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By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By James F. Watson, Jack L. Christian

The austenite to martensite solid state phase transformation in the 300 series austenitic stainless steels was studied over the temperature range of 788° to -423°F. The primary variables controlling this transformation are temperature, plastic strain, and chernical composition. Consequently, temperature effects were studied by measurements at 78", -100°, -320°, ad -423°F; plastic strain was controlled by cold-rolling the alloys varying amounts between 40 and 80 pet; and chemical compositions were varied by using 301, 302, 304 ELC, and 310 stainless steel alloys which exhibit varying degrees of austenite stability. The martensite contents of various alloys were correlated with several mechanical properties including yield and ultimate tensile strength, elongation, and notched tensile strength (Kt = 6.3). The yield and tensite strengths generally increased with increasing martensite content, but ) no correlation was observed between elongation and martensite content. The notched/un-notched ratio (Kt = 6.3) at -423°F exhibited a maximun at about 65 pct martensite. Attempts to correlate austenite stability (as measured by the Ms temperature) with both martensite content, and incremental increases in martensite content resulting from tensile testing were generally unsuccessful because the variable of cold Work could not be separated. As a result, only a general correlation of these variables was obtained. A (111) pole figure of austenite in a cold-rolled 301 stainless steel mas prepared an attempt to further investigate directionality as exhibited by mechan- ical properties. Yield strength was correlated with this pole figure, but ultimate and notched tensile strengths were not. 1 HE literature contains a wide variety of references pertaining to the austenite to martensite solid state phase transformation in austenitic stainless steel, see references 1 through 18. Discussions of the crystallography and kinetics of this transformation are given in references 2, 7, 8, 'and 11, while further discussions of austenite stability and hardening mechanisms are given in references 1, 3, and 10. Two important processing variables involved in this reaction are the degree of cold work and the temperature at which cold work is performed, and the nature of these effects are outlined in references 4 and 12, and 15 and 16 respectively. The latter two references deal primarily with cold rolling conducted at subzero temperatures. The effect of chemical composition on the austenite to martensite reaction was treated in detail by Eichelman and Hull, and they determined an equation for the M, temperature of this type of steel which included the effects of nickel, chromium, carbon, nitrogen, silicon, and manganese.5 Previous studies have shown that austenitic stainless steels of AISI types 301, 302, 304ELC, 310, and 301-N exhibit mechanical properties between 78" and -423"~ that are microstructure dependent, and the dependence of this microstructure on chemistry, temperature, tensile stress, and prior deformation is in general accord with previous investigations which have measured the effects of each of these variables on structure, or more specifically, the austenite-to-martensite transformation.lg The behavior of fully stable alloys, such as ATST type 310, at cryogenic temperatures is

Jan 1, 1962

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By D. W. Carter, K. M. Fagin

Six new oil fields were discovered in the East and East Central Texas district during 1942. The Coke and Quitman fields, in Wood County, at this time appear to be the two most important oil discoveries for the year. The. four other oil fields discovered were Concord, in Anderson County; Kildare, in Cass County; Weiland (ClubLake), in Hunt County; and Larissa, in Cherokee County. The Rodessa lime in the Chapel Hill field, Smith County, provided the only new oil zone in older fields. The Hawkins field, Wood County, was the most active in drilling operations, 125 new wells being completed during the year. The Chapel Hill field tied the Coke field for second place with 30 completions each. The third most active field was Kildare, with 10 completions. Like the other oil-producing districts of the country, wartime restrictions reduced the number of oil and gas-well completions to 265 in 1942, compared with 964 completions in 1941. This represents a drop of 72 per cent and only a little more than one half enough to replace the 437 producing wells abandoned in the district during the year. Tn addition, the number of producing wells temporarily shut down nearly tripled, far two principal reasons: (I) the rule of the Petroleum Administration for War preventing operators from equipping more than, one well on each 10 surface acres with pumping or artificial-lift equipment, and (2) the Railroad Commission's issuance of various orders permitting the transfer of allowable for wells having high water-oil ratios and high gas-oil ratios to other wells capable of producing the same with less waste of reservoir energy. No changes were made in prices of crude oil in the district during 1942. Production and Probation The district produced 158,928,281 bbl. of oil and distillate during 1942, compared with 163,566,695 bbl. during 1941, which represents a decrease of 3 per cent. The East Texas field produced 120,680,595 bbl. of oil, compared with 130,377,793 during 1941; a reduction of 9,697,198 bbl., or 7.4 per cent. The production of this field represents 75.9 per cent of the district total, compared with the 79.7 per cent that it furnished in 1941. The district had an estimated basic daily oil allowable of 623,242 bbl. on Dec. 31, 1942. Approximately 31.8 per cent of the production in Texas during 1942 was supplied by this district, compared with 33 per cent during 1941- Changes in the annual production of newer and flush fields in this district are attributable either to a difference in the number of wells producing during the year or to changes in basic allowable and number of shutdown days due to shifting market dconditions brought on by the war. All regularly prorated fields in the district were shut down 123 days. Major exceptions were the East Texas field, closed128 days; Hawkiis, shut down 106 days; and Cayuga, Sulphur Bluff, Talco, and Rodessa, which

