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By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By H. Conrad, V. V. Damiano, G. J. London

The slip mode activated during the c axis compression of single crystals of commercial-purity ingot SR beryllium, high-purity (twelve-zone-pass) beryllium, and Be-4.4 wt pct Cu and Be-5.2 wt pct Ni alloys in the temperature range of 25° to 364°C was determined using two-surface slip trace analysis, slip-step height analysis, and electron transmission microscopy. All three techniques indicated the occurrence of copious pyramidal {1 122) (1123) slip in the alloys over the entire temperature range, the amount increasing with temperature. Pyramidal slip was also indicated in the high-purity beryllium by slip trace analysis and electron transmission microscopy, but the amount was somewhat less than in the alloys. For the commercial-purity ingot crystals, only a very small number of pyramidal slip lines were observed, and these were in the immediate vicinity of the fracture surface. No pyramidal dislocations could be detected by electron transmission microscopy in this material. Dislocatransmissiontions with Burgers vectors [0001] and +(ll20) were identified by electron transmission microscopy inthe (1122) slip bands, as well as those with the j (1123) vector. This was interpreted to indicate that the edge components of the 3(1123) vector dislocations activated during c axis compression dissociate upon unloading according to the reaction i (1123) — [0001] + 3(1120) THE microstrain c axis compression of single crystals of commercial-purity ingot SR beryllium (99.6 pct), high-purity twelve-zone-pass beryllium (99.98 pct), Be-5.24 pct Ni and Be-4.37 pct Cu alloys was described in a previous paper.1 This paper covers in detail the analysis of slip traces observed on two mutually perpendicular lateral surfaces of these specimens, and a detailed description of transmission electron microscopy studies performed on foils cut from the bulk crystals after they had been deformed to fracture in the c axis compression. Observation of slip traces on single surfaces of deformed single crystals are generally insufficient to positively identify slip or twinning modes. The use of two carefully cut and oriented perpendicular surfaces can greatly aid in the positive identification and index- ing of slip traces, although even this technique may be quite inadequate if more than one type of slip system operates and if an insufficient number of traces are observed on the surfaces. The problem is greatly simplified for symmetric cases like that for c axis compression of an hep crystal such as beryllium, in which the operating slip systems are all equally inclined to the direction of the applied stress, and each slip system of a given slip mode has an equal chance of operating. For such cases, the traces of any given slip mode observed on the surfaces cut parallel to the c axis are symmetrically tilted about the c axis. It is therefore possible to quickly determine whether one or more slip modes are operating. Confirmatory evidence in support of the observations made on the external surfaces can be obtained from foils cut from the deformed crystals and examined by transmission electron microscopy. This latter technique serves to identify not only the operating slip plane but also the Burgers vector of the dislocations which participate in the slip. For this purpose, a simplified technique based upon a double tetrahedron notation is used in the present paper. The planes and directions in the hep lattice are all designated by letters rather than indices and extinction conditions are easily determined if the Burgers vector lies in the plane contributing to the diffraction. RESULTS 1) Slip Trace Analysis. The standard (0001) stereo-graphic projection of beryllium is shown in Fig. 1. The two mutually perpendicular, lateral surfaces of the compression specimen are represented by the diametrical planes AA' and BB', also referred to as surface A and surface B. For the specific case represented (a Be-5.24 pct Ni specimen deformed by c axis compression at room temperature), the A surface is tilted 5 deg to the (10i0') plane and the B surface is tilted 5 deg to the (1120) plane. Two surface trace analyses may be facilitated by examining in turn the intersection of various great circle traces of specific pyramidal planes with two surfaces and comparing the angles made with the (0001) plane with those actually observed on the two surfaces. One then identifies the slip traces by trial and error on a best-fit basis. The (1122) type planes (it was found that slip occurred on these planes) are shown plotted on the stereographic projection in Fig. 1. One obtains directly the angles between the (0001) plane and the {1122) traces by measuring the angle from the periphery to the point of intersection along the lines

