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By William B. Heroy

During 1932 no important changes occurred in the position of Africa as a producer of petroleum. The progress of development and production in each of the areas of interest is described below. Egypt The producing fields of Egypt are Hurghada and Gemsa, located on the west short of the Red Sea, and Abu Durba in the Sinai Peninsula. Most of the production is obtained from the Hurghada field, chiefly from beds of Cretaceous age. To the end of 1930 the Hurghada field had produced 2,831,751 tons of petroleum. The Gemsa field, discovered in 1909, reached its peak of production in 1914, when 88,000 tons were produced. Of late years the production has greatly declined. Total production of the field to the end of 1930 is 182,870 tons. The total production of Abu Durba to the end of 1930 is 7069 tons. The production of Egypt for recent years is as follows: 1928, 269,324 tons; 1929, 271,520; 1930, 281,997 (1,996,000 bbl.); 1931, 288,260 (2,038,000 bbl.); 1932, 253,182 (approximately 1,790,000 bbl.). Mozambique The operations of Inyaminga Petroleum Ltd., which was engaged in drilling in the colony, have been suspended. Angola Drilling operations in this colony, conducted by Companhia de Petroleo de Angola under a concession from the Portuguese Government, were continued. A test well drilled at Cacoba, about 60 miles southeast of Luanda, to a depth of 5651 ft. was not a commercial producer. A second well was being drilled in the vicinity at the end of 1932. Morocco Until last year the search for petroleum in Morocco was in the hands of several private companies but during 1932 the National Office of Liquid Fuels of the French Government took an active interest in the develop-

Jan 1, 1933

By Robert L. Davidoff, Rodney D. Rosenkranz

In order to determine copper resource data and production costs for major market economy mines and deposits, the Bureau of Mines has performed detailed engineering and economic analyses on 271 of the world's most significant copper deposits. At the demonstrated resource level, copper potentially recoverable from these deposits is estimated to be 325 million metric tons, 180 million tons of which would be from Pacific Rim countries. Chile has the largest known copper resources of any country and accounts for nearly 45 percent of the copper avail- able from Pacific Rim countries. At $1.00 per pound, in January 1981 dollars, an estimated 80 million metric tons of copper are potentially economically recoverable from Pacific Rim deposits. At this same price, analyses indicate that these deposits could economically produce about 2 million metric tons of copper per year. Sensitivity analyses reveal that if operating costs were to decrease 25 percent, with copper at a price of $1.00 per pound, total copper economically recoverable from Pacific Rim countries could increase by about 10 percent; a 25 percent increase in operating costs could lower economically recoverable copper by 50 percent. Analyses also indicate that byproduct prices are important. If byproduct revenues increased 25 percent, at a copper price of $1.00 per pound, an additional 2 million metric tons of copper could be recovered; if byproduct revenues decrease 25 percent, about 5 million metric tons less of copper metal would be available. Since the January 1981 date of this study, inflation and decreases in copper and byproduct prices have greatly affected the profitability of the world copper industry. Many producing mines have curtailed or suspended production, and development of many non- producing deposits has been postponed.

Jan 1, 1982

By W. J. Taylor

FURNACE-MEN who have not taken advantage of the use of dynamite in certain blast-furnace troubles, as explained by Mr. Witherbee in his valuable papers read before the Institute some years since, cannot appreciate the quick relief and great advantage that may be derived at times from its judicious employment. Before giving my experience in the use of high explosives in blastfurnace troubles of certain kinds, I will record a method I have used with marked success in " blowing down." Had I not understood, however, the use of powder, I would have " salamandered " effectually the first time I tried it. Early in my straight-furnace experiments, last summer, at the Chester, N. J., Furnace, I wanted to blow down to within 3 or 4 feet of the tuyeres. To do this with a down-comer not lined, and without putting in any limestone to keep the gases cool enough to do no harm, was not an easy task. We could keep the bell and hopper cool by filling them with water, say 12 inches deep; but before we got the stock down 15 or 20 feet the pyrometer in the gas-flue on top mas up to 1300°, and the clowncomer was red-hot, with the heat still rising. In this emergency my assistant, Mr. N. M. Langdon, urged the trial of a plan lie had often advocated, viz., the introduction of water in some way under the bell in the proper quantity, in order that its evaporation might absorb and reduce the heat of the escaping gases to a point where it would not do any harm. He thought the bell

