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By M. B. Bever, J. E. Reynolds

IN several alloys of iron, copper, and lithium as well as in some pure metals, martensite formed on cooling reverts to the parent phase upon heating to a temperature below the equilibrium temperature at which the parent phase becomes stable.' These martensitic transformations, therefore, are thermally reversible, although appreciable hysteresis may be involved. The martensitic reaction has long been

Jan 1, 1953

By Robert M. Rudio

Montana is leading the way in the field of mined-land reclamation with new laws and new ideas. The Montana Department of State Lands is combining new legislation and practical application techniques to all mining operations in the state. Road building, stream relocations, or settling systems can be designed to meet the environmental problems. Mineral exploration now requires a new and closer look at drill site locations, road gradients, and exploration tools. The problems and costs of land rehabilitation must be thoroughly understood by the exploration geologist in order to satisfactorily conduct exploration in Montana.

Jan 1, 1975

By Francis Freeland

An examination of accessible English literature shows that but small space has been allotted to the determination of faults ; most suggestions being confined to Schmidt's rule of the downthrow on the hanging-wall of the fault, or the coal-miner's rule of the obtuse angle. Von Carnall's modification of Schmidt's rule is sometimes given without the important exception, and Zimmermann's rule is

Jan 1, 1893

By Henry Lewelling

An experimental investigation of the relative effectiveness of standard bullets and "shaped charges" in perforating dense, hard formations is reported. A method is described which simulates the conditions under which a shot is normally fired. Results are evaluated on the basis of depth of penetration, extent 01 Fracturing. extent and nature of formation damage, and other physical characteristics. INTRODUCTION A study was made of the relative merits of bullets and "shaped charges'' as applied to well completions in hard, dense formations such as those encountered in the Permian Basin. The planning of the laboratory program stipulated that core samples should be prepared and mounted in such a way that perforation shots of either kind"" could be fired into them, keeping the factors pertinent to good shooting practice similar to what they would be in a well. The shooting was done in a buried tank. with the sample and shooting equipment covered with water. The depth of water was calculated to he sufficient to simulate the inertial effects of well fluids for the duration of an explosion (a few micro-seconds). Flow measurements were attempted on the specimens after perforation. Due to the lack of uniformity of the limestone, shale breaks. etc., these measurements proved to be of little value to the study. The mounting materials were removed. so that the character of the penetration. fracturing, etc., could be observed. METHOD Laboratory samples were selected from the hard. dolomitic sand cores from Block 31 Field. Core pieces having a 3 3/4 in. diameter and a useful length of 10 to 12 in. were used. Selection was aimed at those pieces having a minimum of shale streaks and other irregularities. The ends were cut off square Manuscript received in the Petroleum Branch office June 28, 1951. Paper presented at the Petroleum Branch Fall Meeting in Oklahoma City, Okla., Oct. 3-5, 1951. with the diamond saw. Prior to lbeing mounted. the cores were soaked in water to prevent them from absorbing water out of the wet concrete, thus weakening it. A set of steel capsules was fabricated for holding the core Samples. Seven-in. casing was cut in two-ft lengths. of which one end was closed by "orange-peeling" and welding, and the other was threaded to accept a standard bull plug. The bull plugs were fitted with copper tube connections .so that pressure could be applied when the capsules were made up. The cores were mounted in the capsules by means of wire centralizers whose function was to hold the Core in proper position while concrete was poured and set. A special aggregate was prepared wing a graded sand and gravel mixture