Jan 1, 1969

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By H. T. Green, R. M. Brick

True stress-strain data on alloys of pure iron with up to 2.4 pct Al were obtained in the temperature range +100° to —185°C. Alumi-num was found to reduce yield and flow stresses of iron at low temperatures but to have little or no effect on ductility. The effects of temperature and composition on strain hardening are discussed. SEVERAL independent studies of the behavior of high purity iron binary alloys at low temperatures are now in progress in attempts to evaluate systematically the variables affecting the low temperature brittleness of ferritic steels. This paper reports the results of one such investigation in which the tensile properties of aluminum and aluminum plus silicon ferrites were measured from 100" to —192°C. True stress-natural strain data have been obtained in order to evaluate as many as possible of the parameters which describe the behavior of the materials involved. In comparable studies at the National Physical Laboratory in England, iron and iron alloys of high purity have been produced' and tested at subat-mospheric temperatures.' True stress-natural strain curves were obtained there also. The purest iron contained 0.0025 pct C and 0.001 pct O and N. Even this, as normalized at 950°C following hot rolling, showed little ductility at -196°C. The grain size was ASTM No. 3, and the room-temperature yield strength was 17,800 psi (which seems too high for pure iron). Some of the NPL irons contained considerably more oxygen and demonstrated intergran-ular fracture at —196°C. The authors2 carefully differentiated between intergranular fractures associated with excessive oxygen content and transcrys-talline cleavage with little ductility encountered at —196°C in the purer material. The cleavage stress was half again as great as that associated with inter-granular fracture. Test Material, Preparation, and Procedures Of a number of Fe-A1 alloys produced, eight were considered to be sufficiently pure for testing. Partial chemical analyses (Table I), low observed yield points, and high ductilities indicate these alloys to be comparatively pure for vacuum-melted irons of sizable ingots, 5 Ib or more. To produce the binary Fe-A1 alloys, electrolytic iron was melted in air, cast into slabs, and rolled to strips 0.010 in. thick. These strips, joined into a continuous ribbon and wound into 2 1/2 in. diameter spools, were subjected for four weeks to a moving atmosphere of purified dry hydrogen in a stainless-steel tube at 1050" to 1150°C. Charges of these spools were melted in beryllia crucibles under good vacuums (1 micron), and aluminum (99.97 pct Al) was added to the melts. Compositions of these alloys are recorded in Table I. The ingots were hot forged and then cold rolled at least 65 pct to 3/8 in. rods which were vacuum annealed to the desired grain size, approximately ASTM No. 4, prior to machining into tensile test bars. All tensile specimens had gage sections 1 in. long, with a fillet of 1.5 in. radius to the shoulder. Gage diameters were 0.250 in, except for a few rods where additional cold work required use of a 0.200 in. gage section. After machining, 0.002 in. was removed from the gage diameter using 240, 400, and 600-grit metallo-graphic papers. The final polish with 600 grit left the fine scratches running in the longitudinal direction. By this means, surface metal strained during machining was removed. A few specimens heat treated after machining were similarly reduced 0.004 in. to remove any material affected chemically by the atmosphere during heat treatments, as is discussed in a later section. Tensile tests of the eight alloys at constant temperatures from +100° to —185°C were performed in apparatus which has been described." The essentials include a double-walled insulated metal vessel which contained the liquid heat-transfer medium surrounding the test specimen. A constant temperature was maintained by means of a pyrometer which regulated the pressure of dry air driving liquid air through a copper coil. Temperature variation was less than ±2°C during a specific test. For axial straining, two lengths of case-hardened chain, terminating in simple shackles, loaded the specimen through threaded grips. The lower grip bar passed through a hole in the bottom of the test vessel to which it was joined by a thin-walled

Jan 1, 1955

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett', Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,'. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett', Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,'. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By E. A. Steigerwald, G. L. Hanna

