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By D. J. Carney, R. L. Stephenson

A sampling technique has been developed for procuring a sample of sinter representative of the entire depth of the sintering bed. The sampling method involves the use of an open-bottom metal basket that rides on the grate of the sintering machine and when removed contains a sample of the sintered product. Additional data have been obtained to indicate that the tumbler test is a suitable means of measuring sinter strength. IN the last few years additional sintering facilities have been installed in both the Pittsburgh and the Chicago district of the United States Steel Co. Since the construction of these sintering plants made possible the use of higher percentages of flue-dust sinter in our blast-furnace burdens, it became important to study means of controlling the quality of sinter to obtain optimum results in the blast furnace. For controlling an operating process, it is necessary first to establish standards by which the quality of the product can be judged. For sinter, it appeared that an important property was its strength or its resistance to degradation during transportation and charging into the furnace. Consequently work was undertaken to establish a standard for sinter strength that could be used both for controlling sintering-plant operations and for correlating sinter quality with blast-furnace performance. The first problem in setting up a standard was that of procuring a sample that would be representative of the sinter made under any particular set of conditions at the sintering plant. Since the United States Steel Co. sintering plants discharge the finished sinter either into a large pit or onto a rotary cooler, the sinter becomes inseparably mixed with material sintered 2 hr before or 2 hr afterwards. For this reason the exact identity of the sinter is lost. A sample selected as the cooler is discharged, or as the sinter is removed from the pit, cannot be said to be truly representative of the sinter made at any specific time. Sampling The first attempt to procure a sample that would be representative of a specific sinter mix and of specific operating conditions was made by stopping the Dwight Lloyd sintering machine and removing an entire pallet full of sinter. This method, however, proved very difficult to perform and interfered considerably with the operation of the plant. To overcome this difficulty, a sampling method was devised by technologists at South Works enabling them to secure, without interrupting the sintering operation, a sample of about 1 cu ft of sinter, representative of sinter for the full depth of the sintering bed. The South Works method involves the use of a steel-frame-work basket. A typical basket is shown in Fig. 1. The basket has been used both with and without crossbars along the bottom. As long as the crossbars are in the same direction as the grate bars on the sintering machine they do not interfere with the sintering process. The basket is set on an empty grate of the Dwight Lloyd sintering machine before it passes under the swinging feed spout, see Fig. 2. When the basket is removed after it has travelled the length of the sintering machine, it contains the sample. Just before the basket is removed, the sinter is scored and chipped to facilitate removal of the sample from the sinter bed. A view of the basket after its removal is shown in Fig. 3. Although the sampling method was originally designed for use on a Dwight Lloyd sintering machine, it can also be used on the Greenawalt type of machine. When used on the Greenawalt-type machine, the basket is placed on the sintering grate before the charging car passes over it, and finally it is removed just before the pan is dumped. Testing After a method of obtaining a representative sample of sinter had been developed, the next step was to select a method of measuring its strength. The irregular shape and size of the sinter pieces precluded the use of a simple compression test for determining strength; consequently, the shatter test and tumbler test were investigated. To perform the shatter test, a sample of sinter, approximately 5 lb, is dropped from a hinged-bottom box at a height of 3 ft onto a steel plate. The broken sinter is sieve-analyzed after a specified number of drops. The tumbler test is performed with the use of a standard ASTM coke-tumbling drum. The drum is 3 ft in diam and is equipped with two lifter bars diametrically opposite one another on the inner periphery of the drum. The drum is rotated at a speed of 24 rpm for 200 revolutions, and after tumbling the sample is sieve-analyzed. To express as single numbers the results of sieve analyses after shattering or tumbling, the method suggested by R. E. Powers1 was employed. This method involved plotting the size of the sieve openings on a logarithmic scale and the cumulative per cent larger than each sieve on a probability scale as described by J. B. Austin.' By interpolating from the plotted data, which in most cases approximated

Jan 1, 1954

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55' API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook' was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By J. L. Huitt, B. B. McGlothlin, D. K. Lowe

