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By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By Robert U. King, John W. Vanderwilt

THE Climax molybdenite deposit in Lake County 100 miles southwest of Denver is located in the central part of the mineral belt extending northeasterly across the state. Principal geographic features and geology are shown on Fig. 1. The first period of molybdenite mining, which began in 1918, ended in April 1919 because of limited demand and a price drop to about 72¢ per lb. During this time the ore came from the Leal level and surface outcrops at a higher elevation. Rate of mining was 250 tpd and several million tons of ore averaging 0.7 pct molybdenite were developed. Since April 1924, when the second period* began, Climax Molybdenum Co. has been the only operating company. Production in 1924 was 400 tpd and finding ore was a continual problem. When the White tunnel was extended, however, further ore was encountered. The orebody was thought to be tabular until 1926, when B. S. Butler recognized the relation of the developed ore on the Leal and White levels to a central area of fine-grained hydrother-mal quartz, and by 1929 diamond drilling had blocked out indicated ore reserves in excess of 100 million tons. In 1946, on the basis of information obtained from 25 miles of mine workings and a completed exploratory program involving over 200,000 ft of diamond drilling, the present authors reviewed and brought up to date the geology of the orebody. More recently Sears," employing microscopic techniques, made a study of hydrothermal alteration and mineralization, and Howell and Schassberger'" restudied available geologic data. Production (1953) of molybdenite ore has been expanded to over 25,000 tpd and total production from 1918 through 1953 has been: Tungsten, tin, and pyrite are byproducts and monazite also was produced from 1949 through 1951, after which it was not saved. A maximum of 15 to 20 tons of monazite was produced. Geology of the Area Pre-Cambrian crystalline rocks constitute most of the Mosquito Range for several miles to the north, east, and south of the Climax molybdenite deposit, see Fig. 1. To the west the crystalline rocks are in fault contact with shales and sandstones of Pennsyl-vanian age. Both crystalline rocks and sediments are intruded by dikes and sills of Tertiary age. Numerous faults with small displacements are to be found in the crystalline rocks east of the Mosquito fault and in the sedimentary beds to the west. Pre-Cambrian Rocks: The pre-Cambrian rocks consist of schist and gneiss, identified with the Idaho Springs formation, and granite with minor pegmatite correlated with the Silver Plume granite of the Silver Plume area. The Idaho Springs formation is a general term applied to pre-Cambrian schist and gneiss found over a large part of the Colorado Front Range. At Climax this formation consists largely of biotite-schist and quartz-biotite gneiss with minor quantities of plagioclase and orthoclase, although in places appreciable quantities of feldspar and quartz are present in the more gneissic varieties. Locally, especially along the contact with granite, recrystal-lization of the schist has produced coarser texture and a more pronounced than average gneissic appearance. The gneiss and schist have been mapped as a single unit by Butler and Vanderwilt (1933)" and by Singewald (1951).12 Schist predominates at the higher elevations of the Mosquito Range and in the area to the north and east of Climax. The regional trend of schistosity is northeast with varying dips to the east. Silver Plume granite and associated pegmatite intrudes the Idaho Springs formation. Silver Plume granite in many places and in the Climax district in particular has an irregular form, and many large and small inclusions of schist and gneiss occur within the granite. Granite predominates at the surface in the immediate vicinity of the area of hydrothermal alteration and extends for several miles to the northeast and southeast. As more schist is present at lower levels of the mine than in the upper levels, the suggestion is that the granite is sill-like in form,

Jan 1, 1956

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,' located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI'S were approximately the same as PI'S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By J. E. Steiner, J. M. Hodge, M. A. Orehoski