The influence of work-hardening exponent on the variation of fracture toughness with material thickness was studied for high-strength steel, aluminum, and titanium alloys. The results indicate that, when materials are compared at similar fracture toughness to yield strength ratios, the material with the lower work-hardening exponent undergoes the transition from flat to slant fracture at a larger thickness than material with a high work-hardening exponent. In the thickness range where complete slant fracture is obtained the reverse is true and a lower work-hardening exponent results in a lower fracture toughness. The influence of work-hardening exponent on fracture toughness is, therefore, dependent on the particular fracture mode. In the transition region a low work-hardening exponent is beneficial for fracture toughness while in the 100 pct slant region it is detrimental. THROUGH the use of fracture mechanics analyses, the influence of geometric variables on the crack propagation resistance of structures can be interpreted with reasonable consistency. However, in order to gain a more complete understanding of the fracture process, the influence of material parameters on crack propagation must be defined and coupled to the macroscopic fracture mechanics approach. The work-hardening exponent, which characterizes specific material behavior, may serve as an effective parameter to allow some degree of coupling to be accomplished. In the extension of a crack in a specimen of suitable dimensions the propagation process occurs in a stable manner when the crack extension force is balanced by the resistance to crack extension, which exists in the material at the crack tip. As the applied stress, and therefore the crack extension force, on the specimen increases, the resistance also increases primarily because the effective plastic zone at the crack tip, which is the main energy absorption process, becomes larger. Since the work-hardening rate of a material influences the stress-strain relationship, it will also influence the energy absorption process in the plastic enclave at the crack tip and hence should have an effect on crack propagation. A number of studies have been made correlating the strain-hardening exponent or the strain to tensile instability with the ability of a material to resist fracture. Gensamer1 concluded that a low-strain-hardening exponent would result in a steep strain gradient at the base of a notch. He reasoned that a large work-hardening coefficient would result in high-energy ab- sorption due to the increased area under the stress-strain curve. Larson and Nunes2 experimentally observed in Charpy tests on steels heat-treated to below 200,000 psi yield strength that the energy to failure in the fibrous mode, i.e., above the brittle-to-ductile transition temperature, was logarithmically related to the strain-hardening exponent. In order to avoid the complicating effects present in studying materials which undergo a brittle-to-ductile transition, Ripling evaluated the notch sensitivity of a variety of fcc metals with varying work-hardening exponents.3 The results indicated that the relative notch sensitivity, as determined from tests on specimens with a sharp notch, decreased with increasing values of strain hardening. Although the energy required for ductile or fibrous fracture increases with increasing work hardening, high-strength steels often exhibit improved crack propagation resistance when heat-treated to obtain low values of strain hardening.4,5 An analysis of whether low strain hardening is beneficial or detrimental to crack propagation resistance must depend on the particular fracture criterion involved. At temperatures where the material is relatively ductile and the development of a critical strain is required for fracture, high strain hardening increases the energy required to produce failure. In the transition region and below, however, a critical stress law appears to be valid6 and a low rate of work hardening may produce superior resistance to semibrittle crack propagation. The experimental program is aimed at studying these possibilities and determining the specific influence of strain hardening on the crack propagation resistance of several high-strength materials. MATERIALS AND PROCEDURE The alloys, chosen as representative of various classes of high-strength materials, are summarized in Table I. The heat treatments evaluated along with the smooth tensile properties are presented in Table 11. Pin-loaded sheet tensile specimens were employed to determine the smooth tensile properties. A strain gage extensometer (measuring range 0.200 in.) was used at a strain rate of 0.02 in. per in. per min. The work-hardening exponents were determined from the stress-strain curves generated in the smooth tensile tests and the assumption that the portion of the stress-strain curve beyond the yield point can be described by the power relationship: where a is the true stress, P is the true plastic strain,