Jan 1, 1952

By R. E. Cech, J. H. Hollomon

KURDJUMOV and Maksimova reported experiments with manganese steels and high carbon steels' and with an Fe-Ni-Mn alloy' in which mar-tensite was formed isothermally over a range of temperatures. They found in some cases that mar-tensite formation could be suppressed by rapid quenching to liquid nitrogen temperature. From their microstructural observations of martensite formed isothermally, they concluded that the rate controlling step is nucleation rather than growth. Kulin and Cohen,3 in an attempt to reproduce these experiments, found that with a steel having the same composition as that reported by Kurd-jumov and Maksimova, the transformation to martensite was essentially complete above the temperature range of Kurdjumov and Maksimova's isotherms. The possible reasons for this disagreement were not considered. Recent papers by Das Gupta and Lement4 and Kulin and Speich5 report the formation of isothermal martensite in a high chromium steel and in an Fe-Cr-Ni alloy, but neither paper can be considered a verification of the original Kurdjumov and Maksimova results. Further, in neither case were the authors able to suppress the formation of martensite entirely. Because of the important bearing the Kurdjumov and Maksimova results have to an understanding of the mechanism of martensite reactions it was felt that an experimental investigation directly concerned with checking the validity of their results was in order. This paper describes the results obtained on the isothermal transformation over the temperature range from —79" to —196°C of an alloy of iron, nickel, and manganese. Experimental Apparatus A 15 lb heat of an alloy containing 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn was melted by induction and cast under argon. The ingot was forged to 1-in. bar and a portion rolled to 1/16x1 1/2-in. strip. This strip was pack-homogenized 300 hr at 1100" in a helium-filled sealed iron tube. The composition after homogenization was 73.2 pct Fe, 22.94 pct Ni, 3.73 pct Mn, 0.05 pct C, and 0.015 pct N. The strips were cut to 1/2-in. width for dilatometer and metal-lographic specimens. Only the center portion of the 11/2-in. strip was used in the present investigation. The dilatometer employed was similar in design to one described by Flinn, Cook, and Fellows." A concentric fused auartz rod and tube assembly with hooks for holding the specimen was mounted so as to transmit the specimen dilation to a 1/10,000 in., 1/10 in. travel dial gage. The dilatometer proper was mounted by means of extension arms to a counterweighted sliding member on a vertical standard. This method of mounting permitted rapid transfer of the dilatometer from the austenitizing furnace to the quenching bath and low temperature chamber. A small electrical vibrator on the dilatometer kept frictional effects of the quartz members at a minimum. The austenitizing unit was a vertical, molybdenum-wound, hydrogen atmosphere furnace maintained at a constant temperature ±3°C by means of constant power input. A 12-in. stainless steel jacketed copper liner having 1/2-in wall thickness acted to equalize the temperature in the hot zone of the furnace. This liner, closed at the bottom end and open at the top to permit entrance of the dilatometer and specimen, was kept filled with dry nitrogen gas. A chromel-alumel thermocouple was placed inside the tube to determine the temperature. The 4-in. dilatometer specimens in the chamber varied less than 1/2° across the specimen length except for a 1 1/20 drop at the end nearest the open end of the furnace. The low temperature isothermal holding bath was a double Dewar arrangement similar to one described by Turnbull7. The outer bath was filled with a refrigerant at a temperature lower than the desired holding temperature. The inner bath was filled with Freon "11" or "12" or a mixture of both, depending upon the holding temperature. This inner bath which tended to be cooled by the outer bath was kept at a constant temperature by introducing a small amount of heat with a manually controlled electric heater. Stirring was accomplished by bubbling dry air through the bath. A Leeds and North-rup type K potentiometer was used to measure the inner bath temperature as indicated by a five element copper-constantan thermopile. The bath temperature was maintained within ±0.2°C of the desired temperature by occasionally adjusting the heater current so as to keep the Leeds and Northrup galvanometer at zero deflection with a constant setting of the potentiometer. Isothermal tests were usually continued for 300 to 400 min and another reading made at approximately 1000 min if the bath, unattended overnight, had not deviated in temperature more than 5°C. Transformation curves are drawn dashed (Fig. 1) through the time region where temperature was not controlled precisely. Experimental Procedure Dilatometer specimens of 1/2x1/16-in. strip were cut to 41/2-in. length and holes were drilled for the quartz hooks with proper spacing to give a 4-in. measured length. A thermocouple consisting of 0.012-in. diameter chrome1 and alumel wires was spot welded to the specimen and threaded between the dilatometer rods to binding posts near the dial