Ingots of four steels (1045, 1080, Ni-Mo-V, and Ni-Cr-Mo-V) were cast at pressures varying from about 1 to 760 mm of mercury, so as to obtain a range of hydrogen contents in each steel. The susceptibility of these steels to flaking was evaluated by cooling hot-rolled blooms at a range of cooling rates, varying from water quenching to slag cooling, and studying the occurrence of flaking as a function of cooling rate. The steels exhibited differences in susceptibility to flaking, and a tlzreshold value for hydrogen content for each steel was found, below which the susceptibility was very low and above which the susceptibility increased markedly with increasing hydrogen content. Mechanical property evaluations, metallogvaplzic exantinations, and X-my diffraction determinations o,t retained austenite were made on samples from the blooms. A mechanism of flaking which is consistent with the observed behaviors, the effects of hvdrogen content, and the differences in susceptibility among the steels investigated is postulated, based on the results of mechanical property evaluations and metallographic and X-ray diffraction studies. ThE important role of hydrogen as a factor in the occurrence of "flakes" or "hair-line cracks" in steel has now been established by many investigations. These have included investigations by steel producers and forging manufacturers, to whom the prevention of flaking is a very real and serious problem, and many research studies aimed primarily at establishing the mechanism of this behavior Several investigators3 have reported that steels cast at reduced pressures (absolute pressures of about 1 mm) not only are low in hydrogen content but are essentially insensitive to the formation of flakes. These investigations have shown that a general relationship exists between hydrogen content and susceptibility to flaking. The difficulty of obtaining suitable samples of steels of a given composition with the desired range of hydrogen contents, particularly in the relatively large sections in which flaking most commonly occurs, has been the principal obstacle to quantitative evaluations of these relationships. Steels with intermediate hydrogen contents between 1 ppm, and the 4ppm or higher of air-cast steels are generally not available in commercially produced steels. Laboratory procedures, in which the hydrogen is introduced into solid steel samples by heating in a hydrogen atmosphere under pressure, generally involve a limitation in the size of the sample which can be treated, and thus are not representative of the behaviors in large sections. The availability of a facility at the South Chicago Works of U.S. Steel, in which several ingots could be cast from a single heat of steel at total air pressures ranging from 0.25 to 760 mm of Hg, has made it possible to overcome this obstacle and to obtain ingots of a given steel covering the intermediate range of hydrogen contents desired. These ingots, furthermore, are of a size suitable for the production of product with section sizes large enough to be representative of the products in which flaking most commonly occurs in commercial production. In these experiments, this facility was used to study the relationships between hydrogen content and the susceptibility to flaking of four steels, two plain carbon steels at 0.45 and 0.80 pct C and two low-carbon alloy steels representing a medium and a rather high hardenability level. These flaking studies were supplemented by evaluations of mechanical properties and by metallographic studies on samples from the blooms, in order to obtain pertinent information on the factors other than hydrogen content which influence the susceptibilities of these steels to flaking. Based on the results of these tests, a mechanism for the initiation and propagation of the flaking cracks, which is consistent with the observed behaviors, is postulated. MATERIALS AND EXPERIMENTAL WORK Steelmaking and Conversion. To provide material for the investigation, five 29- by 35-in., hot-topped, big-end-up ingots were cast from each of four 80-ton, basic electric-furnace heats of four different steels (a 1045 steel, a 1080 steel, a Ni-Mo-V steel, and a Ni-Cr-Mo-V steel). A double-slag practice was used on all steels and the two plain carbon steels were Si-A1 deoxidized with an addition of 2 lb of A1 per ton, while the Ni-Mo-V and Ni-Cr-Mo-V steels were deoxidized only with silicon and

Jan 1, 1964

By Walter Miller

NOW, after a year's continued impact of war, the task of the petroleum-refining industry stands out clearly and looms up in larger aspect. This time it is not, as it was so largely in the first World War, simply a matter of increased quantity- more and more of the same petroleum products that had substantially been standard for years. In this era the emphasis is largely on newer and improved materials which had been produced, if at all, in comparatively insignificant quantities, and for which manufacturing equipment was not available on a large scale. At the beginning of 1942 four great product needs (besides a number of lesser one-) confronted the industry: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for aviation and Army equipment service, and petroleum chemicals for synthetic rubber manufacture.

Jan 1, 1943

By Charles B. Henderson

DESPITE the loss, by enemy conquest, of a high percentage of our normal sources of supply for tin, the position of this important metal is easier today than that of rubber and a long list of other strategic materials, many of which are produced in this country. Actually, there is no shortage of tin for essential war purposes, owing to a strict control of its use, to increasing considerably the amount of secondary tin available, and to the foresight of the Government in authorizing the Reconstruction Finance Corp., as early as June, 1940, to acquire and produce certain critical and strategic materials of which tin was one of the most important. The construction of the Longhorn Smelter on the Gulf Coast in Texas is an important part of this program.