Jan 1, 1969

By G. W. Thomas

A mathematical tnodel of forward combustion in an oil reservoir is treated in this paper. The model describes a radial system having a vertical section of essentially infinite thickness, all of which is permeable to gas flow. Combustion, however, is presumed initiated over a limited thickness of the total vertical section. In the interval supporting cotnbustion, the mechanisms of radial conduction, convection and heat generation are taken into account. Above and below the burning interval, heat transport in the radial direction is by cottduction and convection. Vertical heat losses from the ignited interval are accounted for by conduction alone. A general solution is presented for the temperature distribution caused by radial movement of the combustion front. The results show that no feedback of heat occurs into the ignited interval when convection and conduction are acting in the bounding media. Peak temperatures are also 5 to 10 per cent higher than in the case where heat transport in the bounding media is by conduction alone. We arbitrarily define vertical coverage to be that fraction of the total ignited interval which is at 600F above atnbient, or greater, at any given time. The radial distance at which the vertical coverage becomes zero is the propagation range of the combustion front. It was found that an increase in vertical coverage results when the oxygen concentration, fuel concentration or gas-injection rate is increased. Moreover, the combustion front can be propagated 10 to 15 per cent further than in the case where only conduction is acting above and below the ignited interval. INTRODUCTION In the theoretical treatment of forward combustion in a radial system, one of the problems encountered is the determination of the transient temperature distributions caused by an expanding cylindrical heat source. Bailey and Larkin' and Ramey' simultaneously presented analytical solutions to the problem assuming heat transport by conduction alone. In a subsequent publication, Bailey and Larkin3 included the effects of both conduction and convection while treating linear and radial models. In this latter work, however, vertical heat losses were largely neglected. Selig and Couch' dealt with a radial model in which both conduction and convection were acting. Only a limiting case involving vertical heat losses was considered, however. Namely, temperatures on the boundary of the bed of interest were set equal to zero. Solutions thus obtained were representative of a system having a maximum vertical heat flux. Chu5 recently treated a more general case in which a permeable bed was considered bounded by impermeable media. Conduction and convection took place within the bed, and only conduction outside of the bed. The effects of vertical heat losses were included in his study. Solutions were obtained by numerical techniques. This paper is an extension of the theoretical work of other authors pertaining to forward combustion in a radial system. In particular, a mathematical model of the process is treated in which heat generation occurs over a small vertical interval of a larger permeable section. In the interval supporting heat generation, and above and below this interval, the mechanisms of radial conduction and convection are also presumed acting. Heat losses from the ignited interval are accounted for by vertical conduction. An analytical solution for the temperature distribution caused by radial movement of the burning front is presented. The effects of certain process variables are indicated and comparisons with Chu's results are made. THEORY To render the mechanism of forward combustion tractable to mathematical treatment, we idealize the problem to the extent of assuming continuous reservoir media possessing homogeneous and isotropic properties. The following additional assumptions are implicit in this analysis. 1. The thermal parameters, i.e., heat capacities, thermal conductivities and thermal diffusivities are invariant with temperature and pressure. Moreover, the bounding media possess the same thermal properties as the bed of interest. 2. The temperatures of the porous media and its contained fluids at any point and at any time are equal. 3. The reaction rate between the oxidant gas and the fuel is infinite. This assumption implies that the incoming oxygen concentration instantaneously goes to zero within an infinitesimal distance, i.e., the width of the combustion zone is negligible. 4. The rate of gas injection is constant and corresponds to the average rate throughout the lifetime of the project. 5. The fuel concentration is constant throughout the volume of rock swept out by the burning zone. 6. There is complete burnoff of fuel. This assumption demands that the rate of propagation of the burning front equals the rate of fuel burnoff. In a radial system, with a