Jan 1, 1954

Jan 1, 1958

By C. H. Mathewson

Discussion of the paper of C. H. MATHEWSON and ARTHUR PHILLIPS, presented at the New York meeting, February, 1916, and printed in Bulletin No. 109, January, 1916, pp. 1 to 50. ZAY JEFFRIES, Cleveland, Ohio (communication to the Secretary*).¬The authors are to be congratulated for this interesting and valuable contribution. The paper as a whole shows very careful experimentation coupled with rare judgment in drawing conclusions. I have been working along similar lines for the last two years with other metals and alloys. In a short conversation with Dr. Mathewson about July 1, 1915, he mentioned the fact that different degrees of cold work greatly affect the temperature of recrystallization on annealing, Later I determined the recrystallization temperatures of iron, mild steel, and copper, with different degrees of cold work and found that the greater the degree of cold work, the lower the temperature of recrystallization on annealing. In the course of these experiments, I conceived practically the same ideas regarding the reasons for recrystallization as those advanced in the article under discussion. After a metal has been reduced by cold work to about one-fourth of its original area, the differences in orientation of different parts of a given grain can be seen plainly at a magnification of about 1,000 diameters. It is interesting to note that in Fig. A, Plate I, the lines of deformation are not parallel. For example,. in the large grain at the lower left corner of the micrograph, if the lines of deformation about 3g in. from the left edge are continued in a straight line, this line will intersect a straight line drawn as a continuation of the lines of deformation on the extreme right of the grain, at an angle of about 20°. Similarly, if the lines of deformation at the extremities of the large grain in the right central portion of the micrograph are extended, the lines intersect at an angle of about 35°. The individual lines of deformation are not straight. In some of these the parts of the broken lines intersect at angles as great as 15°.

Jan 5, 1916

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

The Sixty-fifth Congress was a "War Congress." Perhaps nothing else than war work should have been expected of it, but it had time and opportunity to do much more. Engineers have good reason for sorrow over the engineering legislation that died merely because there was no opportunity for a vote. The mineral resources of the public lands of the United States are, except the precious metals, locked away from development. For more than eight years there has been an attempt by both the executive and legislative departments of the nation to secure legislation which, under proper conditions and without detriment to the public interest, will open up these lands for development. After eight years of study, argument, conciliation, and compromise, Congress agreed in conference of the two Houses upon a measure satisfactory to it and to the Executive Department and the final draft was passed by the House of Representatives, but in the Senate it was talked to death by Senator LaFollette of Wisconsin. Some of its proponents plan to, reintroduce the bill identically as agreed to in conference into the 66th Congress, where it is hoped that by reason of its peculiar fate in the 65th Congress it will be regarded in the nature of unfinished business and thus receive early consideration and passage.

Jan 5, 1919

By Vernon Taylor

CANADA'S oil production is obtained almost entirely from the Turner Valley gas and oil field, in the Province of Alberta. This field, about 30 miles southwest of the city of Calgary and approximately 115 miles north of the United States border, supplied 92 per cent of production in Canada during 1937. In 1938 considerable development took place in this field and total production for the year amounted to 6,688,716 bbl., an increase of 3,922,146 bbl. over the production in 1937, which increased the percentage of production to approximately 97 per cent of Canada's total. In the British Empire, Canada's production is thus comparable to that of Bahrein Island and Burma, each of which produced approxi-mately 7,800,000 bbl. in 1937, being second to Trinidad's production of 15,500,000 bbl. The total production of the British Empire in that year amounted to 2.07 per cent of the world's total. HISTORY Development of the Turner Valley field commenced in 1913, when a well was started near a gas seepage on the banks of the South Fork of Sheep River in the central part of the Valley. This well found small quantities of a light crude oil in beds of Upper Cretaceous age and pre-cipitated a wild boom in 1913-1914 which ended with the beginning of the Great War in 1914. A small amount of drilling was done in the years from 1914 to 1922 and a few wells found small crude-oil production in the upper sands. In 1922 a few wells were started, including the Royalite Oil Company's No. 4 well (R, Fig. 1), which became the discovery well of naphtha pro-duction from the Paleozoic limestone. In October 1924, this well was completed at a depth of 3740 ft., being approximately 300 ft, in the lime-stone, with an initial flow of 600 bbl. of 72° A.P.I. gravity naphtha and 20,000 M cu. ft. of gas per day. Intense activity was not started until the latter part of 1928, when the Okalta No. 1 well (Q, Fig. 1) was drilled, with an initial production of 500 bbl. of naphtha per day. This well was only 1 ¼ miles from Royalite No. 4, but it was approximately 1300 ft.

