically in Fig. 1. The shaded region between the true curve and the straight-line approximation near the origin represents the contribution of the quartic term. In principle, therefore,

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geophysics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining. Geophysics in Petroleum Exploration During the past twenty years, the petroleum industry has established an effective exploration technique. Geology is the basic tool in those areas where reliable predictions can be made from surface conditions. In the other areas, where the geological studies are inadequate, they must be supplemented with geophysics or direct exploration, such as drilling. Since geophysical work is far less costly than any form of direct explbration, it is used almost exclusively as the means for obtaining the desired subsurface information. The geological and geophysical techniques are credited with locating sites which yielded one producer for three dry holes during the year 1947.&apos; For the wells located without geology or geophysics, there is a ratio of one producing well to sixteen dry holes. From these figures it is seen that the geological and geophysical techniques are more than four times as successful as the nontechnical exploration. It will be in order to consider further this ratio of one producer to three dry holes. The geophysical methods in use today† do not pretend to locate oil directly; their function is to locate anomalies or structures favorable for the accumulation of oil. For a producing oil well we must have not only structure, but also other favorable conditions, namely: petroliferous source beds, the required porosity and permeability in the reservoir rocks, an impermeable cap rock over the reser- voir, and the necessary water or gravity drive to force the oil into the bore hole. Since the geophysical work can only detect and sometimes delimit the anomaly, these other necessary conditions can be determined only by direct exploration. The success of modern geophysical work in locating and limiting the structure itself is remarkably high, probably over 95 pct accurate. Geophysical work renders an important service in the delineation of the structurally unfavorable areas and their elimination from the drilling phase of the exploration program. When attempting to locate any material of scarce occurrence in the earth, it is of paramount importance to know where not to dig. This elimination of barren areas is the least appreciated but is of great economic importance. For illustration, the difference between one producer to three dry holes, and one producer to sixteen dry holes, represents a saving of thirteen drilled wells, which would require an expenditure many times the cost of the geophysical work that might have revealed the nonfavorable structural conditions. The percentage of geophysically-located wells necessarily will continue to increase in the statistics of future years, as the search for oil is extended

Jan 1, 1950

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,&apos;-* iron,&apos; and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4&apos;C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor&apos;s rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor&apos;s rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By George A. Moore

A recent survey of existing analytical results, and an attempt to correlate them with each other and with the known history and behavior of the samples, indicated that none of the commonly applied methods could be considered established as intrinsically reliable. It was. therefore, desired to attempt to establish the reliahility of some one method by external evidence. If this were to be accomplished, other methods could then be evaluated in terms of the method establibhed. The correct method was accordingly to be chosen without regard for cost, speed, or convenience; with the requirements for routine application to be reserved for 1ater consideration. The method of total combustion was chosen and submitted to a limited number of tests against primary standard samples. Considerable experimental difficulty was encountered, indicating that additional work on the experimental arrangements is desirable. While the work to (late by no means represents a completed investigation, it is helieved that the combustion method is basically sound and that its development should be continued. Choice of Method Of the several available methods, mechanical disintegration. electrochemical methods&apos;2&apos;3 modifications of the Sieverts experiment,% and vacuum fusion, were all judged to contain one or more factors of un- certainty not at present completely cvaluated or suhject to complete control. These methods, therefore, were considered currently unsuitable for referee purposes. Solid evolution was considered to be of doubtful significance when conducted in the alpha range. A reasonable chance for a true analysis was found for evolution in the gamma range. Preliminary tests have indicated a very slow rate for evolutioll from gamma iron. indicating a running time of possibly 100 hr. for a one-centimeter sample. Difliculty in distinguishing such slow. evolution from blank gas was anticipated, hence the method was not consitlerctl the most suitable for the present purpose. The combustion method was evaluated as being most sound on fundamental principles. The only important unknown would be to determine that the iron oxide formed did not occlude water at the tcmperaturv of the combustion.with the odvious precautions of using a sound and clean specimen, providing a system sufficiently tight to give acceptable blanks in longtime runs, and providing a suficicntly sensitive measuring system, reasonable, precise, and truthful analytical results could be logically expected. Apparatus The equipment as originally operated is shown in Fig. I, and the glassw-are in its latest modification in Fig. 2. The sulphuric acid drier and small safety tube in the upper right of Fig. I were replaced by a KOH drier and combined manometer safety tube, to permit operation at reduced

Jan 1, 1945

By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By W. R. Hicks, J. E. Pollock, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940