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By Arthur Notman

THE year 1937 started off most hopefully for the metal industry but the prices for nonferrous metals declined after reaching a peak in the first quarter. E. & M. J. average prices for March were: -electrolytic copper f.o.b. refinery for domestic delivery 15.775c., lead 7.19c., and zinc 7.38c. There was the usual talk of shortages and the accompanying peak in the market prices of securities of producing companies. In retrospect it now appears that this was the peak of general security prices as well and of most commodity prices. On Dec. 1 copper was back to 11c., lead to 5c., and zinc to 5.5c. At the same time metal security prices had fallen to less than 40 per cent of their March highs. This has not been a purely domestic phenomenon. Metal prices have followed a similar course in London, in spite of the fact that in all three metals a tariff wall separates the domestic market from the foreign. There is nothing in the record to suggest that planning has so far had any stabilizing effect on prices. It is doubtful whether anybody will he found to claim credit for the planning. Strong evidence supports the conclusion that domestic demand for these and the other metals has been dammed back by the uncertainties confronting those who are considering long term construction commitments. This is particularly true with the public utilities, who are the largest consumers of copper and lead. If the plans were designed to maintain employment rather than to maintain political control of the Government, it would appear that they should be discarded. The course of the steel industry has been followed so closely in the press that no comment is necessary to indicate its similarity.

Jan 1, 1938

By T. M. Geffen, J. L. Sanderlin, F. F. Craig, D. W. Moore

Scaled reservoir models have been used to study the effect of gravity on oil recovery performance in frontal-drive operations; namely, water, gas, or solvent flooding. The difference in density between the reservoir oil and the injected fluid causes their segregation, resulting in a non-uniform advance of the fluid front. In the laboratory flow tests, which simulated both five-spot and linear injection operations in flat reservoirs, the viscous, capillary, and gravity forces present in these operations were scaled. Dyed fluids were used so that the gross movement of the injected fluid could be observed. The studies covered a range of injection rates, formation thicknesses, and rock and fluid properties normally encountered in field operations. The results of the model tests indicate that the volume of the reservoir contacted by the injected fluid at its breakthrough into the producing well is less than that expected based on information which neglects gravity effects. This difference can often be as much as 80 per cent by gas or water injection in uniform sand bodies. Preliminary flow tests on a non-uniform sand body indicate that the uniformity of the flood fronts may in some situations be influenced to a much greater degree by permeability variations within the rock body than by gravity effects. The magnitude of fluid segregation due to gravity is controlled by the average injection rate, rather than day to day or week to week variations. INTRODUCTION One of the important factors controlling the oil recovery from a frontal-drive operation, such as water, gas, or solvent injection, is the volumetric sweep efficiency. This factor is a measure of the gross portion of the reservoir that is contacted by the displacing fluid. The volumetric sweep efficiency is influenced by gravity effects, well arrangements, and variations in rock permeability within the reservoir. The gravity effects are due to the displacing fluid being of different density than the reservoir oil. This causes the displacing fluid to move preferentially toward either the top or bottom of the formation. Non-uniform advance of the flood front can be caused by the relative positions of the injection and production wells. Variations in rock permeability also result in an uneven advance of the displacing fluid. Gas zones, representing paths of low resistance, may result in non-uniform movement of the injected fluid. The more uneven the advance of the displacing fluid, the lower is the volumetric sweep efficiency and thus the lower the oil recovery efficiency. The effects of well arrangement and permeability variations, upon the gross movement of the injected fluid have been the subjects of extensive investiga-ti0ns.1,2,3,4,5,6 Gravity effects have been recognized as being present in frontal-drive operations'.' but there has been little quantitative measure of their magnitude. Very likely the reason gravity effects have not been studied is that this problem does not lend itself to simple experimental or mathematical analysis. The development of reservoir modeling techniques has made possible a quantitative determination of the effect of gravity on fluid segregation and thus upon the oil recovery performance of frontal-drive operations. This paper presents a progress report on a laboratory investigation of gravity effects in fully liquid-saturated, horizontal, uniform as well as non-uniform systems. These results were obtained from scaled experiments on both linear and five-spot systems within the range of conditions normally encountered in secondary recovery operations. This study is concerned with the gross movement of the injected fluid to the time it first reaches the production wellbore. Therefore, it should be emphasized that the results of this paper can not be used to determine the effect of gravity segregation on oil recovery efficiency at abandonment conditions. MODEL SCALING The science of scaling models is relatively new as applied as petroleum production problems, Many of the scaling techniques have been adaptions of those used in basic studies of heat and fluid flow. There are