By R. I. Jaffee, R. M. Evans

IN recent years, the interest in liquid metals as heat-transfer media for power plants has been very great. The possibility of the development of nuclear power plants has increased this interest and served as the impetus behind much research on low melting metals and alloys for such purposes. The principal reasons for consideration of liquid metals as heat-transfer media lie in their high thermal conductivity and consequent high heat-transfer coefficients, stability at high temperatures, and the high ranges of temperature possible. The element gallium possesses some of the requisite properties for a heat-transfer liquid. It is a unique material, having a low melting point and a high boiling point. Pure gallium melts at 29.78oC, and suitable alloying will produce a metal which melts below room temperature. The boiling point is about 2000°C. As it is a liquid metal, the heat-transfer characteristics would be good. Gallium is not now readily available, due in part to a lack of uses for the metal. Nevertheless, it is not a rare element, and a sufficient supply of gallium exists to permit its consideration for this use. Since gallium has some promise as a heat-transfer liquid, owing to its unique properties, research on the subject was carried on at Battelle Memorial Institute at the request of the Bureau of Ships, U.S.N. The research had as its objectives the determination of the effect of alloying on the melting point of gallium, and the study of the corrosion of possible container materials. In this research, alloys were found which had significantly lower melting points than pure gallium, but none which simultaneously fulfilled other additional requirements, chiefly the corrosion problem. Neither was it found possible to reduce the melting point of certain otherwise suitable alloys appreciably by small additions of gallium or gallium alloys. The results gave little hope that gallium alloys can be developed which enhance the good properties and minimize the undesirable characteristics of elemental gallium. Thus, gallium now appears less promising than other metallic heat-transfer media. The experimental thermal-analysis techniques used in this work have been described.' Experimental Results As a first approximation, the development of low melting gallium alloys was based on alloying elements suitable for use in a nuclear power plant, which also lowered the melting point of gallium. Information from the literature, summarized in Table I, indicates that. tin, aluminum, and zinc are the only suitable elements which cause a lowering of the melting point of gallium. Indium and silver also lower the melting point of gallium, but are of little interest for use in nuclear power plants. Of the elements reported not to lower the melting point of gallium, there is some ambiguity on the behavior of copper. Weibke3 obtained solidus arrest temperatures of 29°C for Cu-Ga alloys from 60 to 90 pct Ga, 0.8C lower than the generally accepted melting point. This may be the effect of a eutectic close to gallium, or, more likely, the result of impurities, or experimental error. The seven elements listed in Table I whose effects were not known were of potential interest if they lowered the melting point of gallium. Their effects were determined experimentally for this reason. Binary alloys containing nominally 2 pct of each of these elements were prepared in the form of 2-g melts by placing the components in a graphite crucible and holding them in an argon atmosphere at 370°C for 5 hr. These melts were then subjected to thermal analysis. In all cases. the solidus temperature was the melting point of gallium. Since these elements (As, Ca, Ce, Mg. Sb, Si, and T1) did not lower the melting point of gallium, they were not considered further as components of a eutectic-type alloy. Ga-Sn-Zn Alloys Preliminary considerations of this system for low-melting alloys were encouraging. All three binary systems were of the simple eutectic type. The composition and melting points of the eutectics were as follows: Sn-9 pct Zn (199°C), Ga-8 pct Sn (20°C), and Ga-5 pct Zn (25°C). Therefore, the probability of a ternary eutectic was high. For reasons to be discussed later, aluminum could not be used as an alloying constituent, leaving the Ga-Sn-Zn system as the only one of interest for low-melting gallium-

Jan 1, 1953

By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-' after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

By E. A. Almond

An attempt is made to explain the effect of stress on strain aging by examining the mechanism of yielding for a group of aged dislocations. The experimental results on which the theory is based indicate that a linear relationship develops between the aging stress and the discontinuous yield effect in a low carbon steel THE discontinuous yield effect that occurs in bcc metals after strain aging is usually explained by the interaction of interstitial atoms with individual dislocations. Attempts have been made to interpret the kinetics of strain aging in terms of interstitial segregation to nonrandom groups of dislocations1-3 but apart from Li's4 work little or no effort has been made to examine the effect of groups of aged dislocations on mechanical properties. It appears likely that such groups can be stabilized if a positive load is maintained on the specimen during aging5 and, furthermore, that the enhanced strain aging effect associated with aging under load might be due to the stability of these aged groups. The effects associated with this latter phenomenon have been described by Almond and Hull, Ref. 5, Figs. 2 and 3, and it is found that the upper yield stress, the lower yield stress, and the yield point elongation are increased by aging under load. The yield point elongation reaches a maximum value but the enhanced effect persists in the upper and lower yield stress values even after extended aging treatments when the general level of the flow stress curve rises. The flow stress, as measured at 8.5 pct total strain, however, is independent of aging stress. Almond and Hull5 showed that it was unlikely that the differences in mechanical properties could be caused by stress enhanced diffusion and they suggested that the effect was in some way associated with the different dislocation distributions that are obtained when specimens are aged with and without an applied stress. At that time no explanation was offered for the strengthening effect produced by stabilized dislocation distributions but additional tests have been performed to establish a quantitative relationship between aging stress and mechanical properties, and also to examine more closely the effect of varying the procedure for applying the aging stress. EXPERIMENTAL The material used was an iron wire containing 0.015 wt pct C, 0.002 wt pct N, and 0.006 wt pct 0. Tensile specimens with a 1 cm gage length and 0.08 cm diam were annealed at 850°C for 1 hr in vacuum to establish a grain diameter of 0.032 mm and then aged at 200°C for 24 hr. After this treatment the amount of carbon left in solution would be less than 10-4 wt pct, and ni- as aging time is increased. It is suggested that this observation, and effects that arise from varying the method of applying the aging stress, can be explained by a strengthening mechanism whereby dislocations are more difficult to move when they are aged in piled-up groups. trogen would be the main cause of strain aging. Tensile tests were performed in a hard beam machine at a constant crosshead speed of 0.02 cm per min and the specimen chamber was immersed in a temperature controlled silicone oil bath at 32" * 0.05"C. RESULTS All specimens were prestrained 5 pct before aging under stress and the results in Figs. 1 to 5 show the effect of aging time and aging stress on the following parameters ?UY = auy — ?F(5); i.e., the difference between the upper yield stress after aging,?uy, and the flow stress after prestraining 5 pct, ?f(5). ?LY = sly —sf(5); the difference between the lower yield stress after aging, ojy, and the flow stress after prestraining 5 pct. s8.5 = the flow stress at 8.5 pct total strain after aging at 5 pct strain. Varying the Loading Procedure. Three variations in the procedure for applying the aging stress were examined; i) After prestraining, the specimen was unloaded to a stress of 18 kg mm-2, aged at that stress, and then tested. ii) After prestraining, the specimen was unloaded to 2 kg mm-" then reloaded to 18 kg mm-', aged at that stress, and tested. iii) After prestraining, the specimen was unloaded to 18 kg mm-', aged at that stress, then unloaded to 2 kg mm- before testing. Specimens were unloaded or reloaded by decoupling a clutch in the drive transmission of the tensile machine. This enabled the crosshead to be driven manu-

