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By A. D. Marriott, J. V. N. Dorr

This paper reviews recent developments in the application of classification practice to the origination of fine-grinding flow sheets and traces the history of the mechanical classifier from its initial application for separating cyanide process sands and slimes down to its present six or more distinctly different applications at copper concentrators; it undertakes to show also, by reference to diagrammatic fine-grinding flow sheets and accompanying operating data from nine copper concentrators in western North America, the advantages gained from improved classi-ficiation flow sheets at these properties in terms of reduced grinding costs, improved flexibility of operation or increased recovery. Comparison is only made between different fine-grinding flow sheets at a given plant and no attempt is made to compare different concentrators, on account of ore variations and differences in metallurgical objectives sought,. The adoption of the flotation process in recent years, and especially the development of selective flotation, has brought a demand for much finer grinding than formerly. This has caused much thought to be given to grinding efficiency, and today there is hardly a mill where the grinding flow sheet is not under close study and subject to frequent changes. When closed-circuit grinding was introduced into metallurgy some years ago, its value was recognized at once, and since then the combination of mills and classifiers has been regarded and operated as a grinding unit. Apart from variations in both the grinding and classifying elements of this unit, there have been many variations in grouping tried by different mills to suit varying conditions of ore and plant limitations. Although operators feel that in most cases their present flow sheets are on trial, and the data on present work are often incomplete, we have felt that a discussion of the progress that has been made and an endeavor to show present trends and their results should be of use to the profession. We have therefore prepared flow sheets of some of the larger mills with which we have been in contact and present them with available data as to their results, in the hope that they may be of service now rather than later when practice may have become more standardized and more complete records and analyses have been made. We believe that the data given,

Jan 1, 1930

By B. Ball, D. W. Fuerstenau, P. C. Kapur

A two-phase distributed-parameter model of the flotation process has been extended to allow consideration of the important process parameter, concentrate grade. A simple expression is presented for the grade of concentrate in terms of the zeroth and first moments of the concentrate distribution. An example is given for a binary ore containing two pure minerals each having nondistributed rate constants. For extend-ing the model to the distributed rate constant case, a cubic polynomial zoas utilized to simulate the feed distribution. One particular example is considered and grade-recovery curves are generated to show the dependence of such curves on the initial feed distribution. Operating flotation plant engineers have traditionally evaluated plant performance in terms of the recovery of valuable mineral and the grade of the concentrate. In both operation and research, grade-recovery relationships have been used as a guide for selecting flotation conditions. Weissl illustrated the use of grade-recovery curves in plant operation and considered the grade-recovery relationship to be a metallurgical one. The extensive experimental work of Chi" using standard batch flotation tests on iron ores shows that, even with extensive statistical correlation of data, little insight can be gained into the basic fundamentals of these relations. Such relations must depend on the kinetic behavior of the various mineral species in the flotation circuit. In his flotation text book, Gaudin3 considered the relationship of recovery and of product grade to flotation kinetic indices, but he did not extend his calculations to yield grade-recovery relations. Although Gaudin used a simplistic model for his analysis, he did recognize that variations in flotation rates must result from variations in locking, surface heterogeneity, particle size and shape, among other things. In a recent paper,' we presented a model of the flotation process that could be readily analyzed with an analog computer. This model combines the concept of a distributed set of rate constants"" with that of the two-phase flotation model,8" resulting in a model more powerful and flexible than previous ones. The purpose of the present paper is to show how this model can be used to generate grade-recovery curves and to determine the dependence of such curves on the various kinetic parameters. In this paper, the model will be limited to the semi-batch case, but extension to the continuous case is a straightforward step.