Published correlations for the principal aspects of hydraulic fracturing were combined into a digital computer program to facilitate the study of interrelated variables. The computer program includes individual relationships for fracture width during pumping, fracture area generated, propping agent embedment, flow capacities of propped fractures and transport of propping agents in horizontal fractures. The effects of more than 20 treatment and formation parameters on the predicted results of hydraulic fracturing treatments were studied. The effects of these parameters were determined for (I) fracture width during injection, (2) fracture width after the overburden comes to rest on the propping agents, assumed not to be crushed, (3) generated and propped fracture area, (4) location and concentration of propping agents in the fracture when injection ceases, (5) flow capacities of the various propped sections of the fracture and (6) expected increase in the well productivity. The effects of propping agent, formation and fracturing fluid parameters on well productivity are discussed. The parameters that were found to have the most pronounced effects on hydraulic fracturing treat~nents are injection rate, treatment volume, fracturing fluid coefficient, size and amount of propping agent, spearhead volume, well drainage radius and formation capacity. INTRODUCTION Many correlations have been published for predicting effects of various parameters that are considered in the design of hydraulic fracturing treatments. The Carter equation' can be used to predict generated fracture radius as a function of fracture width, fracturing fluid leakoff and other parameters. Fracture width can be determined by use of the Perkins and Kern correlation' in which the fracture width is related to the fracture radius, fluid injection rate and certain formation and fracturing fluid parameters. Wahl and Lowe et aL4 have reported methods of predicting the location of propping agents in fractures when pumping ceases. The former study is applicable to the case where the ratio of propping agent diameter to fracture width is less than 0.1. The latter is applicable when this ratio is greater than 0.1. These studies showed that the propping agent placement in horizontal-radial fractures depends principally on how the individual particles are transported in the fracture by the carrying fluid. Particle transport in fractures is determined by local fluid velocity in the fracture, fluid and particle properties, and the size of the particle relative to the fracture width. The distribution of propping agents, effective overburden pressure and formation rock strength control the propped fracture width6 by controlling the extent to which the propping agent particles embed into the fracture faces. From the distribution of propping agents and the propped fracture width, fracture flow capacities can be calculated or the various regions of the fracture. The flow capacities and the radial extent of these regions can be combined with reservoir information to predict the productivity increases for fractured wells. In all these studies, the effects of certain treatment and/ or reservoir parameters on one facet of fracturing can be predicted only if other facets which the parameters affect are fixed. For instance, fracture width and radius are interrelated; that is, to calculate the value of one, the value of the other must be known. Also, some parameters influence more than one aspect of fracturing. For example, prop-pant transport is a function of both fracture width and fluid viscosity. but fracture width is itself a function of fluid viscosity. Since these calculations are complex and the parameters interrelated, it is not possible to write an equation with which the over-all effects of treatment parameters can be solved explicitly. For these reasons, the correlations for determining the effects of the parameters which are most significant in hydraulic fracturing treatments have been incorporated into a digital computer program. COMPUTER PROGRAM The program, which was written for an IBM 7094 computer, can be used to predict results of most of the combinations and values for the treatment parameters that are ordinarily considered for fracturing treatments. A spearhead of fracturing fluid and a propping agent-carrying fluid with different fluid properties can be taken into account. Also, the total volumes and relative amounts of the spearhead and carrying fluids can be varied. Two different propping agents (as used in tail-in operations) and a wide range of formation properties and injection rates are considered. The computer program (Fig. 12) consists of several sets of calculations. First, the final flooded fracture radius and average fracture width at the cessation of pumping are calculated. This is done by simultaneous solution of the Perkins and Kern fracture width equation and the Carter equation for flooded fracture radius (equations used in the computer program appear in the Appendix). The next step is to determine local fluid velocity in the fracture as a function of time and radius. Since it is not possible to write this function in closed form expression, a table of velocity values is generated by the program and stored for subsequent use. The time span from the beginning of

By J. J. Frawley, W. J. Childs, W. R. Maurer

The object of this investigation was to determine the growth habit of bismuth and bisrrtuth alloy dendrites as a function of supercooling. To do this, techniques were developed to increase the amount of supercooling in bismuth and bismuth alloys. For pure bismuth, the growth habit was dependent on the amount of supercooling. At low amounts of supercooling, about 10" C, prismatic dendrites were obtained. With increased supercooling, about 20 C, a hopper growth habit was observed. In many cases where hopper growth had occurred, the hopper dendrites were twinned during the growth process. This twinned surface enable prismatic dendrites to nucleate and grow by a twin plane mechanism. When the amount of supercooling was increased to about 25 °C, the growth habit was a triplanar growth. With still greater supercooling, about 3s°C, a branched growth habit occurred. The exposed planes on the prismatic, hopper,, triplane, and branched dendrites have been determined. The growth habit of the dendrites which grew along the crucible wall was found to have the (111) as the exposed plane, with <211> growth direction. It is apparent that dendritic growth of a metal is dependent on its purity and the solidification variables present. One of the solidification variables is the degree of supercooling. Supercooling, although often observed, has not been studied extensively until recent years. For dendritic growth to occur in a pure metal, the metal must be thermally supercooled. After the dendrites grow into the supercooled melt, the heat of solidification raises the temperature of the specimen to the melting point of the material and the remaining liquid will solidify at this temperature. Decanting is the removal of this remaining liquid before complete solidification. This removal of the remaining liquid after recalescence had occurred is a great aid in the study of dendritic growth. In this investigation, decanting was accomplished by a vacuum-decanting technique . Other investigators1-5 have studied the growth characteristics of various low-melting-temperature pure metals and alloys as a function of supercooling. However, large degrees of supercooling were not included. For their study of dendritic growth of lead, Weinberg and chalmersl employed a decanting technique which was achieved by pouring off the remaining liquid, exposing the solid/liquid interface. This method was employed later by Weinberg and Chalmers2 for the investigation of tin and zinc dendrites. The method for obtaining a solid/liquid interface was improved by Chalmers and Elbaum. They employed a triggered spring which was attached to the solidifying section of the specimen. Upon activation, the spring jerked the solid interface away from the liquid melt. In the study of growth from the supercooled state, a metal of low melting point which exhibited a high degree of supercooling was desired. Bismuth gave very consistent supercooling when a stannous chloride flux was employed. The maximum supercooling obtained was 91°C, with an average supercooling of between 65" and 75°C. The consistency of supercooling greater than 50°C was very high. The use of vacuum to aid in the rapid decanting of molten metal has proven to be very successful in this investigation. The vacuum gives a rapid decantation, usually leaving the solidified metal structure sharply defined. The purpose of this investigation was to study the effects of supercooling and the effects of alloy additions on the growth habit of bismuth dendrites. The structure of bismuth has been variously defined as face-centered rhombohedral, primitive rhombohedral, and hexagonal. However, bismuth has only one plane with threefold symmetry, the (111) plane, and the crystal-lographic structure is considered a 3kn structure. MATERIALS The bismuth which was employed in this investigation was obtained from the American Smelting and Refining Co. of South Plainfield, N. J. The accompanying spectrographic analysis data indicated the bismuth to be 99.999+ pct pure. The tin was obtained from the Vulcan Materials Co., Vulcan Detinning Division, Sewaren, N. J. It was classified as "extra pure". Nominal analysis was 99.999+pct. In order to prevent contamination of the bismuth melt from the atmosphere, an anhydrous stannous chloride (Fisher certified reagent grade) was added to each melt. The fluxing action obtained from the use of the chloride provided a large amount of supercooling in the specimen. APPARATUS A 30-kw, 10,000-cps motor-generator set, connected to a 6+-in.-diam air induction coil, was employed to melt and superheat the specimens. The temperatures were recorded by means of a chromel-alumel thermocouple and a potentiometric recorder. The thermocouples were 0.003 in. in diam, and were encapsulated with Pyrex glass to prevent the thermocouple from acting as a nucleating agent and also from contaminating the melt. Fig. 1 illustrates the vacuum-decanting apparatus when a liquid flux was employed. A standard 30-ml Pyrex beaker was placed on top of an asbestos insulating block. A 5-mm-ID Pyrex tube with aA-in. spacer tip attached to its end was used for the decanting tube. The spacer tip contributed significantly to a successful decanting operation. The tip located the opening of the decanting tube about -^ in. from the bottom of the