Jan 1, 1939

By L. C. Uren

THE resistance to flow of mixtures of gas and oil in passing up through the flow tubing of oil wells operated by gas-lift or by natural flow is a factor in oil-recovery technic that has received but little attention. Yet accurate design of a tubing installation for a particular set of conditions, where operation is by either of 'these methods, is impossible without quantitative data on the pressure loss suffered by the oil-gas mixture in its passage through the well tubing to the surface. Because of lack of such information, petroleum production technologists have been compelled to approach this problem by "cut-and-try" methods, which, doubtless in many cases, has resulted in the installation and use of tubing too large or too small for most efficient utilization of the expansive force of the gas used in lifting the oil. Impressed with the necessity for information of this character, the authors have conducted a series of tests with large-scale apparatus in the petroleum engineering laboratories of the University of California, designed to be productive of data that would afford a means of attacking the problem of flow-tubing design on a more scientific basis.

Jan 1, 1929

By M. C. Fuerstenau, W. F. Cummins

The flotation response of quartz in the presence of calcium chloride and various fatty acids is presented. Flotation is not effected with lauric acid until calcium laurate is precipitated in solution, while flotation is obtained with the 9, 10, and 11-carbon members before precipitation of the calcium carboxylate. The active species responsible for flotation is suggested to be a basic aqueous complex, e.g. Ca(OH) (RCOO) (aq), and a possible mechanism of adsorption is given. Most of the previous work on activation in non-metallic flotation systems has involved the use of high molecular weight collectors, such as oleic acid or alkyl aryl Sulfonate.1-7 In these studies the levels of addition of collector and activator required for flotation were much above the concentrations necessary for precipitation of the metal-collector salt. In fact, Clemmer, Clemmons, Rampacek, Williams, and Stacy1 have stated, "Our experiments on a variety of materials have demonstrated that the metal salts which react with anionic collecting agents, as soaps and alkyl sulfates, to form relatively insoluble compounds may be employed as activating agents provided an optimum quantity is used at a proper pH." On the other hand, Gaudin and chang8 obtained flotation with additions of barium and lauric acid below the level required for barium lautate precipitation.

Jan 1, 1968

By Joseph Kuti

Longwall mining is the term used for the underground extraction of a wide and deep panel of coal. Such a panel may be blocked out by one or more entries on either side ("head" and "tail") of a longwall face. If all the entries are pre-driven, the panel extraction is termed longwall retreat mining. With one exception, all the longwall faces in the United States are of this type.1 Prior to the general decline in the rates of production with Continuous Miners, the development of the multiple entries generally kept ahead of the longwall extraction rate. This is no longer the case: longwall extraction rates far exceed the rate of development. In addition to this problem, in newly established mines, the development of a haulage and bleeder system based on multiple entries results in a lead-time of three years or more before longwall mining can be applied.

Jan 11, 1979

By C. L. Meyers, J. L. Lytton, T. E. Tietz

The recovery of tensile flow stress of 99.995 pct A1 under conditions of elastic strain and plastic creep straining was investigated using a fractional recovery parameter. Tensile straining was conducted at room temperature to a true strain of 0.10, and recovery treatments were made under stress in the temperature range from 80° to 198°C. Whereas elastic strains had no appreciable influence on flow-stress recovery, plastic creep straining was found to accelerate the recovery process. Although higher creep stresses gave greater recovery for a given time and temperature, it was found that lower stresses produced greater recovevy at equal ALTHOUGH many studies have been made to date on the recovery of metals from the cold-worked creep strains above about 0.005. This effect was attributed to the coarser, and therefore weaker, substructure developed during creep at the lower stresses. The activation energy for recovery during creep straining at 2075 psi between 160" and 198°C was found to be 25,000 cal per mole. This value was not significantly greater than the value previously obtained for no-load recovery. The activation energy for creep at 2075 psi between 160" and 198°C was 34,000 cal per mole, a value significantly greater than that for recovery under the same conditions. state, little is known concerning some important aspects of recovery behavior. One such area is the effect concurrent strain has on the recovery process. Since metals in structural applications at high temperatures are under stress, the possible effects of the resulting elastic and plastic strain on recovery may be of significant importance.