Jan 1, 1943

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick's Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick's laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.' It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9'10 and adsorption on crack surfaces,' some doubts must be entertained about the validity of Fick's laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick's first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By H. H. Evinger, M. Muskat

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By Michael Perch, Charles C. Russell

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated1 recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be conducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests. Several attempts have been made to derive formulas for such predictions. The relations of both ultimate and proximate analyses to coke physical properties and byproduct yields have been studied. Lowry and co-workers1 correlated statistically the U. S. Bureau of Mines-American Gas Association assay test results with coal analyses, using 90 coals and coal blends. Parry,² Spooner,3 and Gabinskii and Krym4 made similar correlations. Lowry concluded that there were definite relationships between the proximate analyses of the coals and the yields and properties of the products. Although this statistical study was made on test results from carbonizing coal in a cylindrical steel retort, the conclusions are important and provided one of the first steps in the simplification of this complex subject. Studies should be made of other references on this subject just cited. Studies of the coking process reported in the literature frequently were confined to a small number of coals, and very few have included coals from various ranks. It would seem logical, however, that a program for studying factors involved in the formation of coke should be based on a number of coals selected from each of the various classes or types of coking coal. The possible use of the scheme of classifi-

Jan 1, 1950

By Paul J. Sirkegian

A detail of the guide rollers is shown on Fig. I; and Fig. 2 shows a photograph of a guide roller that has been in service for several months on the haul-back cable. The former practice of supporting and guiding the haul-back cable on slusher hoists at Kimberly was accomplished by using the conventional type of snatch-block pulley, but it was found that an excessive amount of cable whipping and unreasonable wear on both rope and pulley resulted from this type of cable support. The guide, which is wholly made in the Corporation's shops, consists of two vertical and one horizontal roll assembled in a frame that is lagged to the cap timber in a slusher drift. In some slusher drifts more than one guide-roller assembly is used, depending upon the length of the drift. The installations usually are placed at 30-ft. intervals. We have found by actual experience that these rollers have increased the life of the haul-back cable approximately 200 per cent, as compared with the usage of the conventional sheave-block pulley. Cable Care The underground rigging crew and the slusher operators are trained in rope splicing. No cable clamps or knots are permitted on slusher cables and all cable "eyes" are spliced. The standard practice has been to use preformed cables of ?-in. diameter for haulage and ½-in. diameter for the haul back. The preformed cables have proved to be important factors for safety in use and speed in making splices. No external lubrication is used on the cables. It has been found that dry ropes have about 400 per cent longer life than those that were lubricated under these operating conditions. An accurate record is kept of all cable life and the tonnage moved by the slushers in each working place, and if the rope wear is excessive in any particular working place, an investigation is made to determine the reason. Wire-rope Sling for Snatch-block Anchor The rope sling is shown by Figs. 3 and 4. These slings support the snatch-block pulley for the haul-back rope. The standard practice at Kimberly is to use a roller-bearing snatch-block pulley 10 in. in diameter. The snatch-block housings are equipped with a clevis attachment in preference to swivel hooks, as it has been found that the more rigid clevis keeps the cable in better alignment. The snatch blocks are hung from the cable sling, which is wrapped around the posts of the drift sets as shown on Fig. 3. This method of anchoring the pulley provides better anchorage and flexibility than those of the rigid or spring-mounted types. When the slusher-drift headings are being advanced, the snatch blocks are hung from a "gin" pole ahead of the last set of timbers' An employee is assigned on each production shift to take care of the lubrication of all slusher hoists that are being used and he is provided with tools for minor repairs.