Jan 1, 1969

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.&apos; One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,&apos; but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-&apos;&apos; to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10&apos;11 Although there have been criticisms both of the shortcomings of the grain shape technique&apos;&apos; and of the different procedures used to determine y at the surface,&apos; it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10&apos; to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By O. B. Bennett

WHEN diamond drilling was introduced in the Rhokana mines in 1939 it was used principally for pillar removal and for completion of the upper portions of shrinkage stopes which were being affected by increasing pressure. This method of drilling long blastholes proved so successful that it was extended gradually to cover stoping, pillar recovery, and hanging cave work. BY 1949 virtually all the ~roduction of Mindola and Nkana was being obtained by this method. At the present time 87,500 ft are drilled each month by the 80 diamond drills in daily operation. Responsibility for control and issue of diamond drilling equipment and crowns, as well as tabulation of all performance figures, was taken over by a sPecially formed Roto drill department, which also investigated the problems encountered with this new method. To assist this department a fully equipped test chamber, Fig. 1, was established underground where performances of various types of machines and equipment could be studied under conditions as nearly uniform as possible. Since the establishment of this department, which was eventually taken over and incorporated into the study department, considerable experimental work has been done on every aspect of the subject. The problems can be classified broadly under four headings: improvement of drilling equipment, crown design, machines, and stoping layouts. One of the major problems with drilling equipment has been to eliminate vibration. Owing to flexing of rods in the hole, severe friction is set up on the back end of the &apos;Ore barrel and On any high spots in the rods, inducing harmonic vibration in the string of rods and causing the crown to chatter against the face. This not only causes premature crown failure but also reduces penetration speeds and increases wear on the machines and rods used. In the early days, when only holes of EX size were drilled, vibration was largely overcome by periodic greasing of rods and core barrel during each run, but with the change-over to the larger BX hole it became obvious that application of grease by hand was inefficient and time-consuming, and attempts were made to perfect a self-lubricating core barrel. A series of these core barrels was made up and tested and a number of the latest type were used under normal operating conditions, but although footages up to 120 ft were drilled without refilling the overall performance was inconsistent, and the idea was shelved in view of the success of the stabilizer rods referred to later in this paper. At the same time tests were made with barrels 5 ft and later 6 ft long instead of the normal 2 ft. Although a slight improvement was noticed, greasing was still necessary. It was found that rod vibration increased as the core barrel became worn, and in an early test chamber experiment crowns drilled with a worn core barrel averaged 95 ft with a diamond loss of 4.76 carats, whereas the same type of crowns with a new barrel averaged 228 ft with a diamond loss of 3.13 carats. until then all BX drilling had been done with B-sized rods, but during a test on a string of BX-sized rods it was noticed that vibration was negligible. Because of the larger surface area of metal bearing on the sides of the hole, however, the friction and resistance of rods of this size rendered them impracticable on any but the most powerful of the machines, The use of stabilizers spaced evenly along the rods was the next logical step, and for this B couplings, see Fig. 2, were set with three tungsten carbide inserts 1 in. long placed around the periphery equidistantly and at an angle of 45" with a right hand lead. These were placed immediately behind the core barrel and then at 12-ft intervals, as it was found that vibration still occurred when the stabilizers were more than 15 ft apart. The effect of these stabilizers was immediately noticeable; holes were drilled with a minimum of vibration, penetration speeds were improved, and as it was no longer necessary to grease the rods there was a marked decrease in the overall drilling time for each hole. While tests were being made with the stabilizer comeb periodic were taking place with a set of tapered threaded rods, and because there was marked improvement in efficiency it was decided to incorporate the stabilizers and tapered threading in all new rods ordered for Rhokana. The feature of these rods is that only four full turns are required to tighten the coupling as against nine for the present type of B rods. Also, as they are self-centering it is virtually impossible to crossthread them. Each rod has a male 5" tapered Acme thread, Fig, 3, on one end and a female at the other, so that separate couplings are unnecessary, and every fifth rod has an