Jan 1, 1943

By CHAS. A. R. LAMELY

In the extreme northeast corner of the State of Washington, on the Canadian border, lies the Metaline mining district. This district is old in history, but young in production. The Metaline district is a zinc-lead area of the replacement type in dolomite and limestone. The ore bodies of the Josephine horizon are in many ways similar to the ore bodies of the famous Tri-State zinc fields. The beds are faulted and folded and have varyng low dips in varying directions, and underlie large areas of the district. Production started in 1927 on a very limited basis. The property is now mining and milling 700 tons per day. The mine is opened by adit tunnels and a vertical shaft. As the ore horizons gained depth, it was necessary to sink inclines to follow the ore horizon (see Fig 1). From 1927 to date, approximately 600,000 ft of diamond drill was put down This work indicated that sufficient tonnage existed to justify a redesigning of the whole operation, surface and under- ground. After four years of general study, the following program was planned :

Jan 1, 1949

By AIME AIME

APPARENTLY unperturbed by any misgiving as to ill luck connected with the mystic number thirteen -for there were exactly that number of Directors on deck-the Board held two sessions on Tuesday, Feb. 21. , . Between the executive session at 5:15 p. m. and the general session at 8:30 p. m., 28 Section and Division delegates were wests of the Directors at dinner. Committee chair- " men and past officers brought the attendance to 75. Messrs. McAuliffe, Merica, Mudd and Tally had expressed their intention to be at the Directors' meeting, but each was prevented unavoidably at the last minute. At the executive session of the Board, J. V. W. Reynders was unanimously chosen to fill the unexpired term of Dr. Becket as Director: and Eugene McAuliffe in like " manner was selected to become Vice-president to fill the vacancy created hy Dr. Becket's assumption of the Presidency. Upon nomination of President Becket the following Executive Committee was appointed: Frederick M. Becket, chairman; Howard N. Eavenson, H. A. Guess, J. V. W. Reynders and William Wraith; and the Finance Committee was appointed as follows: Henry Krumb, chairman; Paul D. Merica and H. G. Moulton. Karl Eilers was reelected Treasurer and A. B. Parsons was re- elected Secretary to serve for the ensuing year, whereupon the executive session was adjourned.

Jan 1, 1933

IN comparing the living conditions of the worker or peasant of the past with those existing today, his-torians might point out many strange contrasts. From the Doomsday Book we learn that at the time of Wil-liam the Conqueror the 1,375,000 inhabitants of Eng-land and Wales owned less than 1000 horses and 5000 oxen. Even as recently as 1871 when England and Wales had a population of 31,845.000, the total number of horses in the country was estimated at 1,110,000. Compare the necessary drudgery of labor in those days with conditions in Canada today where a population of less than ten million people own 3,500,000 horses. Re-member that there is also a turbine installation in` this country of more than four million horse-power, besides steam boilers and locomotive and automobile engines which reduce the traction and hand labor of the farm and factory. Frequently, poetic license has glossed over the poverty and hardship of the common people in the "good old days," and the imagination has created an idyllic world, far from being justified by the condi-tions which actually prevailed. Simon Patten's de-scription of the Middle Ages as "A Thousand Years Without an Ice Box" came nearer portraying the true situation. No one is likely to forget that the discovery of America was an incident in Europe's attempt to find a short route to the Indies, but the fact is usually for-gotten that the summer diet in Europe in 1400-an ice-less age-was such that spices were more precious than gold. Though the glamor of the Indies may never sur-round the modern refrigerator, certainly the modern housewife is likely 'to feel that the applied art called "cookery? may attain to higher levels with the assist-ance-6f such an adjunct. Those who have spoken slightingly of the uniformity of the modern apartment and have eulogized some of the exceptional hand-made furniture which has been bequeathed by former generations, have failed to com-pare modern house furnishings with those in the typical peasant's hovel. Machine-made furniture, though with-out particularly good lines, contrasts quite favorably with the pile of rags in the corner, and the poorest gas or oil stove is better than an open fire on a dirt floor. The scientist's application of the theories of physics, chemistry, biology and mathematics .to practical prob-lems has brought about a series of kaleidoscopic trans-formations in agriculture, industry and commerce. Large scale production, improved means of communica-tion and the prevailing higher standard of living are terms which imply a very human meaning when in-terpreted as actual changes in individual living. Though the student and the teacher may deprecate the influence of commercialism upon science, humanity as a whole has received great benefits from the close relationship which has developed between science and industry, and industry in turn has done much for science through the building and endowment of laboratories and by supply-ing funds to maintain research workers.