Jan 1, 1958

By R. V. Whetsel, V. R. Gargias, J. W. Ristori

WoRld consumption of petroleum and its substitutes in 1941, the amount of which obviously is largely conjectural, is estimated at 2,066,653,000 bbl. This is 48,689,000 bbl. more than the previous year and is an all-time high. Except for the United States, this figure does not include consumption for military purposes. Consumption in the United States also reached an all-time high during 1941, totaling 1,492,000,000 bbl., or 158,230,000 bbl. more than the previous peak year of 1940. On the other hand, it is estimated that civil consumption in countries outside of the United States decreased 109,541,ooo bbl. as compared with the previous year. Demand for military purposes and/or additions to stocks in countries outside of the United States is estimated at 304,507,000 bbl. during 1941, compared with 209,635,000 bbl. in 1940. This increase was due largely to blitzkrieg warfare on several fronts. especially Russia; entailing large expenditures of petroleum by both sides because of the immense area covered by the fighting forces, the long supply lines necessary and the intensity of the fighting. It is interesting to note in this connection that Axis-controlled countries, excluding Japan, had an estimated production of approximately 89,000,000 bbl. of petroleum and its substitutes in 1941. The peacetime consumption of these countries in 1938, for example, was about 183,000,000 bbl. It is believed that the minimum to which civil consumption could possibly be re-duced in wartime is 20 per cent of that of peacetime, which would call for a minimum consumption of 37,000,000 bbl. in these countries in 1941 for civil purposes. This

Jan 1, 1942

By V. R. Gargias, J. W. Ristori, R. V. Whetsel

WoRld consumption of petroleum and its substitutes in 1941, the amount of which obviously is largely conjectural, is estimated at 2,066,653,000 bbl. This is 48,689,000 bbl. more than the previous year and is an all-time high. Except for the United States, this figure does not include consumption for military purposes. Consumption in the United States also reached an all-time high during 1941, totaling 1,492,000,000 bbl., or 158,230,000 bbl. more than the previous peak year of 1940. On the other hand, it is estimated that civil consumption in countries outside of the United States decreased 109,541,ooo bbl. as compared with the previous year. Demand for military purposes and/or additions to stocks in countries outside of the United States is estimated at 304,507,000 bbl. during 1941, compared with 209,635,000 bbl. in 1940. This increase was due largely to blitzkrieg warfare on several fronts. especially Russia; entailing large expenditures of petroleum by both sides because of the immense area covered by the fighting forces, the long supply lines necessary and the intensity of the fighting. It is interesting to note in this connection that Axis-controlled countries, excluding Japan, had an estimated production of approximately 89,000,000 bbl. of petroleum and its substitutes in 1941. The peacetime consumption of these countries in 1938, for example, was about 183,000,000 bbl. It is believed that the minimum to which civil consumption could possibly be re-duced in wartime is 20 per cent of that of peacetime, which would call for a minimum consumption of 37,000,000 bbl. in these countries in 1941 for civil purposes. This

Jan 1, 1942

By Raymond H. Young, Paul Sennett

INTRODUCTION Kaolin clay, consisting largely of the mineral kaolinite, is widely used as a white pigment. In the United States, for instance, pigment kaolin production was nearly 6,000,000 tons in 1976 (1). Production for this year should be significantly above this level. Current prices for kaolinite 'pigments range from about $20.00/ ton to$260.00/tony,depending on the amount of processing needed to make the final product. Although much of this pigment kaolinite is used as an inert filler where product specifications are not very rigid, a large quantity of kaolinite is converted to products where very restrictive specifications exist. These specifications set severe limits on such properties as viscosity in a water suspension, particle size distribution, color, and brightness. This discussion will concentrate on methods available to improve the color and brightness of pigment kaolin and will review the advantages and problems associated with these various methods. The term "brightness" refers to the reflectance of the pigment to blue light (2). Since even the brightest commercial kaolins have a somewhat yellowish color, the blue reflectance (or brightness) is a reasonably good measure of their nearness to a perfectly white material. I KAOLINITE STRUCTURE AND SOURCES The mineral kaolinite is an aluminum silicate and can be represented by the formula (OH) 8Si4A14010. The formula is frequently written