Jan 1, 1955

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55&apos; API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook&apos; was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

By F. W. Schremp, J. W. Chittum, T. S. Arczynski

This paper describes a laboratory study of causes of external casing corrosion and the test work that led to the use of oxygen scavengers to prevent this attack. External casing failures are classified as water-line, casing-casing, collar and body failures. A corrosion mechanism based on principles of differential oxygen availability is developed that is consistent with facts known about each kind of failure. The field use of oxygen scavengers is depicted as a direct result of the laboratory study. A part of the paper is devoted to reporting on the field use of hydra-zine to control external casing corrosion. Results of field measurements made over a period of several years are presented as evidence of the efectiveness of the hydrazine treatment. The first conclusion reached is that the use of hydrazine materially reduces the cathodic protection requirements for treated wells. This result is interpreted to mean that a reduction is taking place in the amount of corrosion on the casing. Results indicate also that hydrazine shows its greatest usefulness within the first 12 to 18 months after a well is completed when pitting corrosion is likely to be most active. INTRODUCTION According to surveys sponsored by the National Association of Corrosion Engineers,&apos; the cost of repairing casing leaks caused by external corrosion may exceed $4 million per year. In addition, well damage and lost production resulting from casing leaks probably costs the petroleum industry an additional $5 to $6 million per year. Concern about the cost of external casing corrosion led to an extensive laboratory study of factors causing this external corrosion and to the development of a new approach to its prevention. This paper presents a discussion of various causes of external casing corrosion, details of laboratory studies and the results of the field use of an oxygen scavenger in well cementing fluids to prevent the external corrosion of oil-string casing. Measurements on test wells over a period of several years show that cathodic-protection current requirements are greatly reduced when hydrazine is used in cementing mud. Reduction of current requirements can be interpreted to mean that removal of oxygen by hydrazine has greatly suppressed corrosion cells on the external surface of the casing and thereby, has reduced corrosion. To date, hydrazine has been used by the Standard Oil Co. of California in more than 200 well completions. KINDS OF CASING FAILURES A survey of a large number of casing leaks disclosed four types of external casing failures — water-line, casing-casing, collar and body failures. These types are identified largely by their location on the casing. Water-line failures are found just below the surface of water or mud in the casing annulus. Casing-casing failures occur on the oil string just below the shoe of the surface string. Collar failures are found in the threaded ends of casing joints where they are screwed into casing collars. Body failures may occur at any point on the body of a casing joint. Ex- amples of each kind of failure have some of the general characteristics that are shown in Fig. 1. Water-line failures usually result in the circumferential severance of an oil-string casing. The corrosive action causing a water-line failure usually is sharply defined and is limited to a short length of the casing. Casing-casing failures usually are accompanied by pitting corrosion distributed around the oil-string casing for distances up to 100-ft below the shoe of the surface string. Casing-casing failures may also sever the casing. Collar failures seem to start on the first thread at the bottom of recesses between collar and casing joint. Corrosion proceeds across the threads by what appears to be a normal pitting mechanism. Both casing and collar are severely attacked. Body failures are the result of highly localized pitting at any point on a casing wall. Besides the pit that perforates a casing, a large number of other pits usually are found along one side of the casing joint. The pits occasionally are filled with corrosion products consisting largely of oxides and sulfides.&apos; Frequently, the mill scale is largely intact on the rest of the casing. Examination of a casing failure does not always reveal the cause of the failure. Frequently, the necessary details are destroyed when the failure occurs. For example, formation water flowing through a perforation at high velocity may enlarge the hole and destroy any remaining evidence of the cause of the failure. One way to obtain undistorted information about a failure is to study the nature of other pits on the casing in the vicinity of the failure. A study of such pits frequently suggests that they are characteristic of an attack resulting from the differential availability of molecular oxygen.