Jan 1, 1946

By M. Muskat, H. H. Evinger

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Hugh D. Pallister, Richard W. Smith

The Alabama flake-graphite industry has flourished only in times of war when importations of foreign graphite for crucible use have been greatly curtailed or cut off. World War I was a boom period and in 1918 some 30 plants produced 7,795,475 Ib. of flake graphite. The industry languished following the war and no graphite was produced from 1929 to 1939. The Federal Bureau of Mines began investigating the Alabama graphite deposits in 1940 and worked out modern recovery methods that were applied to production during part of World War 11. A prospecting program disclosed reserves of over 25 million tons of graphtic schists. In 1942 the War Production Board authorized the enlargement of the only plant then producing flake graphite and the construction of two new plants. Production of flake graphite from these three plants in 1943 is estimated at 8,100,000 lb. Increased imports from Madagascar late in 1943 shut down one of the new plants and curtailed production at the other. Alabama flake graphite has not yet been able to compete with Madagascar graphite for use in the manufacture of any but small graphite crucibles. The future of the industry must depend on meeting the higher carbon content demanded for other uses. Introduction The flake-graphite deposits of Alabama are confined to a narrow belt extending for about 60 miles southwest from the northeast corner of Clay County across Coosa County to the edge of the Coastal Plain in Chilton County (Fig. I). The continuity of the beds is broken by a 10-mile gap between Millerville in Clay County and Goodwater in Coosa County. The Clay County beds extend about 27 miles northwest of this gap, with a width of 3 to 4 miles near Millerville and of less than a mile at the northeast end. The Coosa-Chilton are? is about 33 miles long with a fairly consistent width of 2 to 3 miles. Geologically the graphite belt lies near the northeast boundary of the outcrop of metamorphic rocks of the Ashland series, a complex group of intensely folded and faulted beds of pre-Cambrian age composed mostly of quartz-mica schist, in which the mica is predominantly muscovite; garnet-mica schist, in which biotite is more common; and hornblende schist. Flake graphite is found in commercial quantities only in the quartz-mica schist. The best graphite, both in quantity and quality, is found in schist cut by numerous small pegmatite stringers along the planes of the schistosity. The pegmatites themselves contain little graphite, but the adjacent country rock is normally rich. . The schist was derived through the recrystallization of shale during the intrusion of the pegmatites, the graphite being derived from amorphous carbon in the shale. The intrusion of the pegmatites, and therefore the size and quantity .of the graphite flakes, seems to have a structural control.