Jan 1, 1979

By C. K. Leith, W. J. Mead

One of the most significant developments in the iron industry in recent years has been the discovery and opening of enormous reserves of low-grade ore in eastern and northeastern Cuba. The two principal fields are the Mayari and the Moa, situated on Nipe bag, in the Province of Oriente. A less well-known district of the same type is that of Baracoa, at the east of the island, and another is in Csmaguey Province in central Cuba. In the comprehensive estimates of the iron-ore reserves of the world, published during the summer of 1910 by the International Geological Congress in Sweden,' these Cuban deposits are estimated at about 2,000,000,000 tons. Certain it is that the reserve is a large one. The Spanish-American Iron Co., the Juragua Iron Co. (Bethlehem Steel Co.), the U. S. Steel Corporation, and others have been active in this exploration. The Spanish-American Iron Co. has established a port for the handling of these ores at Felton, has built a railway 16 miles to the ore-fields, and has operied up deposits for steam-shovel mining. Its expenditures have reached an aggregate of about $6,000,000 in preparation for the handling of these ores. Shipment of the ore to Sparrow's Point, Md., has begun and may be expected to rise to a considerable amount in the near future.

Jan 1, 1912

By Donald E. Crowell

In the fall of 1969, ASARCO and Newmont Mining Co. began the design of the 700tpd concentrator at their Black Cloud shaft located near Leadville, Colo. The concentractor would treat by flotation a Pb-Zn-Ag ore containing minor gold values. Flowsheet design was based on laboratory test work performed at the Minerals Research Testing Laboratory of ASARCO. Since the concentrator is located at an elevation of 11,000 ft, cold weather was a major factor in design considerations. The original capacity was designed as 700 tpd but for various reasons an ultimate capacity of 1,000 tpd was desired. This necessitated special consideration in the design of several areas, particularly the grinding circuit. The grinding circuit chosen was a single 9 X 12 ball mill operating in closed circuit with one 20-in. cyclone. The ball mill will operate at low speed and as an overflow type originally. The mill can be speeded up and converted to grate type for handling the larger tonnage when required. Thickeners and filters were oversized and space was left for additional flotation cells in order to handle the increased tonnage in these areas. Pumps were sized so that they could handle the increased tonnage by increasing their speed. Construction began in May 1970; the Black Cloud concentrator went on-stream in April 1791.

Jan 1, 1974

By Daniel Martin

THE dendritic pattern of steels shown by deep etching is used exten-sively as a guide in the inspection and control of the great majority of steels used in ordnance construction and for many applications in indus-try. The value of macroexamination lies in the fact that it enables a qualified observer to make deductions concerning the general quality of relatively large pieces of metal. Not the least of these general character-istics is the nature and extent of the dendritic segregation in the steel, either in the cast condition or after mechanical or thermal treatments. PREVIOUS WORK Detailed methods for macroetching were outlined by Yatsevitch1 and have been standardized by the American Society for Testing Materials. A comprehensive study of the occurrence, origin, and the chemical and crystalline nature of the dendritic structure was given by Keshian.2 The marked persistence of dendritic segregation in nickel steels is fully recognized and has been discussed by Sauveur and Reed' and by others. Very little, however, has been written on the effect of the various elements on the macrostructure of steels, and the purpose of this report is to submit evidence concerning the influence of chromium, nickel and molybdenum on the macrostructure of some 4 by 4-in. ingots cast and treated under closely controlled conditions.

Jan 1, 1939

By R. S. Archer

BERYLLIUM has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it, is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to the strength and corrosion resistance of the aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a pound if the metal were produced on a large scale. It seemed, therefore, that low-beryllium alloys offered the greater commercial possibilities except for very special purposes. It was partly for this reason that in the present work emphasis has been placed on beryllium alloys of low beryllium content.

Jan 1, 1928

The War Department is appealing to skilled workmen and scientifically or technically trained men to enlist in any one of a large number of engineering troops needed for immediate action in France. Any registrant under the selective service law, who has not actually been called to service, may be immediately inducted into an engineer organization at his own request. Application for induction should be made to the Chief of Engineers, giving a complete statement of the applicant's qualifications. Any man who is physically qualified, between the ages of 18 and 21, or between 31 and 40, may voluntarily enlist for an engineer organization, provided he proves to the recruiting officer that he is experienced or skilled in any engineering trade, or is a handy main who is' especially suited for engineering work. There are about 600 recruiting stations in the United States, and an officer at any one of these will enlist a candidate for an engineer organization if he is suitable. Enlistment is in the grade of private. Subsequent promotion to the rank of non-commissioned officer is secured by merit. It is intended to fill many of the vacancies which will occur from time to time among the commissioned officers by selection from the ranks. A few of the special services, of most interest to mining and metallurgical workmen, urgently needed by the army, are as follows: Crane Operating and Maintenance Regiments; Depot Detachments; Electrical and Mechanical Regiments; General Construction Battalions; Mining Regiments; Quarry Regiments; Battalions for the construction, maintenance, and operation of railways; Road Building Battalions; Sapper Regiments; Supply and Shop Battalions; Surveying, Ranging and Map Reproduction Regiments; Water Supply Companies; and many others. All of these organizations will be assigned to such duties as competent

