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By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,' Rutter and Chalmers,' Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-', c',, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c', — c",), , , = tic', (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick's first law it follows that uc',,(s = 0) (1 ~K) == - D(dc',,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By E. S. Mardock, Robert E. Bush

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in 'Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.'."".'" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Robert E. Bush, E. S. Mardock

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in 'Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.'."".'" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. Development of the new units was prompted by a desire for solution of the following problems: 1—The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pct of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be pro- vided in the event that air lines were no longer available. 2—Drill performance has increased beyond the capacity of present 3-in. drifter machines. 3—The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4—Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5—Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6—In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1—It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1953

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. Development of the new units was prompted by a desire for solution of the following problems: 1—The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pct of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be pro- vided in the event that air lines were no longer available. 2—Drill performance has increased beyond the capacity of present 3-in. drifter machines. 3—The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4—Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5—Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6—In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1—It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1953

By B. Ancker, E. R. Parker

The small-angle dislocation-boundary density of nickel and some of its alloys was investigated as a function of strength. It was found that the strength is a linear function of the density for pure nickel and for Ni-Ti alloys, but not for Ni-Co alloys. The results are interpreted in terms of dislocation theory. THE processes by which metals deform are still poorly understood, even though there has been a concentrated research effort in this field during the past fifteen years. Single crystals and individual grains in polycrystalline aggregates often develop a subgrain structure when deformed. Substructure formation occurs as a result of local plastic bending and its development is augmented by annealing at moderate temperatures.' Investigations made to date, largely qualitative in nature, have shown that the substructure is composed of a network of small-angle boundaries. The purpose of the present paper is to present some quantitative data on substructure (obtained by X-ray techniques) and to correlate the results with the strength of the metal in which the substructure existed. Nickel and some of its alloys were used for the experiments. The presence of certain kinds of foreign atoms greatly alters the formation and effect of the substructure. Polycrystalline tensile specimens were prepared from high purity nickel, two Ni-Ti alloys, and two Ni-Co alloys; the composition of these materials is given in Table I. Tensile specimens having a reduced section 1/4 in. diam by 3 in. long were machined from materials which were refined, cast, forged, and swaged in the authors' laboratories. The specimens were annealed for 1/2 hr at 1150°C, a treatment which produced grains having a diameter of approximately 0.5 mm. This rather large grain size was used to facilitate later examination of the substructure. Duplicate specimens of pure nickel and of each alloy were strained various controlled amounts in tension at room temperature and recovered for 1 hr at 800°C. (This strain induced prior to recovery will be referred to hereafter as the "prestrain.") One of each of the recovered specimens was pulled in tension at room temperature to obtain the stress-strain curves. The other bar was cross-sectioned in the gage length, carefully polished, and deeply etched to remove all cold-worked material. This specimen was then examined by the X-ray microscopic technique2 to determine the nature and magnitude of the substructure. The use of duplicate specimens permitted a direct correlation between tensile properties and substructure characteristics. X-ray microscopic studies were made with an apparatus constructed to have an average resolving power of about 4 microns. The monochromatic radiation reflected from grains which were oriented favorably was recorded on fine-grain photographic plates. These were examined at Xl00 which represents the true magnification, since there was essentially none in the X-ray system. This permitted detection of angular differences between subgrains of as little as 10 min. A very large number (over 100) of grains for each specimen was examined at this magnification and the number of substructure boundaries per grain was tabulated. An accurate relative measure was obtained under fixed experimental conditions, e.g., same grain size, resolving power, magnification, etc. The greatest source of error lay in counting the subboundaries, but this proved to be surprisingly small when repeated counts were made by different investigators. Furthermore, as the subsequent analysis indicates, whatever human error was introduced was not significant. Analysis of the Substructure Data When the number of substructure boundaries per grain was plotted against the frequency, skew (asymmetrical) distribution curves of the type shown in Fig. 1 were obtained. These are smoothed curves for the 1 atomic pct Ti in nickel alloy subjected to various prestrains and are representative of the curves obtained with all the metals. Since skew-distribution curves cannot be analyzed by elementary statistical methods, detailed investigations were undertaken in order to 1—test the consistency