Jan 1, 1971

By L. E. Young

THE progress of mineral industry education will be limited to the period prior to World War II and will be considered as primarily a division of engineering education. Its relation to progress in the mineral industry and to the activities of the American Institute of Mining and Metallurgical Engineers will be emphasized. The history of mineral industry education has been recorded most completely and authoritatively by Dr. T. T. Read in his recent volume in the Seeley W. Mudd Series of American Institute of Mining and Metallurgical Engineers publications, entitled, The Development of Mineral Industry Education in the United States. Therefore, most of the historical details will be omitted from the discussion and an effort will be made to point out significant developments and to analyze trends. INTRODUCTORY STATEMENT AND SIGNIFICANT POINTS IN PROGRESS Among the significant points in the development of mineral industry education in the United States since 1871, the following deserve particular mention: I. The number of institutions offering undergraduate instruction has increased, particularly during the years 1890 to 1925; the number of students enrolled in undergraduate study has increased greatly, largely on account of the development of courses in petroleum engineering and increasing interest in metallurgy. 2. The selection of students to be admitted to undergraduate courses has been improved through the advisement, counseling, and guidance programs sponsored by the Engineers' Council for Professional Development. 3. Improved instruction methods and the training of the teaching staff have been promoted by the educational institutions themselves, but with the most effective stimulus and guidance of the American Society for Engineering Education and the Engineers' Council for Professional Development. 4. The accrediting of undergraduate curricula through the Engineers' Council for Professional Development, considering both qualitative and quantitative criteria, has done much to improve standards of instruction in engineering education for the mineral industry. 5. Undergraduate curricula and courses are revised currently to meet the needs of the American mineral industry. New curricula are developed currently to permit specialization in technical fields, particularly in the fourth year of undergraduate work. 6. There has been a strengthening of the fundamental courses in mathematics, physics, mechanics, and chemistry, and at the same time these courses are being adapted to the most recent developments in the industry, including metallurgy, geophysics, petroleum engineering, petroleum technology, ceramics and so forth. 7. There has been continuing improvement in plant and laboratory facilities of the educational institutions.

Jan 1, 1947

By R. M. Bird

Few persons outside of the foundry trade have any conception of the great variety of sands now regularly specified and furnished, nor of the differences in foundry practice frequently resulting from apparently minor changes in sands. Conditions in each locality where the sands are mined and prepared necessitate special equipment designed to perform the work efficiently. The description that follows of the foundry-sand producing operations is typical of the areas in New York and New Jersey, and particularly refers to the operations of the George F. Pettinos Co. A few years ago the so-called Albany sands were dug by simple methods and hauled by horsecart to railroad. Depletion of sand near railroad sidings and extended use of automotive power have appreciably extended the area from which sand is now being dug. It is not unusual to haul 5 miles to the railroad. As stripping is quite shallow, 6 to 18 in., and the banks of usable sand generally run from 12 in. to 4 ft., it is economical to work the bank by benches so narrow that the overburden can be thrown by hand shovel to the exposed bottoms. In effect the top soil goes back to where it was, but on a lower level. Consequently the general surface appearance of a mined acreage is the same as before. This condition is in fact cutomarily required when a farm owner sells his sand in the ground. After such replacement, in the course of 3 to 5 years the soil is no less fertile than it was before mining. The sand itself varies as to grain and bond vertically and also along the breast. No mechanical equipment has been developed to compete with hand shovels and no machine has as yet been devised that grades the sand as required. Uniformity of sand, as shipped, depends first, last and all the time on the man on the job. Mixing equipment can change the appearance of the sand and mask its lack of uniformity, but it will never correct wrongly graded sand, dug from the bank. Modern methods of testing are helpful in setting up standards against which the man in the bank can compare his sands, but a good bank foreman is the only assurance that the sand, as dug, matches the required sample.

Jan 1, 1926

By A. L. Labbe, J. J. Donoso

Hard-won experience in the operation of smelting plants has pointed the way to the most efficient design and economical operation of a baghouse system for recovery of metallurgical fumes. This paper treats of the principles governing bag filtration and the factors most directly affecting bag life. Methods for temperature conditioning of smoke previous to filtering are described and the evolution of bag shaking mechanisms is brought up to date. THE history of the bag filter process, as applied to the recovery of metallurgical fumes, goes back to 1876, when the Lone Elms Works of Joplin, Missouri, erected a two-section baghouse for filtering fumes from Scotch Hearth lead smelting furnaces. By modern standards this installation was crude, but the basic operating principles remain essentially the same today. Great progress, however, has been made in the mechanization of the process by the use of devices for mechanically and automatically cleaning bags of adhering fumes, in the use of instruments for recording and controlling the variables affecting baghouse operation, and in the conditioning of the smoke previous to filtering. The principles governing bag filtration of fumes were investigated in 1929 by A. J. Seitz of American Smelting and Refining Co., and he arrived at the following conclusions: 1. Pressure on Bags at Constant Volume: The rate at which the pressure builds up in a bag with constant volume is directly proportional to the time, with the same kind of smoke and dust burden (fig. 1). 2. Pressure on Bags for Change in Volume: With equivalent smoke and dust burden, the bag pressure increases with the square of the increase in volume. The rapid increase in pressure is due to (1) increase in volume, (2) increase in amount of dust on the bag, and (3) more intense packing of the dust at higher velocity (fig. 2). 3. Effect of Intensive Filtering on Pressure: Since the pressure builds up directly as the square of the volume, with the same smoke and dust burden, it is necessary to shake the bags in that increased ratio, and vigorously, to keep the pores of the bag open and pressure down. This increases the wear on the bags and the dust losses. 4. Effect of Shaking on Dust Losses: The losses are in direct proportion to the frequency of shaking because the loss takes place immediately after shaking, before the bag seals itself. Tests show that with hand shaking the last 20 pct of the removable dust requires seven times more shaking per unit weight of dust than the first 80 pct. 5. Effect of Fineness of Dust on Losses: The fineness of the dust particle increases the loss in two ways: (1) When the bag is clean a greater percentage of it will pass through before the bag seals itself; (2) fine material penetrates farther into the bag pores, building up pressure faster and necessitating more shaking, thereby increasing the loss. The physical principle of operation of the bag filter is simply the separation of solids from a gaseous carrier through a porous medium, and is analogous to the filtration of solids from liquid carriers. Basically, the mechanics of the process are as follows: Fume-laden gases drawn from the operating fur-