Jan 4, 1918

By B. D. Cullity

INTRODUCTION THIS investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy-the thermoelectric efficiency-has been discussed by Telkes1 in a recent review of the subject. She gives the thermoelectric efficiency as: [ ] For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of properties. BISMUTH-SELENIUM ALLOYS Work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson,2 who gives the diagram reproduced in Fig I. There are two intermediate phases in this system, BiSe and Bi2Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedral crystal

Jan 1, 1948

By R. L. Fleischer

IN 1925 a criterion for localized deformation in a single crystal was derived by Taylor and Elam.' They noted that for a single active slip plane the slip plane area is constant, but the direction of the stress with respect to the slip direction changes during deformation so that, when the increase in stress due to this rotation is large enough relative to the work hardening, instability occurs. (By instability is meant continued slip on the active slip plane.) The instability criterion may be written t>dt/d?/m tan2? [1] where t and ? are resolved shear stress and strain, m the Schmid factor for resolving shear stress, and ? is the angle between the slip direction and the axis of tension. The formula points out that regardless of the atomic mechanism involved, for large flow stresses and low work hardening rates, slip on a single plane—once started—should continue. The case of alloying provides a direct possibility of adjusting the parameters in Eq. [I]: As an alloying element is added to a pure metal, the flow stress is raised and the work hardening in easy glide may be either decreased2 or unaltered.3 Since flow stresses in easy glide may rise to the kg/mm2 range for alloy crystals while easy glide slopes may be less than % kg/mm2, 2 it is possible for the inequality to be satisfied. Indeed Garstone and Honeycombe3 report that slip becomes coarser with increasing stress in the easy glide range, where the flow stress would be increasing and the slope would be essentially constant. Another case where high flow stresses and low hardening rates accompany coarse slip is that of quench hardening.4 Maddin and Cottrell report that quenched aluminum crystals display slip markings resembling those of a brass. A similar effect has been observed after irradiation.'

Jan 1, 1960

By J. A. Herbst, K. Rajamani, Y. C. Lo

In spite of potential theoretical and economic advantages of large-diameter ball mills, many manufacturers elect not to build them owing to what is perceived as an excessively large design risk. This is because traditional predictions for mill scaleup to large diameters are not always accurate. Alternative methods of analysis and scale-up are required. Recent studies have shown that detailed population balance models which account for important grinding subprocesses (grinding kinetics, material transport, and classification) are capable of predicting the performance of small- and intermediate-diameter mills (up to 4.3 m, or 14 ft) from small-scale batch tests. These same models are used in the current study to predict the performance of a "borderline "large ball mill (4.7 x 5.5 m, or 15 x 18 ft) at Asarco's Sacaton operation, a ball mill (5 x 5.8 m, or 16.4 x 19 ft) at Kennecott's Chino operation, and one of the world's largest ball mills (5.5 x 6.4 m, or 18 x 21 ft) at Cities Service Pinto Valley operation. Model parameters required for scale-up have been estimated in a 380-mm-diam (15-in.-diam) batch mill. Predictions are compared with the results of detailed plant sampling in the three plants. For the Sacaton and Chino operations, the error of the predictions was found to be less than 2.5%, while the corresponding error for the Pinto Valley operation was less than 2.7%. It is concluded that proper representation of the major subprocesses of grinding in the model equations is the key to achieving accurate scale-up. Of special importance is the need to account for the size distribution of the grinding media and the influence of the size distribution environment in the mill on grinding kinetics.

Jan 1, 1986

By William C. Maurer

A survey of 25 novel drills has shown that spark drills have potential for drilling oil wells and blastholes at higher rates than rotary drills. Available laboratory and field data were extrapolated to drilling rates of 70 to 280 fph for full-scale spark drills. Most of the data used in these extrapolations were from small-scale laboratory tests at atmospheric pressure. Accurate extrapolation of the small-scale spark drill tests to full-scale field drills was complicated by the fact that the effect of fluid pressure in the well bore and the effect of spark size were not known. In order to answer these questions and to more accurately evaluate the potential of spark drills for drilling blastholes and oil wells economically, a high-voltage spark discharge system was assembled. This equipment produced powerful sparks (10,000 joules) equivalent to those that would be used on a 100-kw full-scale field drill. These sparks are 100 times more powerful than those previously used on spark drills, thus eliminating extrapolation of the spark size. In addition, a pressure chamber was modified to enable using these sparks to produce craters in rocks at fluid pressures up to 15,000 psi, thus eliminating extrapolation from atmospheric pressure to the high pressure existing in deep oil wells. These tests have provided considerable information for more accurately evaluating spark drills for oil-field drilling. MECHANISM AND THEORY OF SPARK DRILLING Spark-Drilling Mechanism When a high-voltage capacitor is discharged across two electrodes, the dissipated energy produces a high-temperature, high-pressure plasma for a few µsec. When these sparks are discharged in air, they undergo considerable expansion (Fig. 1) and produce low-pressure pulses (103-