Jan 1, 1970

By Shiou-Chuan Sun, R. F. Wesner, J. D. Morgan

0. C. Ralston and F. Fraas—Dr. Sun and associates have presented an interesting paper not all of which is comprehended by us. The data assembled measure the deflections of particles in an electrostatic field as a function of a number of independent variables and some dependent variables that are not sharply differentiated. These data are all based on a Johnson type machine of definite, well-described geometry, something not often done in electrostatic separation literature. One new fact brought out by this technique is the effect of coal dust on admixed pyrite and quartz. The effects are opposite in character, as should be expected and we do not agree with the authors that these effects are negligible. Fraas' also used a multiple cell "distribution analyzer" and gives in fig. 5 of his paper a straight line plot with no humps or curves. This is not necessarily at variance with Sun's results because Fraas used a larger gap between electrodes and had no evidence of particles adhering to or dropping off the charged electrode. The section of Sun's paper on effect of surface conductivity contains a speculation that the dielectric constant "represents more or less the electrical conductance of the bulk body instead of the surface of the mineral particles." A simple picture of the meaning of the dielectric constant is that it is the specific inductive capacity of a dielectric when used as the dielectric between the plates of a condenser. It is at once evident that the above speculation confuses capacity with conductance—two definitely independent variables. We ask the authors to state in what group or subdivision their garnet belongs; what method and units were used in calculating the data of col. A, table I and their meaning; what was the temperature of the carrier roll and, finally, has any effort been made to investigate the effects of particle shape on distribution in the electrostatic field? S. B. Hudson—I have read this article with great interest. We have been engaged in research work on the principles of electrostatic separation in this laboratory for some time now, and our findings agree with those of the authors in many respects. The article shows evidence of careful and valuable research in the field of electrostatic separation. A "distribution analyser," very similar to that described in an earlier article by one of the authors," was incorporated in an inclined plate-type electrostatic separator designed and built in the Melbourne University laboratory in 1948 for investigation purposes.22 The actual splitting edges were machined from y! in. per-spex, and the paper hoppers were supported on linen thread immediately below the perspex dividers. These dividers fitted into machined slots in a framework to give accurate Yz-in. spacings. The hoppers (staggered) fed directly into a rack of test tubes, which is supported on a vertical pantograph arrangement. The rack was positioned with guides on the horizontal pantograph stand, and this ensured positive alignment when replacing the rack after making weighings. In later work, when much heavier feed rates were used, of the order of 30 to 40 Ib per in. per hr a rack fitted with rectangular metal containers and similarly aligned was used. Some work was done here on comparing the distributions of minerals when passed separately and when passed as a mixture, and it was found that there was quite an appreciable difference in the two results.= However, in our separator the particles do not pass down the plate in a single layer, and this difference is probably caused by collisions of one mineral particles with the other mineral particles. In most of the investigational work here, the change of the center point of the distribution is measured to establish the effect of a variable, such as voltage. Two minerals (zircon and rutile) have been studied rather exhaustively, and it was found that their distributions are very nearly normal. Owing to the sharpness of the distribution curves, the usual method of obtaining the mean or median was inaccurate, and was not used; instead the mean (also the median), calculated on the assumption of a normal distribution, was used to locate the center point of each distribution and proved satisfactory. The effect of polarity becomes very apparent in the plate-type separator where frictional charges play a very important part when using highly resistive minerals such as zircon. With rutile, a comparatively conductive mineral, polarity of the electrode has little effect. On the other hand, the magnitude of the voltage has a far greater effect on conductive than on resistive minerals. Shiou-Chuan Sun (authors' reply)—Thanks are extended to Drs. Ralston and Fraas for their keen interest in this paper. Their questions concerning coal dust,