Jan 1, 1885

By R. J. Wygal, J. Naar

An equation for three-phase (water, oil, gas) imbibition oil permeability is developed, assuming the water to be the dominant wetting fluid. Oil isoperms are obtained for consolidated sandstones characterized by 1/pc2 = CS*. The evolution of an oil-gas system imbibing water from Swi to(Sw,imb )max is shown to proceed along a line of constant oil saturation with increasing oil permeability and decreasing gas saturation. When the gas satuation cannot be reduced further, the system evolves along a line of constant Sg with decreasing oil saturation and permeability. The initial gas saturation is shown to reduce markedly the effect of complete wetting by either oil or water on flow performance. INTRODUCTION Imbibition oil isoperms are required for performance prediction when a well is producing water, oil and gas. This situation occurs in multiphase displacements such as underground combustion, steam injection and the water flooding of highly depleted reservoirs. In a recent paper,1 a model was presented for the prediction of two-phase imbibition characteristics. This paper extends the imbibition model to the case of three phases by assuming that the water is the dominant wetting fluid. The following results were obtained from the model: (1) an analytical expression of oil isoperms; (2) oil isoperrns as functions of reduced water, oil and gas saturations, valid for all sandstones having a capillary pressure curve which can be approximated by 1/PC = CS*; and (3) evaluation of the three-phase flow performance as dictated by complete wetting by either oil or water. The agreement between predicted and observed oil recovery in the presence of a gas phase, reported in Ref. 1, is a partial support for the present development. However, experimental data are not available at this time to check fully the model predictions. Perhaps this paper will stimulate the collection of such data. The imbibition model of a porous medium has been described previously, and the reader is referred to the paper of Naar and Henderson1 for details. In brief, the model is formed by the random interconnection of straight capillaries, with a provision for the blocking of the non-wetting phase by the invading wetting fluid. The following expressions were derived from the model. 1. The amount of oil blocked by the invading water is

By L. Zwell, H. A. Wriedt

In describing their procedure for measuring the lattice parameters of solid solutions, Abrahamson and Lopata report (p. 77) the final heat treatment of their alloy specimens as "700°C for 100 hr, followed by a furnace cool". The isothermal part of this treatment may be expected to precipitate solute in excess of the stable a solid-solution limit at 700°C; the subsequent slow cooling is likely to reduce the dissolved solute still further. Fig. 1 (upper) presents the data for titanium alloys so he;rt-treated and shows the lattice parameters of solid solutions containing up to 3.5 at. pct Ti; Fig. 17 (lower) shows 2 at. pct Ti as the solubility limit in a iron at 700°C. Figs. 1 and 17 are thus incompatible. The paper contains comparable incon~patibilities for zirconium alloys, for niobium alloys, and for tantalum alloys. The final heat treatment at 700°C may also be responsible for the anomalous "knee" in the lattice-parameter data for nickel alloys, Fig. 3. The "knee" composition is located near the 700°C limit of the stable a solid-solution field;37 alloys of the experimental composition range with more nickel than the "knee" composition are two-phase at 700 C and prolonged heat treatment of them at 700°C would tend to produce inhomogeneity rather than homogeneity. In Figs. 4 and 7, the composition ranges of the zirconium, hafnium, and niobium alloys examined terminate at alloy concentrations of 0.1 to 0.2 at. pct. These metals form very stable oxides and their partial removal from solid solution in iron by impurity oxygen may be expected. We believe that the authors should have reported the procedure by which they distinguished the amounts of alloying elements in solution and in oxide. The diagrams pertaining to copper in Figs. 3 and 18 (lower) are almost certainly incorrect. Three recent investigations of this system38-40 all substantially agree on the solubility of copper in a iron, finding it to be much larger than that reported by Abrahamson and Lopata. The change of the lattice parameter with composition reported by Abrahamson and Lopata is too large by a factor of three to five, as seen by comparison with the findings of other investigators.41738 Moreover, the authors violate, in Fig. 18, the accepted Fe-Cu constitution diagram37 by ignoring the eutectoid at about 850°C.