Jan 1, 1951

By J. F. Smith

ELASTIC constants of yttrium and eleven of the rare earth elements have been measured. This has been accomplished by measuring the propagation velocities of ultrasonic pulses. The velocity measurements were made by noting the elapsed time between an applied pulse and the appearance of successive echoes. The pulse-echo technique has become relatively common, and the basis of the measurement is outlined in several standard tests, e.g., Heuter and Bolt.1 Two important assumptions are made when using this method for the determination of elastic moduli. First, the pulse is assumed to propagate as a plane wave. To justify this assumption, the cross section of the test specimen should be large compared to the wave length of the transmitted pulse. For these measurements on the rare earth elements the minimum cross section wave length ratio was about 20. A second assumption which must be made when using polycrystalline specimens is that the grains are sufficiently numerous and randomly oriented so that the specimen may be approximated as elasti-cally isotopic. The grain size in the as-cast specimens which were used is believed to be sufficiently fine for this approximation, and the degree of preferred orientation is believed to be small. Supporting this viewpoint is the fact that elasticity measurements by the pulse-echo technique on as-cast specimens of other metals give results which are in satisfactory agreement with values obtained by other techniques. Hence, it is believed that the measured elasticity values for the rare earth elements are not apt to be seriously in error due to the assumption of elastic isotopy. The apparatus used in this determination was a modified Sperry Reflectoscope with a precisely calibrated time base circuit. Piezoelectric transducers were used both to generate the pulse and to detect the echoes. X-cut quartz crystals were used for the longitudinal modes, and Y-cut quartz crystals were used for the shear modes. Frequencies of 2.25 and 5 megacycles per sec were employed. Most of the specimens were 2.5 to 5.0 cm in length. Results Table I is a tabulation of the measured propagation velocities of longitudinal waves and of shear waves, together with densities obtained by Sped- ding, Daane, and Herrmann2 from lattice parameter measurements. The shear modulus, Poisson's ratio, and Young's modulus were calculated from the data in Table I through use of the following relationships: µ = pv32 [1] s=2-(vb/vs)2/2[1-(vb/vs)2] [2] and Y= 2µ(l+s) [3] where s is the shear modulus, Y is the Young's modulus, s is Poisson's ratio, p is the density, V0 is the longitudinal wave velocity, and v, is the shear wave velocity. The calculated quantities are shown in Table 11. Compressibility values can be computed from the relationship and the computed values may be compared with measured values obtained by Bridgman.8 Table III lists the data for such a comparison. The agreement is satisfactory, being particularly good for neodymi- um and gadolinium, poor for samarium, and intermediate for the other elements. Some variation is expected since Bridgman's measurements are isothermal, whereas the present measurements are adiabatic. In addition there may be some effect due to small variations in purity. Though most of the rare earth metals measured by Bridgman and all of the metals used in the present measurements were prepared at this laboratory, minor purity variations might exist since the samples came from different lots. Also, any imperfections such as dislocations, vacancies, voids, grain boundaries, microcracks, etc., should contribute to the volume change of a com-