Jan 11, 1927

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these' the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert's law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957

By Thomas Brownfield

Development and production activity in Oklahoma during the year 1940 was of routine nature. Production, according to the Corporation Commission's figures, averaged 409,100 bbl. daily as compared with 421,000 bbl. for the year 1939. Discoveries were of minor importance except for the Cumberland pool in Marshall and Bryan Counties, in the southern part of the state. Maintenance of a relatively stable producing rate is attributable to the drilling of new wells and the recompletion of many old wells in the previously established producing areas. During the year 1785 new wells were drilled, a decline of approximately 10 per cent as compared with the previous year. Of the wells drilled, 962 were oil wells with a combined initial production of 241,000 bbl. daily, 172 were gas wells having aggregate capacities of 1205 million cu. ft., and 651 were dry holes. Wildcat activity increased 20 per cent over 1939 and 227 such wells were completed during the year; that isl 43 oil wells, 16 gas wells, and 168 dry holes. In addition to the new work completed, 603 wells were recorded as having been drilled deeper or plugged back to test new horizons; included were 334 producing wells with total initial production of 65,000 bbl. daily, 37 gas wells with initial aggregating 305 million cu. ft., and 232 abandonments. Footage drilled amounted to 4,730,000 ft., an average of 2650 ft. per well as com-pared with an average depth of 2600 ft. recorded the previous year. The principal new pools discovered as a result of the exploratory drilling were Cumberland; East Cromwell, in Okfuskee County, and Prague, in Lincoln County. At the end of the year Cumberland had 13 completed wells, which averaged 700 bbl. initial through tubing from the Simpson Bromide formation (Ordovician) at 4750 ft. East Cromwell had 10 wells with average initial of 435 bbl. in the Cromwell sand (Pennsylvanian) at 3460 ft. Prague had II wells with an initial average of 220 bbl. from the Senora sand (Pennsylvanian) at 3260 ft. There were notable extensions to the Dill pool, Okfuskee County, and to the Hewitt pool, Carter County. At the end of the year, 19 producing wells had been drilled in the former, with initials averaging 1000 bbl., and 63 wells averaging 150 bbl. daily in the latter. There were no notable changes in the policy of State conservation authorities with respect to proration. The Bureau of Mines recommendations for the year averaged 413,000 bbl. daily; the State author-ities fixed allowables at an average of 406,000 bbl. daily, while, as noted above, production averaged 409,100 barrels. The most important development in the older areas occurred in the following pools: Billings.—Seven oil wells with an average initial production of 2500 bbl. and two dry holes were completed during the year. Production from the Simpson horizon averaged 6025 bbl. daily as compared with 5950 the previous year. Production from this field has been almost steady since reaching its peak early in 1937. The major portion of the pool is efficiently operated as