Jan 1, 1962

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By W. Luyken

A NUMBER of articles have been published, notably those by R. S. Handy, R. T. Hancock and A. P. Watt in Engineering and Mining Journal, dealing with the calculations involved in ore dressing.. These publications demonstrate both, the importance of the subject and the lack of success in developing a generally recognized method for comparing enrichment effects. Considering that we may wish -to compare enrichment results on similar or dissimilar ores, that we may desire to make the comparison on the basis of either the absolute or the economical efficiency, and that the number of factors upon which the result depends is large, the question arises whether it is possible to set up a positive method for such calculations. In the following pages it is our aim to show that a sure, complete and successful way to overcome existing difficulties has been found. GRAPHICAL ANALYSIS OF ORE-DRESSING PROCESSES The following is from Truscott's Text Book of Ore Dressing (London, 1923) x = assay of ore treated (feed). y = assay value of the concentrate. z = assay value of the tailing. a = weight of feed. b = weight of concentrate. c = weight of tailing. C = fractional concentration = b/a= x-z/y-z (1) K = ratio of concentration = 1/C = a/b =y-z/x-z (2) R = fractional recovery = yb/xa = Cy/x. (3) 100R = percentage recovery. Copt = theoretically best concentration. 100 - Copt = waste in the feed.

Jan 1, 1929

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By C. R. Kuzell

INTRODUCTION KNOWLEDGE of the thermal capacity of gases is of great importance in making metallurgical calculations. The metallurgist is, frequently called upon to investigate and determine furnace efficiencies in which the heat carried into or out of the furnace by gases is a large item in the heat balance. Not only do such problems present themselves in the determination of furnace efficiency, but also in the study of the application of heat is accessory apparatus, such as stoves, regenerators, waste-heat boilers, driers,.etc. The thermal effect of the use of excess air in the combustion of fuel, the theoretical temperatures of combustion, the quantity of heat in hot blast at various temperatures, the effect of hot blast on furnace temperatures, are a few more examples of frequently occurring calorific problems involving gases. So many are the applications of the data on the heat capacity of gases that the subject merits careful study. The heat in a gas maybe due to its heat of combustion, if it is a combustible gas, and to its temperature. The latter is called its sensible heat and is the heat absorbed or evolved by a gas as its temperature is raised or lowered. The heat of combustion of gases is well established and is commonly known. The values can be found in almost any mcdern treatise on metallurgy. The sensible heat of gases has not been so well established because it is in most cases a function of the temperature, and the values of specific heats of gases over a wide range of temperatures have only recently been determined. It is the purpose of this paper to deal with the sensible heat of gases.

Jan 8, 1914

By Reginald S. Dean

THE commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese. A method for the production of electrolytic manganese was developed by the Bureau of Mines in 1936 and commercial production was begun in 1938. At the present time (June 1951), production is about 12 tons per day but appears likely to be substantially increased. Electrolytic manganese is deposited from an aqueous electrolyte containing manganese and ammonium sulphates and is marketed as cathode fragments about 1/8 in. thick. The impurities in its composition are as follows: iron, 0.0015 pct; copper, 0.001; arsenic, 0.0005; cobalt, 0.0025; lead, 0.0025; molybdenum, 0.001; sulfide sulfur, 0.017; sulfate sulfur, 0.014; insoluble, 0.002; carbon, 0.002; hydrogen, 0.015. These figures are from Bulletin 463, U. S. Bureau of Mines. From an alloying standpoint, the most important impurity is hydrogen. This can be removed by heating; 95 pct of the hydrogen can be removed in this way without introducing significant amounts of oxygen or nitrogen. Much of the commercial electrolytic manganese used in alloys is dehydrogenited by the producer, since the amount

Jan 1, 1953

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.' It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)'/2af.]' [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954