Jan 1, 1958

By G. E. Johnson

The problem of efficient reclamation of zinc base die cast scrap became interesting early in 1930. Die Cast Metal, as referred to in this paper, is a zinc base alloy with various proportions of aluminum, copper, magnesium, antimony and tin. Many attempts were made to work out some means of reclaiming the discarded die cast metal for re-use as new die cast metal. Difficulties in such reclamation were attributable to contamination by lead and tin from solder, chromium and nickel from electroplated coatings, and iron from iron inserts. This paper relates the experiments that led to the development of a specialized muffle furnace for the treatment of zinc base die cast scrap for the production of zinc oxide and zinc, and describes the development of the muffle furnace and the equipment now used commercially for these purposes. The Eagle-Picher Co. acquired all patent rights' for these developments from the International Smelting and Refining Co. in connection with their purchase of the East Chicago Plant. Zinc Base Serap Situation About 1935, the die cast scrap situation became increasingly acute for scrap dealers. This scrap was accumulating from dismantling automobiles and household appliances which contained die cast parts. Efforts to find an outlet for this type of scrap were intensified. The International Smelting and Refining Co. began to study the possibilities of a commercial process for the recovery of values from die cast scrap. At that time most of the die cast metal reclaimed was melted down in small kettles of from one to five tons capacity, the iron inserts being removed by skimming. The dross was skimmed off and disposed of as a zinc dross. The drossed metal was cast into slabs and was given the trade name "die cast slabs.". Distribution of the products produced by melting die cast scrap in kettles is shown in Table 1. American Process Experiments A method considered for the production of zinc oxide from die cast scrap was an adaption of the standard American Process of zinc oxide manufacture. Thus some die cast scrap was mixed with oxidized zinc materials and charged to Wetherill grates. The zinc oxidized to zinc oxide but, while the aluminum and copper largely remained in the residue, the color of the zinc oxide produced was impaired by copper contamination. As the proportion of die cast scrap was increased, liquation took place; that is, the metal trickled through the charge then solidified in the openings of the grates. French Process Experiments Several hundred tons of die cast scrap were purchased for test purposes and converted into die cast slabs. These slabs were charged into a French Process (horizontal retort) zinc oxide furnace with some electrolytic zinc. A satisfactory grade of zinc oxide was not produced. Distillation in Belgian Retorts It was then decided that, rather than attempt to use scrap die cast metal or scrap zinc for the production of zinc oxide, it would be advisable to redistill the die cast slab metal in a Belgian retort furnace. The opportunity to do so was provided by the closing of the zinc smelter of the Illinois Zinc Co. at Peru, Ill. Arrangements were made for the operation of a Belgian retort furnace for such redistillation purposes. The results of this experiment are summarized in Table 2.

Jan 1, 1950

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By Henry A. Stiff, and Lawrence E. Davis

The authors previously presented a method for predicting the tendency of oil field waters to deposit calcium sulfate. The present paper gives a similar method for calcium carbonate. Methods for predicting calcium carbonate scaling tendencies in fresh waters have been available for some time, but these could not be used for brines. By experimentally deriving the value of the K term in the Langelier equation, a method has been developed which applies to waters of high salt content. A statistical study is included which shows that the experimentally derived values of K are in good agreement with actual conditions. Several applications of the final equation to production practice are given. INTRODUCTION The authors previously presented a method for predicting the formation of calcium sulfate scale in oil field waters.' Although calcium sulfate deposition is important in production operations, the majority of scale problems involve calcium carbonate. The present communication discusses a method by which the formation of this type of scale in oil field waters can be predicted. Calcium carbonate precipitation is caused by a shift toward carbonate in the carbonate-bicarbonate-carbon dioxide equilibrium. When equilibrium shifts in the other direction, the precipitate goes back into solution. Since there is usually considerable delay between the establishment of an equilibrium and the precipitation or solution of calcium carbonate, unstable conditions exist in which a water will precipitate or dissolve calcium carbonate on standing. Tillmans? who did a major part of the early work on carbonate scaling, pointed out that the condition of equilibrium not only indicates the tendency of a water to scale but also is an indication of its corrosive properties. Previously precipitated calcium carbonate combines with iron to form a dense crust which inhibits corrosion. If the water tends to dissolve carbonate, the scale becomes porous, and electrolytic corrosion takes place. Tillmans1 work was extended by several investigators until in 1934 Langeliers developed an equation setting forth the conditions of carbonate equilibrium. By the use of this equation the pH of a water at equilibrium can be calculated. If the actual pH is higher than the calculated pH, the water has a tendency to form scale. If it is lower. the water has a tendency to be corrosive. Langelier's equation can be expressed in a simple form as follows: SI = pH-pCa-pA lk-K where: SI is the stability index. A positive index indicates scale formation. A negative index indicates corrosion. pH is the pH of the water sample, as actually determined. pCa is the negative logarithm of the calcium concentration. pAlk is the negative logarithm of the total alkalinity. K is a constant, the value of which depends on the total salt concentration and the temperature. This equation has been shown to apply to waters with totaI solid concentrations as high as 4.000 ppm. In fact, control of fresh water treatment by means of this equation has been standard text-book practice for a number of years. Nomographs have been worked out so that the stability index of a fresh water sample can be determined in a matter of minutes. Most oil field waters, however, contain well over 4,000 ppm of salts and for this reason the usual application of Langelier's equation can not be made. By an empirical method we have extended the application of the Langelier equation to waters of high salt concentration. By the use of this equation the tendency of oil field waters to deposit calcium carbonate can be predicted.