Jan 1, 1941

By Thomas Brownfield

Development and production activity in Oklahoma during the year 1940 was of routine nature. Production, according to the Corporation Commission's figures, averaged 409,100 bbl. daily as compared with 421,000 bbl. for the year 1939. Discoveries were of minor importance except for the Cumberland pool in Marshall and Bryan Counties, in the southern part of the state. Maintenance of a relatively stable producing rate is attributable to the drilling of new wells and the recompletion of many old wells in the previously established producing areas. During the year 1785 new wells were drilled, a decline of approximately 10 per cent as compared with the previous year. Of the wells drilled, 962 were oil wells with a combined initial production of 241,000 bbl. daily, 172 were gas wells having aggregate capacities of 1205 million cu. ft., and 651 were dry holes. Wildcat activity increased 20 per cent over 1939 and 227 such wells were completed during the year; that isl 43 oil wells, 16 gas wells, and 168 dry holes. In addition to the new work completed, 603 wells were recorded as having been drilled deeper or plugged back to test new horizons; included were 334 producing wells with total initial production of 65,000 bbl. daily, 37 gas wells with initial aggregating 305 million cu. ft., and 232 abandonments. Footage drilled amounted to 4,730,000 ft., an average of 2650 ft. per well as com-pared with an average depth of 2600 ft. recorded the previous year. The principal new pools discovered as a result of the exploratory drilling were Cumberland; East Cromwell, in Okfuskee County, and Prague, in Lincoln County. At the end of the year Cumberland had 13 completed wells, which averaged 700 bbl. initial through tubing from the Simpson Bromide formation (Ordovician) at 4750 ft. East Cromwell had 10 wells with average initial of 435 bbl. in the Cromwell sand (Pennsylvanian) at 3460 ft. Prague had II wells with an initial average of 220 bbl. from the Senora sand (Pennsylvanian) at 3260 ft. There were notable extensions to the Dill pool, Okfuskee County, and to the Hewitt pool, Carter County. At the end of the year, 19 producing wells had been drilled in the former, with initials averaging 1000 bbl., and 63 wells averaging 150 bbl. daily in the latter. There were no notable changes in the policy of State conservation authorities with respect to proration. The Bureau of Mines recommendations for the year averaged 413,000 bbl. daily; the State author-ities fixed allowables at an average of 406,000 bbl. daily, while, as noted above, production averaged 409,100 barrels. The most important development in the older areas occurred in the following pools: Billings.—Seven oil wells with an average initial production of 2500 bbl. and two dry holes were completed during the year. Production from the Simpson horizon averaged 6025 bbl. daily as compared with 5950 the previous year. Production from this field has been almost steady since reaching its peak early in 1937. The major portion of the pool is efficiently operated as

Jan 1, 1941

By Walter Miller

ALTHOUGH confident of its ability to meet any demands which may be made, the petroleum refining industry is not complacent about the situation and realizes that the quantities of petroleum products to be furnished are so enormous and so far beyond what was previously estimated that the full co-operative effort of the industry must be exerted. Establishment by the President in May of the Office of Petroleum Coordinator for Defense with Secretary of the Interior Ickes at its head, plus the formation of the Petroleum Industry Council for Defense, in November, provide the channels for united endeavor within the industry and the means for gearing that endeavor within the industry and the means for gearing that endeavor in full harmony with the nation?s needs. Great strides have been made and a rapid understanding of the situation and the magnitude of the task is being attained by all concerned.

Jan 1, 1942

By Joseph E. Pogue

THERE are two methods employed in the development of oil pools. The older and dominant method is one in which the primary object is the protection of the underground deposit from drainage through competing wells, and considerations of efficiency of extraction and cost of production are subordinated thereto. The newer and less prevalent method is one in which maximum efficiency and minimum cost are the first objectives and developments to these ends may proceed undisturbed by the exigencies of competitive drainage. The second method has developed mainly in pools under single ownership and the term "unit operation" has come to be applied to this procedure. A single ownership, however, is not essential to the method, for unity of operation may be achieved by agreement under split ownership, or even by a concert of enlightened purpose. There are examples of unit operation where neither the ownership nor the management is a unit, but merely where unity of procedure has been attained, as is the case of the Yates pool. .Throughout this paper unit operation is used in its broad sense without implying sole ownership or single management, although unit operation is more conveniently attained where these conditions are present.

Jan 1, 1930

By Bradley Stoughton

AT THE meeting of the Board of Directors on May 20, the resignation of Bradley Stoughton as Secretary of the Institute was presented and regretfully accepted by the Board. The letter of resignation follows : Gentlemen: About two years ago, I indicated to the President and some members of the Board my belief that the office of Secretary of the Institute should not be a permanent one. It is my observation of events, not only in our own Institute, but also in several sister societies, that too long a tenure of office by the Secretary inevitably leads to a situation which is not good either for him or for the society. After submitting this in writing to the Directors on February 17, 1920, I was overpersuaded by members of the Board to defer resignation until a more convenient time for the

Jan 1, 1921