Jan 1, 1955

By R. W. Fountain, J. F. Libsch

ONSIDERABLE time and effort have been ex- pended recently in research designed to provide a better understanding of the solid state transformations leading to the permanent magnet qualities of many commercial alloys. The knowledge derived from these investigations has resulted in the development of new magnetic materials as well as improvements in some of the older materials. The permanent magnet qualities of the newer alloys having high residual inductions and high coercive force values, have been attributed to the precipitation of a second phase or an order-disorder transformation in a solid solution. The ternary Co-Fe-V alloys provide an interesting group of magnetic materials having a wide range of magnetic properties. The low vanadium alloys' possess soft magnetic properties similar to the binary Co-Fe alloys, while at higher vanadium contents (about 10 pct) interesting permanent magnet properties are obtained.2,3 Previous work by Nesbitt' on the ternary Co-Fe-V permanent magnet materials, resulted in the conclusion that the precipitation of a second phase, ?, was responsible for the permanent magnet qualities of these alloys. However, unlike the conventional precipitation hardening alloys, the ? phase, which is stable at high temperatures, is precipitated in the low temperature a phase upon aging. Recent work by Geisler and Martin"." has established that the order-disorder reaction inherent in the binary Co-Fe alloys is also present in the ternary Co-Fe-V alloys. On the basis of their investigation, it was proposed that ordering of the a phase is also a possible explanation of the mechanical and magnetic hardening in these alloys. Thus, it appears that the Co-Fe-V alloys are rather unique in that two solid state transformations are taking place which may account for the properties of these alloys. In view of these facts, the present investigation was undertaken to study the mechanism of mechanical and magnetic hardening in the 10 pct V-Co-Fe alloy with particular reference to the role of the ? phase; and to correlate the results of this study with other magnetic properties. In addition, the influence of increasing vanadium contents on the transformation of Co-Fe alloys was also undertaken to supplement the main objective of the investigation. Experimental Procedure The Co-Fe-V alloys used for study consisted of: 1—a commercial lot of Vicalloy I, a 10 pct V alloy, and 2—alloys prepared by powder metallurgy and containing 52 pct Co and 0 to 14 pct V, balance iron. The commercial alloy was received in the cast and forged condition and was used primarily for the detailed study of hardness, electrical resistivity, and magnetic properties of the 10 pct V alloy. The powder metallurgy alloys were prepared from electrolytic iron, commercial cobalt, and ferro-vanadium powders. The processing cycle was as follows: 1—Elemental powders were weighed and mechanically mixed for 24 hr. 2—Mixed powders were pressed at 60,000 psi into the form of bars 5/8 x 5/8 x 5 in. 3—Bars were sintered in an atmosphere of purified dry hydrogen for 24 hr at temperatures ranging from 1380" to 1340°C, depending upon the vanadium content. The as-sintered bars were cut in half; and one half was machined to 7/16 in. diam for thermal analysis. The remainder of the bar was hot forged to approximately 0.050 in. for X-ray diffraction analysis. Additional details of sample preparation are presented subsequently according to the type of test performed. Thermal Analysis Measurements One of the simplest and most widely used tools for determining phase relations as they change with temperature and composition is to study the rate of change of temperature of a material as heat is supplied or extracted at a constant rate. The thermal analysis method used in this investigation is the inverse-rate method described by Smith.'