Jan 1, 1967

By J. T. Norton, A. L. Mowry

S. J. SINDEBAND*—(1) Discussing the properties of the powders used, Mr. Rostoker mentioned a silicon powder as being between 150 and 325 mesh. We always had much difficulty in measuring particle size of silicon powder by screen analysis, because of its tendency to agglomerate. I would be interested in the method used to measure these particle sizes. (2) Mr. Rostoker maintains that the measurement of magnetic properties is more accurate in determining complete homogenization of an alloy, than is the X ray diffraction technique. I wonder whether this is really true. Even when diffusion is complete, magnetic properties will change during continuation of the heat treatment, due to change in density and pore shapes, as has been demonstrated by Mr. Rostoker himself. Which effect is faster, the diffusion of the alloy components or the attainment of final density, will, in my opinion, depend very much on initial material and sintering conditions used. For magnetic applications, of course, the magnetic measurements are most suited for determining the point at which equilibrium conditions are reached. (3) I was glad to see that Mr. Rostoker had used sample sizes which are similar to those I had used previously, and I believe that ring samples of about 2 in. od will become more or less standard samples for the determination of magnetic properties of powder metallurgy products. I should like to ask how the density was changed for the samples on which the effect of porosity was investi- gated, and, further, why the sintering temperature used for this series of experiments was so low. It is somewhat surprising that a 24-hr treatment at 850°C acts so much more to spheroidize the pores than a treatment for 1 hr at 1100°C. But the effect seems to be indisputable. I have made an investigation of the influence of sintering temperature for longer times on the maximum permeabilities of iron powder compacts which was presented at the International Powder Metallurgy Conference in Graz, in 1948, and I hope that these results will be published here within a short time. The results of this investigation are confirmed by Mr. Rostoker's findings that the change of time from 1 to 24 hr changes the permeability behavior considerably in the direction as indicated by Polder and Van Santen for spheroidiza-tion of pores. I do not quite understand Mr. Rostoker's explanation of the influ-

Jan 1, 1950

By John Henry Harden

THIS shaft, located in the northern anthracite coal-field about 2300 feet southwest from the court-house at Wilkes-Barre, in the County of Luzerne, Pa., is the property of the Lehigh & Wilkes¬Barre Coal Company. The sinking and cribbing to the solid rock (see isometrical view on Plate IX) was conducted by Mr. W. W. Kenrick. Dimensions of the earthwork to the foundation of the cribbing, 51' 1/2" long, 17' 4" wide, 31' deep. Total amount of excavation in cubic yards, 998.5. Dimensions within the permanent cribbing, 45' 4" long, 11' 16" wide, 31' deep, divided into six parts by buttons 8" x 12", each division, 7' x 11’ 16". Permanent cribbing 12" x 12"; temporary cribbing 8" x 10"; backing, 3" thick ; clay puddle to ex¬clude surface water, 12" thick; conductors, 8" x 5"; lining, 1" thick from top to bottom of the shaft. In the latter part of the year 1871, Mr. H. Murray & Son contracted with the company for the continuation of the work at the rate of four hundred dollars per yard in depth, to a point 100 feet below the Hillman seam of coal ; for the succeeding 100 feet the price to be increased twenty-five dollars per yard, and so on until the bottom rock of the Baltimore seam of coal was found. The size of the shaft within the cribbing timbers is 45 feet 4 inches by 11 feet 6 inches, having six divisions of equal dimensions, 7 feet by 11 feet 6 inches, giving room for what is known as the" standard diamond" car, whose capacity when level full is 100 cubic feet, but when loaded by the miner 4 inches above the top contains 112 cubic feet.* Two divisions of this shaft are intended for hoisting coal from the Hillman seam, two from the Baltimore seam, one for ventilation, and one for pumps. The works were planned for two pairs of direct-acting, high-pres¬sure engines, twenty-four boilers, and for an estimated output of 2500 tons of coal per day from the two seams. * Size of the "standard diamond" car, 8' 10” x 4' 3" x 2’ 8” = 100.1.4; loaded 4 inches above the top, 8' 10” x 4’ 3” x 3’ “0"= 112.7.6.