By George R. Cowan

A number of studies hare been reported of the effects produced in metals subjected to deformation by shock waves with maximum pressures ranging from tens to hundreds of kilobars. On the basis of the equations for the flow of mass, momentum, and energy through a stationary shock front, the macroscopic stress-strain curve for the resulting shock deformation can be calculated within narrow limits from the experimentally determined Hugoniol curve. In relatively weak shocks which are preceded by an elastic wave, the stress rises above the clastic limit only as plastic deformation proceeds cold thus the shock has a long toe. In strong shocks that override the elastic wave a high stress is applied without prior plastic deformation. A more important effect of increasing the shock pressure is the generation of shear stresses, called supercrilical shear stresses, that exceed the strength of the perfect lattice. A change in the mechanism of deformation is expected to result from the onset of supercritical shear. The shock disordering of ordered Cu3Au in strong shocks appears to be an example of such a change. It is suggested that the formation of fine twins in copper and nickel and the formation of structures which enable visible twins to be formed in the rarefaction ware, observed in copper and presumably in disordered Cu3 Au, are related to the occurrence of supercritical shear in shock dcformation. In recent years several studies1,2 have been made of the changes in structural and mechanical properties of metals produced by the passage through the metals of strong shock-compression waves ranging from about 50 to 800 kbar pressure. Recent work involving dynamic measurements of the shock compression "Hugoniot" curves 3-8 of many metals has developed techniques and provided data required to obtain the shock pressure and the (transient! plastic deformation produced in the shock-conlpression experirnents.9 Shock deformation has been found to be much more effective than slow deformation in changing the mechanical properties of metals, when the two are compared on the basis of equal plasti strain, Holtzman and Cowan9 made quantitative estimates of the shearing stress occurring in a shock front in a metal by assuming that the shearing stress is similar to that occurring in a shock front in a viscous, heat-conducting fluid, with the addition of a yield stress. Taylor&apos;s solution9 for a weak shock was used to estimate pairs of values of shearing stress and thickness of the shock front obtained by assumed choices of the ratio of effective kinetic viscosity to thermal diffusivity. It was noted from these values that. unless the shock front is extremely thin. heat conduction has slight effect, and the shearing stress is nearly independent of the mechanism of deformation. This mechanism does, however, determine the thickness of the shock front and the rate of strain. Furthermore, since the maximum possible shearing stress occurring in shocks of moderate strength does not greatly exceed the shear stress occurring in conventional slow deformation, the mechanism of deformation is not expected to be qualitatively different. The greater effectiveness of shock deformation in changing the mechanical properties of metals can be attributed partly to the fact that dislocations, when driven by near-conventional stresses, cannot keep up with the shock front, thus necessitating a higher dislocation density than required for an equivalent slow strain. The fast uni-axial strain occurring in the thin shock front would also be expected to cause a larger number of dislocation intersections to occur. In the upper range of shock pressures that have been studied the estimated values of the shearing stress exceeded the estimated shear strength of a perfect crystal. Under these circumstances it is reasonable to expect that the mechanism of deformation might be considerably different from that involved in slow deformation. Except for the observation by smith1 of twins in shocked copper, the effects of shock waves on metals did not show any obvious or large changes in properties that would indicate the onset of a change in the mechanism of deformation. The recent investigation of the effect of shock waves on ordered and disordered specimens of Cu3Au by Beardmore, Holtzman, and ever" showed a spectacular decrease in the amount of long-range order retained by initially ordered Cu3Au when the shock pressure was raised from 290 to 370 kbar. Since Dr. Holtzman and I suspected that this behavior probably was due to the onset of a shearing stress in the shock front in Cu3Au which exceeded the limiting shear strength of the perfect crystal. it was considered appropriate to examine directly the shock-front equations for a solid. and to obtain a sound estimate of the shearing stress occurring in the front using equation of state data obtained from shock studies. In this paper an estimate is made of the

Jan 1, 1965

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management&apos;s most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of &apos; particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10&apos; which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers&apos; approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By Lok W. Home