Jan 1, 1954

By A. S. McLatchie, R. A. Hemstock, J. W. Young

Much attention has been given in the past few years to methods of increasing the recovery of oil from proven reserves. Numerous laboratories have made investigations to evaluate the possibilities of increased oil recovery by high-pressure injection of dry gas, injection of a propane slug followed by dry gas, solvent flooding. and by the injection at relatively low pressures of gases enriched with ethane and propane. Several years ago, Whorton and Kie-schnick' published the results of laboratory studies on high-pressure gas injection which showed that, in the case of light oils, recoveries could be considerably increased by sweeping the reservoir with dry gas at pressures in excess of 3,000 psig. The increase was attributed by those authors to the vaporization of oil at the invading gas front and viscosity and solubility effects produced at the front by the invading gas. Later, Stone and Crump' presented the results of a series of displacement experiments in which a light under-saturated crude oil was displaced from sand-packed columns with unusually high recoveries when the displacing gas was a rich condensate or a dry gas enriched with ethane or propane. They also conducted similar experiments at higher pressure on heavy undersa tu rated crude oil, although in this case the increase in recovery was not as great as in the case of the light oils. In both cases, viscosity reduction and swelling of the by-passed oil behind the invading gas front were believed to be responsible for the more favorable recovery of the original oil in place. Within the past year, other investigators", ' have presented the results of laboratory studies of miscible slug and solvent flooding recovery processes. This paper describes the laboratory methods developed for evaluating benefits to be obtained by enriched gas drive in specific reservoirs, and presents the results of several displacements of crude oils which possess a wide range of physical properties. The displacements were conducted at reservoir conditions of temperature and pressure. The apparatus used in the following experiments consisted of a sand-packed tube which served as the model reservoir, a cylinder of injection fluid, and a mercury pump. The stainless steel tube, 8 ft long and 0.53 in. I- was packed with a graded quartz sand. The high-pressure pump discharged mercury into the bottom of the injection fluid cylinder at a constant rate as low as 1 cc/hr. The average porosity and permeability of the sand column were 34.6 per cent and 3.25 darcies, respectively. In each case the tube was charged by the displacement of salt water by the reservoir oil under consideration. Recently a project was initiated to evaluate oil recovery by enriched gas drive from three oil reservoirs. Samples from a fourth reservoir (in this case high-viscosity oil) were studied with a view to obtaining recovery information of general applicability to low-grade, high-viscosity crudes. The oils from these four reservoirs exhibited a wide range of physical properties, and the reservoir conditions of pressure and temperature simulated in the laboratory represented several typical field conditions under which enriched gas drive might be employed. One of the reservoirs selected for laboratory displacement experiments produced an intermediate-gravity crude (29.6" API) by solution gas drive and a weak water drive. A low recovery in the range of 10 to 20 per cent was anticipated. Four displacement experiments were made to determine the effect of injection gas composition and initial gas saturation upon recovery of oil from the laboratory model. Two types of reservoir oil were used in these experiments. In the first run, a desaturated crude with a bubble point of 395 psi was charged to the tube. In the three subsequent runs, a simulated original reservoir oil was charged at 2,000 psi and produced by solution gas drive to 300 psi before beginning gas injec-

By R. A. Morse, C. R. Stewart, F. F. Craig

This paper preFents the results of a series of model flow test on a number of large limestone cores, having different pore configurations. For limestone cores having substantially sandstone type porosity, the production characteristics for solution and external gas drives are similar. For cores whose pore spaces were microscopically heterogeneous (i.e., consisted of combinations of solution cavities, matrix. and fissures), the production characteristics lor solution and external gas drives vary widely. The degree of divergence between gas-oil relative permeability relationships calculated from solution or external gas drive tests is an indication of heterogeneity of rock pore structure. The results of water floods on cores depleted by solution gas drive for each of these two general types of limestone porosity are also shown. Generalizations are made on the water flood recovery that could be expected from each of these two types of limestone porosity. The similarity between solution drive field performance and model solution drive performance on cores from the same formation is shown for several cases. This indicate? the feasibility of predetermining limestone field performance from such large core tests. Photomicrographs of plastic-impregnated rock thin sections of the samples tested are presented as an aid in understanding the flow test performances. INTRODUCTION During the past 15 years. reservoir engineers and research workers have developed methods of testing rock and fluid samples and applying the results, through calculation, to allow reasonably satisfactory predictions of oil recoveries and performances to be expected in sandstone oil recervoirs. It has been determined that representative fluid flow data can be obtained on rock samples as small as three-fourths in. in diameter by one in. long in most sandstones. However, little has been accomplished toward the laboratory determination of fluid flow characteristics in limestones. There has been a great deal of speculation as to the influence of variations in pore size, shape, and degree of interconnection upon oil recovery processes, and a great deal of thought has been given to the interpretation of limestone field perfomance. It has been generally recognized that predictions of reservoir performance based on oil displacement tests on small limestone core samples the size of those used for sandstone tests can often be misleading because of the improbability of obtaining a representative sample in such a small core. Obviously, if there are present in the rock, pore openings of the magnitude of 1/16 in., or fractures or solution channels up to one in. or more in length, it will be impossible to cut any sample less than one in. in any dimension which would represent the flow geometry of the gross rock system. In some formations, the individual openings in the rock are of such size that it would be impossible to obtain a good sample of the flow system even in the total core available from conventional-sized well cores. However, by increasing to the maximum the size of the sample used, it should be possible to obtain representative flow data from the majority of limestone reservoir materials which can be used for prediction of future primary production performance or response to be expected from secondary recovery measures. The only alternatives to obtaining good laboratory test data to serve these purposes are extrapolation of primary performance data obtained by partial depletion of a field, or obtaining information from pilot tests. It has been shown previously, and will be demonstrated further by the work reported in this paper, that extrapolation of solution gas drive performance for an estimate of gas injection response can be very misleading in reservoirs of heterogeneous type porosity. Although it cannot be expected that laboratory information can ever eliminate the necessity of small-scale pilot operations, it is expected, as is now the situation with sandstone reservoirs, that laboratory tests should provide reliable information for screening of

Jan 1, 1953

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969