Jan 1, 1877

By L. F. Stutzman, George Thodos

The friction factor plot presented by Cornell and Katz4 and developed for the flow of fluids through consolidated formations has been directly adapted for handling fluid flow problems involvitrg both linear and radial flow. In this adaptation the friction factor plot is used directly for the solution of problems and thereby eliminates the use of conventional equations which are specific to laminar (Darcy) or turbutent flow. This upproach overcomes the disadvantages inherent in the use of these conventional equations. It eliminates the necessity of checking the type of flow occurring in order to identify the specific equation which must be used. In radial flow problems, because of the increasing mass velocity of the fluids as they approach the wellbore. the type of flow may no longer remain laminar. Consequently, it is necessary to use more than one equation in a problem and to identify the range over which each equation should be applied. Finally, in practice it has been found that much of the flow of gases through consolidated media occurs in a range that is neither laminar or turbulent. For this transitional region, no convenient equations are available. The method and presented friction factor plot are appficahle to both liquids and gases. INTRODUCTION The flow of fluids through unconsolidated media in packed beds has been treated extensively by a number of investigatorsl,2,3,5,7,8 Most of these studies present friction factors as a function of modified Reynolds number similar to those developed for conventional fluid flow through pipes. These friction factor plots are presented for linear flow; however, Elenbaas and Katz have extended these concepts to apply to radial flow. All of these studies on unconsolidated materials require a knowledge of packing properties such as sphericity. porosity, and particle diameter. Sphericity and particle diameter cannot be defined at the present time for consolidated formations such as those commonly found in gas or oil reservoirs. As a result many investigators have not utilized friction factors and Reynolds number in the study of fluid flow through consolidated media. However, Cornell and Katz4 present a plot (Fig. 1) for the flow of fluids through consolidated porous media, in which the friction factor defined as: The turbulence coefficient, P, is related to the formation permeability, K, as presented in Fig. 2. Three different types of flow may exist in the flow ot

Jan 1, 1957

By Erwin S. Sperry

Brass or bronze chips, grindings, buftings, washings, and miscellaneous scrap metal sooner or later find their way into the hands of the so-called metal-smelter or " refiner," whose refining or smelting operation consists simply in melting the material, adding the requisite amounts of other metals, and then casting it in the form of ingots, which are afterwards sold