Jan 1, 1952

By O. E. Palasvirta

Close examination of most so-called n.eu processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual para-magnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Desire Korda in Paris in 1905,' and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field. The present investigation was prompted by the apparent success of the German installations and by the discovery of iron ores on this continent which may be amenable to high-intensity separation. The objective was to gain better insight into the underlying principles of separation in a high-intensity field and to use this knowledge in selecting or designing an optimum separator. THEORETICAL CONSIDERATIONS he well known low-intensity magnetic separators are. without exception, of the the magnet type with more or less similar field shapes. It is therefore permissible to speak of their comparative strengths in terms of field intensity alone. However, proper understanding of the high-intensity magnetic separation process requires somewhat deeper analysis of the relationship between the magnetic field and the attractive force. Contrary to a widely held belief, a magnetic field of parallel lines of flux exerts no attractive force on a magnetically susceptible particle, but merely aligns its poles parallel to the lines of flux. On the other hand, a non-uniform field attracts a magnetically susceptible particle in the direction of the converging lines of flux. Thus the force of magnetic attraction varies as the product of the field intensity and the field gradient: dH ds As the induced-rotor magnetic separator is primarily intended for separating feebly magnetic materials, it is important that maximum attraction be attained. For the designer, then, the relationship between the magnetic field and the attractive force has the following implications: 1) Insofar as possible, the separation gap must be saturated with flux. 2) The rotor surface must be shaped to insure maximum convergence of lines of flux toward the rotor. 3) The primary pole face (opposite the rotor, on the other side of the separation gap) must be shaped so that the lines of flux do not diverge from it at any location in the effective separation zone. The actual attractive force of the rotor, and its critical speed, can be calculated as shown by Runo-linna, provided that the true flux density, the field gradient, and the magnetic susceptibility of the mineral can be measured with sufficient accuracy. The irregular shape of the rotor surface makes flux measurements difficult, but it can be done if a suitable gaussmeter is available (see Fig. 2). Calculations by the author, and comparisons with the centrifugal force exerted by the rotor, indicate that the force pinning a hematite particle to the rotor is of the same order of magnitude as the force holding a

Jan 1, 1960

By H. J. Beach

This paper describes the properties and uses of cementitious mixtures containing 10 to 20 per cent bentonite and 2 per cent or more sodium chloride. Salt additions improve bentonite cement by increasing early strength and stabilizing viscosity without changing thickening time. The volume yield of cement is increased 20 per cent or more without lowered early strength. The unique properties of salt in this type of system make savings of more than 10 per cent possible where light-weight, low-strength cementitious material is adequate to fill behind pipe. The density range of these mixtures is 12 to 13 1b/gal and the filtration rates are medium-low, aiding the placement of long columns in primary cementing. Where available, sea water is an ideal salt source in preparing these slurries. INTRODUCTION Accelerators increase the rate of cement hydration. In speeding reaction with water, they can affect cement performance by reducing thickening time and increasing early strength after set. Accelerators that cause both effects can be considered "total", and those which produce only one effect can be called "partial". Materials that act conversely to accelerators are retarders. and they also can be total or partial. Partial retarders. make high-temperature cementing possible by prolonging thickening time while impairing early strength only slightly. Most known accelerators are total. A useful partial accelerator would increase strength without altering thickening time. This report concerns material combinations in which a normally total accelerator exerts unique partial properties. Utilizing these limited effects improves bentonite cement. SEPARATE EFFECTS OF SODIUM CHLORIDE AND BENTONITE ON CEMENT Sodium chloride and calcium chloride are commonly used in cement, and at low concentrations their effects are similar. Ludwig1 studied sodium chloride in API Class A and Class E cements.' Figs. 1 and 2 sum- marize his data taken at 140°F on slurry pumpability and early strength. Normal water-to-cement ratios are 0.46 and 0.40, respectively, for Class A and Class E cements. At saturation the salt content is 12 to 14 per cent of the weight of cement solids. The illustrations, therefore, cover the range of salt solubility in the mixing water. The data show that sodium chloride is a total accelerator of the Class E cement studied over the range of solubility. It is total in Class A cement to 6 per cent. Above this concentration salt becomes a retarder— partial from 6 to 10 per cent and total above. These results are general for different brands of Class A cement, although the shift from acceleration to retardation may occur at different salt concentrations for different temperatures. The results are specific for the Class E brand studied. In discussing his data, the investigator emphasized that different Class E cements might respond erratically to salt, depending on the brand chosen. Morgan and Dumbauld3 escribe the properties of bentonite cement in a paper that is a standard reference in using these systems. Bentonite functions in cement as an enabling agent; each bentonite addition equal to 1 per cent of the weight of dry cement makes possible the further addition of 4.5 per cent water.' Thus, 10 per cent bentonite in Class A cement, normally slurried neat with 46 per cent water, enables the slurry to contain another 45 per cent before settling. Water is one of the lightest and cheapest cement extenders; it reduces density and cost. Bentonite cements produce uniform slurries having low susceptibility to solids separation. After set, they offer low resistance to perforation.