INTRODUCTION Today, raise drilling (boring) has become the stan¬dard method of raising throughout the Western world. It is estimated that the majority of raise footage com¬pleted in 1977 was accomplished by the raise drilling method. Extensive replacement of the drill and shoot system by mechanized raise drilling has occurred be¬cause users have recognized one or more of the follow¬ing advantages. In a direct cost per meter comparison, mechanized raise drilling is economically more attractive than drilling and shooting. Mechanized raise drilling offers improved personnel safety over the drilling and shooting method. Mechanized raise drilling is a faster and more predictable method for excavation than is drilling and shooting. The raise cost per unit of length becomes less as the raise length increases, offering greater flexibility in the overall design of mines. Mechanized raise drilling provides a substantial reduction in labor requirements. 6) Mechanized raise drilling improves the working environment. 7) Mechanized raise drilling improves the rock in¬tegrity of round, unblasted raises. Increasing acceptance of the raise drilling technique is enhanced by continuing equipment development. Today, a wide range of machines and capabilities is available, machine drive systems have been improved, reliability has been increased, and cutter technology is being improved quite rapidly. Table 1 lists the four major manufacturers of raise drilling machines, cutters, and reamers, together with the approximate number of machines that each company had in operation at the end of 1977. Although Reed and Smith are major suppliers of reamers and cutters, they do not manufacture the drilling machines. Four or five other relatively minor suppliers have built machines, reamers, and cutters for raise drilling, but they did not have a substantial num¬ber of machines in the field at the end of 1977. MACHINES FOR MECHANIZED RAISE DRILLING There are three principal arrangements for making machine-bored raises. They include the use of standard raise drills, reversible raise drills, and blind-hole or box¬hole raise drills. Standard Raise Drills The standard raise drilling machine is set up on one mine level or on the surface, and a pilot hole is drilled from that level or surface to a level below. When the pilot hole has been drilled, the raise then is reamed back from the lower level to the upper level or the surface. This arrangement is illustrated in Fig. 1. Reversible Raise Drills The reversible raise drilling machine is set up on a lower level of the mine, and a pilot hole is drilled up¬ward to a higher level. The raise then is reamed back from the upper level to the lower level. This arrange¬ment is illustrated in Fig. 2. The machines used for this type of raise drilling normally are capable of being used as standard raise drills. Blind-Hole or Boxhole Raise Drills The blind-hole or boxhole raise drilling machine is set up on a lower level of the mine, and a full diameter raise is bored to a higher level without the use of a pilot hole. This type of machine is illustrated in Fig. 3. Drill Recommendations If access to upper and lower mine levels is equal, the standard raise drill should be used. The complexity of the equipment and associated handling procedures for boxhole drilling far outweigh any mechanical advantage or reduction in the number of operations, provided that access to an upper level is available. If there is good access to a lower level but only limited access to an upper level, the use of a reversible raise drill should be considered. If there is no access to an upper level, a blind-hole or boxhole raise drill is the only practical mechanized system. MACHINE SELECTION There are six major considerations in selecting a machine for raise drilling. These include operating range, cutter loading, machine structure and main¬tenance, drill string configuration, drive system, and automated controls. Operating Range As shown in Table 2 and Figs. 4 through 6, raise drilling machines are available for a wide range of hole sizes. Standard raise drill ratings range from raises of 0.9 m (3 ft) diam and 120 m (400 ft) length up to raises of 3.5 m (12 ft) diam and 900 m (3000 ft) length. Boxhole raise drilling machines are available for raises ranging from 0.9 m (3 ft) to 2 m (6 ft) diam with lengths up to 90 m (300 ft). Table 2 lists, among other criteria, the torque and thrust of typical machines; torque and thrust are the main criteria for analyzing the capacity of a machine. The raise sizes shown in Table 2 assume a condition of medium hard to hard rock formations and optimum cutter loading. The recommended raise size for a given machine can be exceeded when raising softer rock formations or when the operator is willing to accept a lower level of performance; the performance is related directly to the 1093

Jan 1, 1982

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here&apos; and abroad.&apos; Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.&apos; When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000&apos; to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By S. F. Reiter

The paper presents isothermal recrystallization curves for 0.08 and 0.15 pct C steel at subcritical temperatures following small amounts of plastic deformation. The effects of deformation, temperature, and aging on nucleation and growth rates ore described. The free energy of activation for grain boundary migration in steel is given. SEVERAL excellent reviews of the literature have appeared concerning the recrystallization of metals.&apos;-&apos; The present investigation follows the approach advanced by Mehl, Stanley, and Anderson,6-7 in which the rate of recrystallization was analyzed in terms of N, the rate of nucleation, and G, the rate of growth of recrystallization nuclei. Two lots of low carbon, capped steel of the analysis given in Table I were studied. Each lot consisted of a 150 lb coil which had been hot rolled to 0.083 in. and then cold rolled to 0.042 in. at the mill. Strips 0.930 in. wide were sheared perpendicular to the rolling direction. Both steels were normalized before studying their recrystallization characteristics. The strips were cleaned, painted with a magnesia-acetone paste, and made into packs of equal weight, wrapped in 0.002 in. copper foil. The packs were placed in a salt bath at 900°C for 30 min and air cooled. A relief anneal followed in a second salt bath for 15 min at 650°C. The relief anneal was found necessary from early tests in which a longer incubation period and slower rate of recrystallization were observed in relief-annealed lot A steel than in similar material which was strained and recrystallized directly after being normalized. This effect, which indicates the presence of transformation and/or cooling stresses in steel air cooled from above the A, temperature, has also been observed by Samuels8 and Masing.9 Figs. 1 and 2 show the microstructure of lot A and B materials and illustrate the rather uniform No. 8 ASTM grain size produced by this heat treatment. Winlock and Leiter10 observed that strip specimens which had their sharp edges removed elongated more uniformly than those which were not polished. Similarly, when the sheared edges were removed on a belt grinder, it was found in the present investigation that such samples recrystallized more uniformly than did unpolished strips. Therefore, all strips were carefully rounded prior to their extension. The approximate strain limits for the production of large recrystallized grains are from 6 to 12 pct extension." It was found that for the purpose of this investigation, 8 and 9 pct elongation were suitable deformations. The strain rate employed was 0.01 in. per in. per min and produced a yield point elongation of 4 pct. Winlock and Leiter found that mild steel of No. 8 ASTM grain size gave the same yield point elongation when extended at 0.012 in. per in. per min. All of the lot A and B strips extended in tension developed a straight, stretcher strain line at each grip when the upper yield point was reached. The lines were parallel and made an angle of 55" with the edge of the strip. They approached each other with increasing strain and met near the center of the sample at the end of the yield point elongation. Immediately thereafter, a small drop in load was observed and then the load increased in a regular manner with increasing extension. The grips were initially 8 in. apart. After extension, the 6 in. gage length was carefully cut into 1 in. samples. The remainder of the strip was discarded. After a flash pickle in hot 50-50 hydrochloric acid, six samples, each of which had been taken from a different strip, were placed in a basket and submerged in a lead pot for isothermal recrystallization. Although no recovery effect was observed, strain aging did occur after extension. Therefore, samples were always recrystallized within 24 hr after their cold deformation. After recrystallization, the samples were etched with a solution comprised of one part by volume of nitric acid with three parts of water. Bromide printing paper was exposed directly at low magnifications and later used with a mask to measure the desired quantities. First, the average diameter of the largest grain visible in each sample was determined using dividers. Next, the number of recrystallized grains per unit area was counted and recorded as n. Then, for each sample, the combined area of the recrystallized grains was measured by transcribing the grain outlines to standard graph paper. Many determinations of the area of the recrystallized grains were repeated five times and indicated a standard error that was not greater than 25 pct. The average area for six samples was divided by the area of the mask to yield the percentage recrystallized. Recrystallization of 0.08 Pct C Steel The progress of recrystallization at 670°C after 8 pct elongation of lot A steel is shown in Fig. 3, a through f. The shapes of the growing crystals are approximately equiaxed, as is assumed in the