Jan 1, 1899

By H. H. Waller, D. L. Monroe, D. P. R. Smyth

ORIGINALLY slusher drift development was conventional, advancing the drift full 10x13-ft size at 6 ft per round. This proved dangerous and costly because the weak fractured rock of the orebody cannot be left raw for any length of time without its reacting with air to cause spalling. With this method of drift development ground conditions were worsened by many blasts and the length of time it was necessary for the drift to remain open. The problem was practically solved by driving 5x7-ft pilot drifts, then enlarging to 10x13-ft raw size by slashing with 50 to 60-ft diamond drill holes. Calculated explosive charges are used to avoid wall and roof shattering. Still more recently jacklegs and sectional steel replaced the diamond drills, resulting in the same work for less than half the cost, see Figs. 1 and 2. Crosscuts at right angles to the main haulage drifts, which cross through the center of the ore-body, divide the ore into 200-ft blocks. Eight slusher drifts on 50-ft centers draw from one block. The slusher floor is 11 ft above the rail, inclined at 1 pct grade, and the top is 18 ft below the undercut. The finished slusher drift is 102.5 or 120 ft long, depending on whether it is north or south of the crosscut. Drawpoints are staggered on each side at 17.5-ft centers. The completed drift is concreted and has an inclined ramp and a vent at the back. When crosscuts and gangways have been excavated and concreted and slusher stations installed, slusher drift development is carried out in 10 clear-cut stages: 1—Pilot drift is driven full length, 5x7 ft. 2—Station is excavated at half-way point in pilot drift. 3—Pilot drift is enlarged to slusher drift size by drilling. 4—Lower part of slash is blasted and mucked for floor concrete. 5—Floor is poured. 6—Inside upper half of slusher drift is blasted, mucked, and concreted. 7—Outside upper half of slusher drift is blasted, mucked, and concreted. 8—Drawpoints are excavated. 9—Drawpoints are concreted. 10—Concrete ramp and sheave protection recess are constructed at back end of slusher drift. A 5x7-ft pilot drift is driven full length on the center line of the proposed slusher drift using a jackleg and detachable bits on 7/8-in. hexagon steel. A 10-hp air-driven slusher and 36-in. scraper pull muck directly into cars in the main haulage crosscut, see Fig. 2. Operations are on a three-shift basis. One man mucks the previous round, drills, and blasts his round in a shift. Average advance is 5 ft per shift. When the pilot drift is completed, 7 ft of drift in the center section is enlarged to full raw slusher drift size of 10x13 ft, for the set-up to drill long slash holes. The pilot drift is slashed to full raw size from this station with jacklegs and tungsten carbide chisel bits on 7/8-in. sectional steel. Crews line the holes without trouble, working from controls established by the engineers, and the pattern of holes for the slash is arranged to give the least shattering effect

Jan 1, 1955

By J. E. 214-000-000-010 Warren, M. R. J. Wyllie, T. Meidav, L. Scharon, R. Uhley, A. J. deWitte

By considering the stoichiometry of the underground combustion process, an equrztion was derived relating the point velocity of the combustion front as a function of the air flux, fuel content, efficiency' of oxygen uitilization, hydrogen:carbon ratio, and ratio of carbon dioxide In carbon monoxide produced. In addition, an equation for cnlcrllating the amount of injected air necessary 10 produce the oil from I Cu. ft of reservoir space was derived. This equation has a direct bearing on evaluating compression costs for the process. Values calculated from these equations are in good agreement with experimentnlly obscrvcd values obtained from laborator) tube runs reported in the literature. The equations are also u\eful for atlcrlyzinf: experinlental data for inconsistencie.r.. I NTRODUCTION The injection of energy in the form of heat into an oil-bearing formation as a means of increasing the recovery of oil has been the subject of much discussion and experimentation as far back as 1920. The ideas have ranged from the injection of steam to the direct use of electricity as a means of getting thermal energy into a formation. However, most laboratory and field studies have been confined to the process whereby a portion of the crude in the reservoir is burned to generate the necessary heat to increase the mobility of the oil by reducing its viscosity. A recent paper by W. L. Martin, et al.', described the results of a number of laboratory experiments in which the combustion process was studied in a sandpack. Studies such as this indicate that with the temperatures involved, the oil is partially coked in this process and it is this coke which provides the fuel for combustion. The combustion of this residual coke can be analyzed theoretically by applying simple stoich-iometric principles to the combustion process. It is the purpose of this paper to compare the results reported in these experiments with those obtained from theoretical considerations. The variables studied by Martin, et al, among others, include combustion front velocity, air flux, oxygen utilization, fuel concentration, ratio of carbon dioxide and carbon monoxide in combustion gases, and the hydrogen:carbon ratio of the residual fuel. All these variables come into consideration when the stoichiometry of the combustion process is studied. The experimental conditions and results are tabulated in Tables 3 and 4 of Ref. 1. For purposes of comparison with calculated results, it was necessary to change the units of a number of the variables. UNDERGROUND COMBUSTION STOICHIOMETRY The combustion or oxidation of the carbonaceous residue or "coke" on the sand can be described in terms of the equation: where n is atomic ratio of hydrogen to carbon, m is ratio of moles of CO2 to CO produced, and CH. is taken as the unit molecular weight, realizing that actually the coke has a large range of high molecular weights. Assuming that all the fuel laid down in the sand is burned, the ratio of moles of oxygen consumed to moles of coke can be written as follows. Moles 0MolesMolescoke In terms of moles O2 per pound of coke, where 12 + n is the molecular weight in pounds per mole. If the 0, consumed is measured in standard cubic feet (60°F and 1 atm) and the coke in pounds per cubic foot of formation, 2, then:

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz'ng' temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp'' have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.'2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

By R. H. Hiltz

Three titanium alloys, known to provide a mechanically unstable p structure after quenching, were selected as material for a study of the Origin and nature of stress-induced transformation. Data from hardness and tensile tests were used to study the initiation of marten site and the effect of the transfornation and transformation products on the mechanical properties of B titanium, particularly the stress-strain relationships. With the exception that the materials investigated showed a natural aging reaction in the P condition, their behavior is analogous to that of' stress-transforming stainless steels. The transformation starts after initial yielding and is essentially complete just prior to .maximum loading. Once initiated, the martensite itself is capable of propagating the transformation. The deforn-ing materials show low strength, high ductility, and a high strain-hardening exponent. In metallic systems which undergo a diffusionless transformation on cooling, it is possible to produce a similar transformatiorl by plastic deformation under special conditions. Dewez' in delineating Ms temperatures for the titanium-rich end of most titanium binary systems:, established the point of intersection of Ms with room temperature for those particular alloys. Alloy compositions which would quench to mechanically unstable p were established from these data. The first investigation into the possibility of stress-induced transformation occurring in titanium met with little success. It was concluded that such a transformation in titanium was possible only under very special conditions. Continued effort in this direction, however, showed certain Ti-Mo binaries to be highly susceptible to this phenomenon. This fact was utilized by Liu to study the habit planes of martensite and by Machlin and wenig5 to study the effects of stress and plastic deformation on the P to a prime transformation in titanium alloys. The first investigation of the mechanical properties of these alloys was conducted by Holden and his coworkers at Battelle Memorial Institute.' The potentiality of the alloys i3s sheet-forming material was recognized, and the data reappeared in a survey of this type of titanium material.? The initial optimism was tempered by the difficulties in obtaining homogeneous 2i-Mo alloys in commercial-size ingots. The increasing need for good sheet-forming material kept investigation in this direction active, resulting in the development of a commercial alloy of this type.' This study was undertaken to obtain a clearer picture of the mechanism of stress-induced transformation in titanium. MATERIALS AND TEST PROCEDURE Three alloys were selected for this investigation: one a Ti-Mo alloy; another a Ti-Cr-Mo alloy, known to deform martensitically; and the third, a Ti-V alloy with an Ms below room temperature and an Md above room temperature, but known to contain w phase in the quenched condition. The compositions of these alloys are given in Table I. These alloys were cast as 5-lb experimental ingots, employing skull melting. The ingots were hot-forged into 1-in.-round bars. Two 72-in.-thick slices were cut from each bar for hardness testing; the remainder was cut into 0.252-in. tensile blanks. The tensile blanks and one hardness disc from each bar were heated in salt to a temperature 100°F above the 0 transus, held 2/2 hr, and brine quenched. X-ray analysis showed the pieces to be 100 pct 8.* *Omega cannot be distinguished from p by the technique employed. Tensile blanks were machined to size after this treatment. TO prevent transformation due to machining stresses, the shoulders and gage length were ground. True stress-true strain curves were

Jan 1, 1960

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.' Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer's number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.' Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" ' found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na' exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