By Stanley L. Lopata, Eric B. Kula

The problem of preferred orientation has been considered in quantitative phase analysis by X-ray diffraction techniques. The average intensity of a diffraction peak can be obtained by integration over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. For rod or wire, where the pole figure shows rotational symmetry, the intensity is measured along a radius of the pole figure. Where no symmetry is present, rotational symmetry is imparted by rapid rotation of the sheet around its surface normal during measurement. These methods are applied to the determination of aus-tenite in an Fe-31 pct Ni rod and Fe-28 pct Ni sheet. X-RAY diffraction techniques are frequently used for quantitatively determining the relative amounts of two or more phases present in a structure.1,2 Briefly, the method requires a measurement of the intensity of a Bragg reflection for each phase. The method is based on the principle that the intensity of a Bragg reflection, IA, is directly proportional to the volume fraction of the given phase present, CA: T KRACA/2µ [1] where K is a constant independent of the diffracting phase, RA can be calculated and depends on the Bragg angle ? and the particular reflection measured, and µ is the linear absorption coefficient of the mixture.' For a mixture of two phases A and B, IA = RAcA [2] IA/IB=RAcA/Rbcb and CA+ CB = 1 [3] This allows the volume fraction of a phase to be calculated directly from the measured integrated intensities of the two phases present. This method is frequently used for quantitatively determining retained austenite in steels, but can be used for the quantitative determination of in titanium alloys, as well as phases in other alloy systems. The intensities are generally measured by diffracting only from planes whose normals are perpendicular to the specimen surface, with the implicit assumption being made that this intensity is typical of reflections from planes whose normals lie at other angles to the surface. If the specimen contains a texture or preferred orientation of the crys- tallographic planes by virtue of previous mechanical working, however, this measured intensity is correct only if the intensity level fortuitously is one times random. Examination of pole figures for actual rolled sheet shows that the intensity level at the center of the figure is seldom at the random level, and can very easily differ by a factor of five or more, leading to a commensurate error in the calculated amount of the phases. Textures have been commonly found in materials which are cold-rolled or recrystallized after cold rolling. This problem is becoming of greater importance since structural materials in use today, such as the high-strength stainless steels, frequently are further strengthened by cold rolling, and hence contain textures. Although high-strength carbon-containing alloy steels generally do not contain textures, some of the newer thermomechani-cal treatments will impart a texture even in these cases. In the case of hexagonal metals, such as titanium, probably every wrought sample will show some anisotropy. Since the standard X-ray techniques are inapplicable in all these cases, there is a clear need for some method of taking this anisotropy into account. The specific problem is to obtain the integrated intensity of a Bragg reflection for each phase, averaged over all orientations of the sample with respect to the X-ray beam. This can be done either by purely mechanical means or by a mathematical averaging. Mechanically, a small spherical speci-

Jan 1, 1965

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By M. H. Pilkuhn, H. Rupprecht