Jan 1, 1953

By E. R. Borcherdt

IT is notable that the first large-scale mine operation equipped entirely with detachable bits was the Badger State mine of the Anaconda Copper Mining Co. in Butte, Montana, just 30 years ago. This mine in 1922 was producing approximately 1200 tons of ore per day. Much of the data presented in C. L. Berrien&apos;s article&apos; describing the development and installation of the Hawkesworth detachable drill bit were obtained from these operations. As in any pioneering effort, no precedent existed and many difficult problems required solution, so that the changeover to detachable bits at all Butte hill mines was not completed for 6 years. There was widespread disbelief as to the probable efficiency of the new installation. Some attempts were made in 1931 by the owners of the Hawkesworth patents to interest Ontario gold mine operators in the bit. These efforts were not successful, but they undoubtedly stimulated thinking which resulted in the invention and patenting of several well-known Canadian detachable bits, one of which is now a widely used throwaway bit. The success of the Butte installation also led to the development of the threaded type of bit connections by several well-known manufacturers, and in 1935 these bits were introduced to the mining industry on a national scale. The original Hawkesworth bit was not provided with a water hole but, depended upon water passing through the clearance opening between the tongue in the bit and the groove in the rod to flush cuttings from the drill hole, see Fig. 1. In December 1935 it was found that this method of introducing drilling water to the bit face resulted in high dust counts. To correct this a water hole was drilled on the central axis of the bit, passing through the tongue. Unfortunately, quenching water would rise through the small water hole, spot-hardening the tongue to cause breakage, never completely eliminated. In the fall of 1936 large-scale tests indicated that savings would be effected by use of a threaded type of bit, which was therefore adopted as standard for all Butte mines. This type of bit was used until 1947, when it was superseded by a one-use slip-on type. Since the first use of the Hawkesworth bit every detachable bit of importance has been investigated, and where advantages which might reduce costs or increase efficiency were indicated, substantial tests of the bit were carried on in the Butte mines. When tests demonstrated the advisability of changing from one kind of detachable bit to another the change was made at one level or in one area each day until the new rod and bit equipment was used throughout the mine. This involved a minimum of cost and disruption of drilling. Intelligent selection of a detachable bit to obtain optimum results requires careful consideration to achieve a balance between the three principal types of equipment used in the drilling process: 1—drill bits, 2—drill steel, and 3—drilling machines. Optimum results imply maximum output and minimum cost per unit of output. Since every rock type differs in drillability and it is generally impractical to provide equipment for more than one or two types of rock which may occur in one operation, selection of equipment must encompass average drilling conditions. However, on exceptional occasions several widely differing conditions may make it mandatory to provide equipment best suited to each condition. The choice of rock-drilling equipment is a most controversial subject and one that is further complicated by unreliable and frequently misleading performance claims. Small operators without the means for making accurate evaluations of equipment frequently suffer from these over-enthusiastic claims. It is apparent from experience in rock drilling throughout the world that rock drillability is not alike in any two places, and that selection of proper equipment can only be made after conducting thorough trials of various types of equipment. Some recent drilling tests in tactite and hornstone at the Darwin, California mine of the Anaconda Co. present some interesting clues on rock drillability. Microscopic examination of thin sections of these rocks reveals that mineral composition and rock texture are equally important in governing drillability. The Darwin hornstone is at times so abrasive that the carbide bit cutting edges become flattened to 3/32 in. in 2 to 4 ft of drilling, and some carbide bits were dulled to this point after 9 to 10 in. of drilling. This wear was determined to be the proper point for resharpening to eliminate carbide insert breakage or breakage of the steel rod when drilling with 1½ to 1?-in. bits, with a drifter of 2 3/4-in. diam and 90 to 100 psi air pressure, see Supplement A. Before considering the merits of various bit designs it may be well to review the mechanics of drilling rock with percussion drills. A sharp bit cuts by penetration and chipping. The amount of penetration governs the amount of chipping and depends upon the contact area of the cutting edge, the foot-