By H. A. Wahl

This paper presents methods of designing hydraulic fracture treatments in formations saturated with slightly compressible liquids. Howard and Fast describe the fluid-loss control resulting from the viscosity and compressibility effects of the reservoir fluid in terms of a fracturing fluid coefficient. However, for horizontal fractures, this coefficient is applicable to infinitely thick reservoirs. These methods of evaluating fluid loss from horizontal fractures during treatment differ from previous methods in that: (I) formation thickness is incorporated in the velocity function describing the rate of fluid loss to the formation; and (2) for a given thickness the relative position of the fracture to the horizontal boundaries of the reservoir or any interrnediate permeability barrier is incorporated in the design procedure. This theory is applied to several actual and hypothetical field cases. The results of these calculations demonstrate that the eflect of formation thickness on fluid loss from horizontal fractures may result in fractures several times larger than predicted by other methods. INTRODUCTION Hydraulic fracturing has been the dominating well-stimulation technique during the last decade. From the time it was commercially available, fracturing has had a very favorable success ratio compared to other stimulation methods. However, numerous wells that were successfully stimulated remained economic failures. Only in the last few years has the oil industry recognized the importance of designing treatments for each well which will yield the maximum profit. This implies that for a given set of treatment conditions the size and general physical characteristics of the fracture can be determined. One of the outstanding contributions in the field of fracture design was presented by Howard and Fast.' In their paper, three flow mechanisms that control fluid loss from the fracture to the formation are defined: (1) viscosity effects of the fracturing fluid, (2) viscosity and compressibility effects of the reservoir fluid, and (3) wall-building effects of a treated fracturing fluid. The rate of fluid loss to the formation adjacent to a fracture is shown to be a function of time. For each flow mechanism the velocity function v(t) is expressed as a constant or fracturing fluid coefficient divided by the square root of time. This form of v(t) can be used in the Carter equation, as developed in the Howard and Fasc paper, to estimate the areal extent of fractures. This equation may be written as In the following sections the effect of formation thickness on fluid loss from horizontal fractures is evaluated when the controlling flow mechanism is the viscosity and compressibility of the reservoir fluids. The major assumptions inherent in the Carter equation are brought out in subsequent mathematical developments. THE EFFECT OF RESERVOIR FLUIDS ON FRACTURE EXTENSION When a fracture treatment is performed using a fracturing fluid identical to the reservoir fluid, the only flow mechanism controlling fluid loss is the viscosity and compressibility effects of the reservoir fluids. In developing a fracturing fluid coefficient for this mechanism, Howard and Fast considered a segment of the formation bounded by a unit area on the fracture face and extending to infinity in the direction of leak-off as shown in Fig. 1(a). The direction of leak-off z is normal to the fracture face. The equation governing the linear isothermal flow of fluid into this segment is where a = Eq. 2 is a form of the diffusivity equation. It is derived from the equation of continuity, Darcy's law and Eq. 3

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By B. L. Averbach, Morris Cohen, S. A. Kulin