p layers on n-type substrates of GaAs were prepared by difhsion of zinc into these substrates. Experimental details about the diffusion technique will be presented. It will be shown that inhomogeneity in the substrate doping level and crystal shucture defects cause nonplanarity in the junction plane. These nonplanarities give rise to high threshold current densities. From incremental sheet-conductivity measurements the zinc profile is derived. Data about surface concentration and gradient of the zinc concentration at the junction are presented. Finally, some results of laser diodes, which were made of wafers with extremely planar diffusion fronts, are discussed. ThE investigations reported here are part of a program concerned with the materials aspect in the fabrication of GaAs laser diodes. This includes studies of the influence of crystal defects introduced both during the growth of the crystal and as a consequence of subsequent diffusion. Compared with the progress made in the investigation of structure defects, for instance by X-ray microscopy in materials like silicon, no similar results are known so far for the case of GaAs. The further progress in laser diodes will depend very much upon our knowledge of these structure defects and subsequently upon our ability to avoid them. Laser diodes of GaAs had been made mostly by diffusing an acceptor impurity, normally zinc, into an n-type substrate. This procedure was found more convenient than the inverse one for various technical reasons. We will follow this line and restrict ourselves to zinc diffusion only in this paper. DIFFUSION TECHNIQUES AND EXPERIMENTAL DETAIL In order to set a refgrence for our experiments, we used a standard procedure for the diffusion runs. The diffusions were carried out in a sealed quartz tube for 2-1/2 hr at 850°C. One milligram zinc arsenide (ZnAsz) per cu cm of the tube volume served as zinc source. Under these conditions the junction depth was between 25 and 30 p. It is assumed, according to the investigations of the zinc arsenide system by V. Lyons and V. ilvestri,' that ZnAs2 dissociates completely at 850°C into ZnsAsz and Asg. Since there is a condensed phase of ZnsAs2 in the tube at 850°C, the partial pressure of zinc is controlled by the pressure of the arsenic formed by the dissociation of ZnAs2. Due to the fact that the zinc partial pressure resulting from the dissociation of ZnsAsz is only a weak function of the partial pressure of arsenic, the amount of the initial ZnAs2 is not very critical. Experimentally, we found that the junction depth, as well as the surface concentration, was practically the same, if the ingots of ZnAs2 varied between 0.2 and 5.0 mg per cu cm. The wafers were oriented with the main faces in (100). Surface damage due to cutting and lapping was removed by a chemical-etch treatment in a rotating beaker (etch solution: HzSOr, H202, and HzO in a ratio 3:l:l). The GaAs substrate material was n type and doped with tellurium, selenium, silicon, or germanium. It was grown by means of horizontal or Czochralski techniques. After the diffusion process, junction depth and planarity were checked either by grooving with a

Jan 1, 1964

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum were grown by multipass zone melting in an electron beam apparatus. Tension tests of these crystals at 4.2 x 10&apos;* per sec-gave a resolved louler yield stress of 7300 psi at with a chisel edge; total uniform deformation increased from 1 to 2 pct at 77°K to over 20 pct at 300°K. This, and slip traces, indicated that deformation is more inhomogeneous at lower temperatures. Deformation occurred exclusively by slip in <III> directions, on planes in the <111> zones. Cross slip was frequent, particularly for those orientations where the resolved shear stress on the cross system was comparable with that on the primary plane. The existence and magnitude of the upper yield point were found to be sensitive to orientation. This effect was related to the circumvention of dislocations which were "locked" by interstitial atoms, by double cross slip, or composite slip, of screw dislocations. Prestrainirg at 300°K did not remove the upper yield point in subsequent tension at 77°K. Also, this treatment was found to cause yield points, where none existed for the unprestrained material. This behavior was also rationalized in terms of the circumvention mechanism. The mechanical properties of polycrystalline tantalum have been investigated by several workers,1"4 and may be summarized by pointing out the following features: a) Sharp rise of yield stress with decreasing temperature below room temperature. b) Response to strain aging at 300" to 400"C. c) Yielding with upper and lower yield-point phenomenon at and below room temperature. d) Low strain hardening below room temperature. e) Reluctance to twin except at very high strain rate. Furthermore, tantalum is ductile at ordinary strain rates as low as 4.2"K.&apos; This feature, in particular, makes tantalum unique among the high melting point, bee transition metals of Groups V and VI in the periodic system. Therefore, a more fundamental and detailed knowledge of the low-tempera- ture deformation of tantalum is required. Since high purity and the absence of grain boundary effects make such a study most productive and unambiguous, the method of electron beam zone melting was selected for the preparation of test specimens. This technique has the further advantage that crystals may be seeded in order to obtain any desired orientation. EXPERIMENTAL The electron beam zone-melting equipment was constructed as a modification of that described by Calverley, Davis, and Lever? All crystals were made by three passes of the molten zone at 4 mm per min to achieve an optimum purity commensurate with economy of time and material. Table I reports the chemical analyses of the starting and refined metal. It will be noted that there remain some 50 to 70 wt ppm of interstitial elements, while all substi-tutional elements have been removed by evaporation. Tungsten is picked up by evaporation of the cathode filament wire. Crystal seeding was normally successful within 3 deg, and the orientation of all crystals are given in the standard stereographic triangle in Fig. 1. Tensile bars were prepared from the crystals by centerless grinding to the shape in Fig. 2. Specimens were then electropolished to remove 10 pct of the diameter in order to remove worked material and to prepare a metallographic surface for subsequent deformation trace observations. All specimens were held in the split bushing grips as indicated in the cross section view of Fig. 2. All tests were made at a strain rate of 2 112 pct per min in an Instron testing machine.