Jan 1, 1954

By C. N. J. Wagner, E. N. Aqua

The bee alloys of the terminal solid solution of rhenium in niobium were investigated by X-ray diffraclion methods. The analysis of the broadening of the powder pattern peaks from the niobium-rich alloys, cold-worked by filing, showed evidence for faulting on (211) planes. The alloys with larger rhenium concentrations were brittle, and fractured when filed. The analysis of the shapes of the diffraction profiles from powders produced by hammering with steel plates) of these brittle alloys indicated that the broadening was due predominantly to platelets bounded by clibe planes. This result was consistent with the Laue patterns from single-cleazlage facets which showed evidence for clearage fracture on {100} planes. The influence of faulting on the mechanical properties of face-centered cubic (fcc) metals and alloys, i.e., how faulting affects the various dislocation configurations in fcc metals, is well-known.&apos; The important question is whether or not faulting occurs in body-centered cubic (bcc) metals and alloys, and, furthermore, if faulting does occur, to what extent it affects the mechanical properties. Theoretical calculations indicate that the stacking-fault energy is rather high in most bcc metals.2 The results of sev-eral studies using transmission electron microscopy have indicated that faults are present in well-annealed and lightly deformed bcc metals and alloys, such as tungsten,3 vanadium,4 and Mo-Re alloys.5,6 These faults, as have been observed, may be stabilized by the presence of interstitial (C,N,O) atom segregation to the extended dislocations. In addition, there is considerable X-ray diffraction evidence for faulting in bee metals,7-8 using the same techniques that were successful for the study of faulting in fee metals and alloys.7 This X-ray diffraction method is currently the only technique applicable for the investigation of faulting in metals with high stacking fault energies, i.e., when severe amounts of deformation are required to produce sufficient amounts of faulting to be detectable by X-rays. The thinned films of heavily deformed metals will become opaque in the electron microscope due to the high dislocation densities present. In a previous investigation of faulting8 in bee metals of group Vb and VIb, the authors observed that niobium was ductile when filed at room temperature, and showed the highest density of faults on the (112) family of planes. A niobium-base alloy system was therefore chosen to study the effect of alloying on the occurrence of faults in a bcc alloy. There is a large range of terminal solid solubility of rhenium in the alloys of the bee refractory metals. All of the Group VIb-rhenium alloys, i.e., Cr-Re, Mo-Re, and W-Re, exhibit solid solution hardening without loss of ductility.9 In fact, the ductility reaches a maximum for alloys with compositions near to the limits of solubility. This enhanced ductility has been attributed to the lowering of the stacking-fault energy in the alloy; i.e., the increased amounts of twinning provide an additional mode of deformation, resulting in the observed high ductility.&apos; Because of this demonstrated effect of rhenium in bee alloys, it was decided to study a series of alloys of Nb-Re. Using the same X-ray diffraction methods as described in the previous investigation,&apos; one is able to identify the possible causes of broadening of the powder pattern peaks, e.q., particle size, microstrains, stacking faults, and/or twin faults. The separation of these various contributions to the measured peak shape is accomplished by the Warren-Averbach analysis.7 I) EXPERIMENTAL PROCEDURE A series of seven bee solid solution alloys containing from 2.5 to 21.5 at. pct Re (remainder niobium) were prepared at the General Electric Research Laboratory. Buttons, weighing 25 g, were alloyed from electron-beam-melted niobium chips and random rhenium sheet by arc melting in a water-cooled copper crucible, under an argon atmosphere. The buttons were inverted and completely remelted to promote homogenization. The nominal alloy compositions are listed in Table I. Samples of the cold-worked alloys were obtained by filing to produce a powder for the X-ray study. Alloys too brittle to be filed were hammered with steel plates. The resultant filings or brittle impactings were screened through 150-mesh classifiers and compacted to the required shape for the diffractometer holder. The X-ray diffraction peaks were automatically recorded by fixed time counting at uniform 28 intervals, or by continuous registration with a ratemeter. In all cases, the (110)-(220) and (200)-(400) pairs of peaks and the (211), (310), (222), and (321) reflections were measured on a GE-XRD5 diffractometer using CuKa radiation with nickel filter or MoKct radiation and a LiF monochromator in the diffracted beam. The first part of the data reduction, completed with the aid of a series of programmed computations,10 was the analytical resolution of the Kol component of the diffraction profile. Subsequent computations were then made with reference only to the resolved Kol peak shape. These included the measurement of the

Jan 1, 1967

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1&apos;2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:&apos; Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal&apos;3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.&apos; Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968