Jan 1, 1948

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By R. E. Zimmerman

The separation of fine sizes of coal from its impurities by means of various flotation methods has become of increasing importance in the coal industry. This, no doubt, will be even more so in the future as the quantity of high grade coal is depleted, particularly that used for metallurgical purposes. The purpose of this paper is to describe and report the results of research work done under the auspices of the Pittsburgh Coal Co. to determine the amenability of their bituminous fine sizes of coal to flotation, to investigate the value of various reagents and factors affecting their use, and compare the results between froth flotation and bulk oil flotation. Compared with the preferential flotation of complex minerals, or ores, the flotation of coal is comparatively easy. However, this statement should not lull one into the feeling that there are no special problems involved. For instance, the separation of coal from pyrite in high sulphur coals is still far from being 100 pet successful. Size consist has considerable effect on reagent consumption and recovery. Other factors will be described and finally it must be remembered that in the flotation of coal a low priced material is being treated and thus economic considerations govern more closely its application than is generally the case in treating other minerals. As a result of the research work done by the Pittsburgh Coal Co. on the flotation of coal, it was concluded that it was practical to clean the —48-mesh coal commercially by froth flotation and after several different types of flotation units and circuits were investigated by means of pilot plants, large scale units were installed at their Champion Nos. 1, 4 and 5 Preparation Plants for the cleaning of —48-mesh slurries. These large scale operations have been recently described by D. H. Davis.' C. P. Proctor and C. B. Carlson2 in their chapter on Froth Flotation of Coal in the AIME Seeley W. Mudd series book on Coal Preparation describe some of the practical applications of our Pittsburgh Coal Co. laboratory work in actual plant practice as well as summarizing part of the investiga-tional work. The author presents this paper, however, as a supplement to their reports, and records the basic research accomplished in the laboratory investiga-tional work as well as the results of experiments using bulk oil flotation. In presenting this work the author wishes to state much more work must be done in applying the principles of flotation to cleaning coal, especially in view of recent studies and practices in other mineral beneficiation fields. Methods of Conducting Laboratory Tests The bulk of the research work was conducted in the laboratory of the Champion No. I Preparation Plant. This plant has elaborate facilities for sampling and analyzing coal and proved to be an admirable location for the investigational work. Four types of laboratory flotation ma-

Jan 1, 1949

By Hugh D. Pallister, Richard W. Smith

The Alabama flake-graphite industry has flourished only in times of war when importations of foreign graphite for crucible use have been greatly curtailed or cut off. World War I was a boom period and in 1918 some 30 plants produced 7,795,475 Ib. of flake graphite. The industry languished following the war and no graphite was produced from 1929 to 1939. The Federal Bureau of Mines began investigating the Alabama graphite deposits in 1940 and worked out modern recovery methods that were applied to production during part of World War 11. A prospecting program disclosed reserves of over 25 million tons of graphtic schists. In 1942 the War Production Board authorized the enlargement of the only plant then producing flake graphite and the construction of two new plants. Production of flake graphite from these three plants in 1943 is estimated at 8,100,000 lb. Increased imports from Madagascar late in 1943 shut down one of the new plants and curtailed production at the other. Alabama flake graphite has not yet been able to compete with Madagascar graphite for use in the manufacture of any but small graphite crucibles. The future of the industry must depend on meeting the higher carbon content demanded for other uses. Introduction The flake-graphite deposits of Alabama are confined to a narrow belt extending for about 60 miles southwest from the northeast corner of Clay County across Coosa County to the edge of the Coastal Plain in Chilton County (Fig. I). The continuity of the beds is broken by a 10-mile gap between Millerville in Clay County and Goodwater in Coosa County. The Clay County beds extend about 27 miles northwest of this gap, with a width of 3 to 4 miles near Millerville and of less than a mile at the northeast end. The Coosa-Chilton are? is about 33 miles long with a fairly consistent width of 2 to 3 miles. Geologically the graphite belt lies near the northeast boundary of the outcrop of metamorphic rocks of the Ashland series, a complex group of intensely folded and faulted beds of pre-Cambrian age composed mostly of quartz-mica schist, in which the mica is predominantly muscovite; garnet-mica schist, in which biotite is more common; and hornblende schist. Flake graphite is found in commercial quantities only in the quartz-mica schist. The best graphite, both in quantity and quality, is found in schist cut by numerous small pegmatite stringers along the planes of the schistosity. The pegmatites themselves contain little graphite, but the adjacent country rock is normally rich. . The schist was derived through the recrystallization of shale during the intrusion of the pegmatites, the graphite being derived from amorphous carbon in the shale. The intrusion of the pegmatites, and therefore the size and quantity .of the graphite flakes, seems to have a structural control.

Jan 1, 1948