Jan 1, 1970

By John Sullivan

Resources for Freedom, a report by the President's Materials Policy Commission, commonly termed either the Paley report, after its chairman, or the PMPC report, was issued in June 1952. The data collecting and assembly work for its preparation were done in 1951. The statistical base in most cases was 1950. It reviewed our economy and predicted what it will be in 1975.* The bases for the predictions were given. Consideration was given not only to statistical data and trends but also to technological changes taking place and likely to take place in the ensuing 25 years that will affect our economy. The supply of raw materials was studied and predictions made as to the availability of supply and the sources in 1975. One of the industries covered was iron and steel. For the most part the report did not attempt to provide a curve showing annual growth for any industry or commodity. It contrasted 1950 with the probable status in 1975. Interpolation between these dates is difficult and the Commission did not intend that it be used for short interim intervals. It is possible in 1958 to show the actual changes from 1950. The magnitude of the changes illustrates the agreement with some interpolation of the Paley report. Statistical comparisons can be general only because the Commission did not postulate a linear change. A study of the iron and steel industry will show if the general predictions have been realized or if gross errors were made. This paper is concerned with such an analysis. It is concerned with the production and consumption of crude, not fabricated products. It attempts to bring various facets of technical and statistical information on the industry up to date.

Jan 8, 1959

By C. A. Heiland

For a long time it has been known that it is possible to deduce conclusions about the physical constitution of the interior of the earth from the records of natural earthquakes obtained by stationary seismographs. In view of this fact it is surprising how late, relatively speaking, geologic prospecting by seismic methods has been taken up, although the first suggestion was made 40 years ago—that travel-time curves of artificial explosions might be used for the study of the change of the velocity of seismic waves as depth. Further suggestions of practical applications of artificial explosions for geologic purposes were made by Belar12 by von dem Borne,3 by Benndorf and by Galitzin,5 but it was not .until 1919 that Mintrop obtained a patent on the seismic prospecting method which he has applied commercially on a large scale ever since. Dr. Mintrop came to this country with his method at about 1923. Since that time, several American oil companies have developed seismographs of the mechanical type for the vertical component similar to that of Mintrop's (Humble Oil Co., Dr. Ricker). Other consulting geophysical companies designed other types of seismic devices, the simplest of them for the recording of the first impulse being the geophone (McCol-lum Geophone Co.). The galvanometric recording method as first proposed by Galitzin is being used (Geophysical Research Corpn.?) and use is being made even of the piezoelectric properties of crystals for portable seismographs (F. Rieber). There is such an enormous variety of all kinds of portable seismographs, vibrographs, accelerographs, etc., that it is difficult to decide just what kind is preferable. Unfortunately, nothing has been published as yet about American designs of portable seismographs, except the Wood-Anderson torsion-seismometer. After Mintrop's design of portable seismographs, other constructions were made

Jan 1, 1929

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.' In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By E. K. C. Williams, Nathaniel Arbiter

INTRODUCTION The surface processes involved in preparing ores for flotation and for operations depending on their flocculation/dispersion characteristics * vary widely in agitation dependence. Most of the reagents used for these purposes are added to grinding circuits, pump sumps, launders, or directly to flotation cells with the turbulent flow conditions usually adequate both for mixing reagents and for surface reactions without special conditioners. However, some reagent systems do require specific control of agitation intensities and reaction times, the more important of these being the following: 1. Activation of ZnS with CuSO4. With the usual conditions pH about 10, with collector added with the CuSO4, Cu 2+ is almost completely precipitated as basic compounds and as collector salt. As a result the levels of reagent in solution are extremely low which probably accounts for the need for separate conditioning. The agitation intensities are at about the 0.01 HP/ton level.** 2. Flocculation with natural or synthetic polymers. In this case the agitation problem is two-fold; first, to insure adequate initial mixing of the viscous stock solution of the

Jan 1, 1980