Jan 1, 1962

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen&apos; to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By R. L. Smith, I. G. Greenfield

The binary system Ga-Sb has been investigated by thermal, X-ray, and metallo-graphic methods. &apos;The intermetallic compound GaSb melts at 705.9OC and forms a eutectic with antimony at 11.8 atomic pct Ga. This eutectic melts at 589.8OC. A eutectic appears to be formed at 29.8°C but is too close to the composition of pure gallium to be detected. IN the course of an investigation of the semiconducting properties of the intermetallic compound, GaSb, the phase equilibrium between gallium and antimony has been investigated. Recently, the phase diagram of similar systems, such as In-Sb,&apos; In-AS,&apos; and Bi-As3 have been determined. These diagrams have the same general appearance in that an intermetallic compound is formed at 50 atomic pct and a eutectic is formed on both sides of the intermetallic compound. Jenny,& who has been investigating the semiconducting properties of intermetallic compounds, has concluded from thermal data of several alloys that the phase diagram of the Ga-Sb system resembles those mentioned previously. This paper represents a more detailed study of the Ga-Sb equilibrium. Experimental Procedure The gallium that was used to prepare the alloys was obtained from A. D. Mackay Inc. and the Aluminum Co. of America; the latter reported the purity as 99.95 pct. The antimony was obtained from Bradley Mining Corp. who specified a purity of 99.997 pct. Since the intermetallic compound of GaSb was prepared primarily to be used for further studies of the semiconducting properties, additional purification by a standard zone-melting technique under an atmosphere of hydrogen was performed. Hall-effect measurements on this material indicated an impurity content of less than 3 ppm.5 The antimony also was purified by zone melting and used in conjunction with the compound GaSb to make the necessary alloys for the determinations of the antimony-rich side of the phase diagram. The antimony-rich alloys were chill cast in Vycor tubes which were evacuated to a pressure of less than one micron. Since these alloys expand on freezing, precautions were taken to prevent oxidation of the ingot in the event the tube fractured. To insure homogeneity, the brittle alloys were ground and then placed in the furnace for the thermal-arrest determinations. Since the cost of gallium is high, the experimental procedure was complicated somewhat because of the necessarily limited sizes of the melts. In order to economize, the gallium-rich side of the diagram was determined by using a 35 g ingot of pure gallium initially and adding increasing amounts of antimony in order to obtain additional alloys. The furnace used in the determination of the cooling curves is illustrated in Fig. 1. A 2¼ in. quartz tube, sealed at one end, was fitted with a brass flange which was attached with DeKhotinsky cement. The brass collar was water cooled to prevent the cement from softening. An "0" ring was used to provide a seal between the brass collar and the furnace cover. Nichrome ribbon was wound around a 2 ½ in. asbestos-covered copper core which was used to reduce the thermal gradient in the furnace. The insulation consisted of alternate layers of asbestos and aluminum foil surrounded by sil-o-cel refractory and

Jan 1, 1956

By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.&apos; The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country&apos;s annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg&apos;ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

OF THE many categories into which scientific knowledge has been arbitrarily divided, the one which has proved most applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. To one who has had no such course or whose auld acquaintance with the subject has all but been forgot, such application is all too often thwarted by the abstruse presentations of the subject found in many of the available textbooks. AS a tool for the control of a complex process involving many chemical reactions, physical chemistry can become very valuable. The specialist who is using this tool for many purposes and perhaps contributing to its development will want to know a great deal more about it than can be included in this book. He will be interested in its history, its accomplishments and limitations, and its applications to many and varied problems. To the steelmaker or metallurgist, however, it is only one of a number of tools that he must use. He is willing to forego the detailed study of its inner workings in order to concentrate upon the development of skill in its application. It is the purpose of this chapter to present a simplified view of physical chemistry as a tool of great potential usefulness. This purpose and the desire for brevity have required the elimination of many of the gadgets with which the tool is usually adorned. It is hoped that this simplification will be conducive to clear understanding. The beginner is urged not to overlook the more extended treatments of the standard textbooks.* He is assured at the same time that the basic tool is sound and serviceable and is guaranteed to give satisfaction if regularly lubricated with common sense. Certain parts of physical chemistry require rather formidable mathematics for their complete development, but in the main those applications in which we are here interested can be expressed in fairly

Jan 1, 1944

By Maurice Cook

NORMALLY the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 min., for example, would, for many purposes, he regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals and alloys that take place on annealing, and a number of generalizations have been reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results, however, that are not covered by these generalizations can be obtained, which, in some instances, may even appear to he contradictory to them. According to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which, according to ordinary standards, would be classified as coarse or large.

Jan 1, 1938