The martensitic transformation can be initiated by elastic stresses at temperatures above M. in a steel containing 20 pct Ni and 0.5 pct C. Shear strains and normal tensile strains acting on a potential habit plane promote the transformation but compressive strains oppose it. THE strain sensitivity of the martensitic transformation has long been recognized. It is now well known that martensite formation can be induced by plastic deformation at temperatures below, and not too far above, the M, point.' However, the exact role of elastic vs. plastic strains and of the concomitant stresses has proved to be a very elusive matter. Many investigators2-' of the steel hardening reaction have made use of the stresses resulting from volume changes to account for such observations as the existence of retained austenite and its variation across the section of a bar, the change in the amount of retained austenite with quenching rate, and the self-stopping nature of the transformation when the cooling is stopped. The effect of applied strain as an independent variable has been studied in 70 pct Fe-30 pct Ni alloys by Scheil7 and McReynolds.8 Some data are also available for lithium and Li-Mg alloys,9 Cu-Zn,10 Cu-Sn and Cu-A1 alloys," and aus-tenitic stainless steels."-" It has been found that martensite formation can be induced isothermally, even at temperatures above M,, by mechanical deformation of the parent phase. The competitive nature of plastic yielding by slip and by the martensitic reaction has been depicted by Scheil.7 Basically, Scheil postulated that: 1—at temperatures not too far above M, (where austenite is less stable than martensite), a critical resolved shear stress (within the elastic range) is required to promote the transformation to martensite; 2—at and below M,, the austenite lattice becomes mechanically, as well as thermodynamically, unstable and shears over spontaneously into martensite without the application of external stress; and 3—at temperatures sufficiently far above M8, the critical resolved shear stress for martensite formation increases to a level above that required for slip, and plastic flow then supersedes the transformation when external stress is applied. Scheil's concepts were tested by McReyno1ds8 ho found no change in the elastic moduli (measured both statically and dynamically) of 71 pct Fe-29 pct Ni alloys in the vicinity of the M, temperature. Since the moduli did not approach zero or become negative on cooling to M,, it was concluded that the austenite lattice does not become mechanically unstable at M2, as postulated by Scheil. McReynolds also reported that M, is not raised by elastic stresses. Accordingly, plastic deformation was considered to stimulate the transformation by generating martensite nuclei in the distorted regions of the parent phase. The above issues with regard to the role of applied stress require clarification, if a basic understanding of the martensitic transformation is to be obtained. For example, in the reaction-path theory,'"," it is postulated that strain embryos exist in the austenite that provide part of the activation energy for the nucleation process. These embryos are visualized to be regions of localized strain in which the atoms in the austenite lattice are displaced part way along the path to their ultimate positions in the martensite. Consequently, it would

Jan 1, 1953

By C. L. Dake

Iron is much more soluble in the ferrous than in the ferric form. Where, as in the case of the ferrous silicates and. the sulphides, the iron is already in the ferrous form, it may go at once into solution and be removed, upon the breaking down of the parent rock. If in the ferric form, it must first be reduced; usually by the decay of organic matter, the demand of the decaying carbonaceous matter for oxygen being so great that the latter is abstracted from the ferric compounds and the iron is thereby reduced and rendered soluble. The iron may go into solution as the sulphate, or in the presence of excess CO2 as ferrous carbonate. It is probably soluble as salts of the organic acids.' Recent work indicates that these are important in the formation of bog ores.2 There is considerable variety of opinion concerning the behavior of these organic compounds.3 The secretions about the roots of plants and trees also cause the solution and removal of iron and a consequent bleaching of the soil,4 While the matter is not yet well understood, we can probably say definitely that the so-called organic acids are a group of colloids which possess slightly acid properties, and the salts of which are partly soluble and partly insoluble.5 Their iron salts readily change from the ferrous to the ferric form, and their solubility is greatly modified by the presence of ammonia.

Jan 1, 1916

By H. E. Rowen

As high grade iron ore deposits dwindle and costs rise, sintering becomes more and more important. The steel industry is now faced with beneficiation problems once peculiar to nonferrous work. Succeeding articles describe recent advances in this field. Here is presented the first chapter of a history still being written. SINTERING, for the purpose of this discussion, is defined as the art of burning a solid fuel with 90 to 95 pct ash content. Considering problems of combustion involved in keeping a home furnace burning properly with 12 to 20 pct ash in the fuel, it is evident that combustion represented by the definition has to be right or nothing is going to happen. Our forefathers discovered that many ores containing metals essential to the steadily rising standards of living were associated with elements such as sulfur and arsenic, which had to be removed before refining. This they did by utilizing the solid fuels they had available-the sulfur or other readily combustible components-to create roasting heat. One of the early methods is demonstrated in an old woodcut of the roast heap, Fig. 2. Ore was broken into chunks, piled on an ignition layer of solid fuel-logs in this case-and then. ignited. The sulfide ores roasted as the sulfur burned out. As shown in the background, the countryside was rapidly denuded of all vegetation by the great quantities of SO2 and other liberated gases.

Jan 1, 1961