Jan 1, 1951

By Shiou-Chuan Sun, R. F. Wesner, J. D. Morgan

0. C. Ralston and F. Fraas—Dr. Sun and associates have presented an interesting paper not all of which is comprehended by us. The data assembled measure the deflections of particles in an electrostatic field as a function of a number of independent variables and some dependent variables that are not sharply differentiated. These data are all based on a Johnson type machine of definite, well-described geometry, something not often done in electrostatic separation literature. One new fact brought out by this technique is the effect of coal dust on admixed pyrite and quartz. The effects are opposite in character, as should be expected and we do not agree with the authors that these effects are negligible. Fraas' also used a multiple cell "distribution analyzer" and gives in fig. 5 of his paper a straight line plot with no humps or curves. This is not necessarily at variance with Sun's results because Fraas used a larger gap between electrodes and had no evidence of particles adhering to or dropping off the charged electrode. The section of Sun's paper on effect of surface conductivity contains a speculation that the dielectric constant "represents more or less the electrical conductance of the bulk body instead of the surface of the mineral particles." A simple picture of the meaning of the dielectric constant is that it is the specific inductive capacity of a dielectric when used as the dielectric between the plates of a condenser. It is at once evident that the above speculation confuses capacity with conductance—two definitely independent variables. We ask the authors to state in what group or subdivision their garnet belongs; what method and units were used in calculating the data of col. A, table I and their meaning; what was the temperature of the carrier roll and, finally, has any effort been made to investigate the effects of particle shape on distribution in the electrostatic field? S. B. Hudson—I have read this article with great interest. We have been engaged in research work on the principles of electrostatic separation in this laboratory for some time now, and our findings agree with those of the authors in many respects. The article shows evidence of careful and valuable research in the field of electrostatic separation. A "distribution analyser," very similar to that described in an earlier article by one of the authors," was incorporated in an inclined plate-type electrostatic separator designed and built in the Melbourne University laboratory in 1948 for investigation purposes.22 The actual splitting edges were machined from y! in. per-spex, and the paper hoppers were supported on linen thread immediately below the perspex dividers. These dividers fitted into machined slots in a framework to give accurate Yz-in. spacings. The hoppers (staggered) fed directly into a rack of test tubes, which is supported on a vertical pantograph arrangement. The rack was positioned with guides on the horizontal pantograph stand, and this ensured positive alignment when replacing the rack after making weighings. In later work, when much heavier feed rates were used, of the order of 30 to 40 Ib per in. per hr a rack fitted with rectangular metal containers and similarly aligned was used. Some work was done here on comparing the distributions of minerals when passed separately and when passed as a mixture, and it was found that there was quite an appreciable difference in the two results.= However, in our separator the particles do not pass down the plate in a single layer, and this difference is probably caused by collisions of one mineral particles with the other mineral particles. In most of the investigational work here, the change of the center point of the distribution is measured to establish the effect of a variable, such as voltage. Two minerals (zircon and rutile) have been studied rather exhaustively, and it was found that their distributions are very nearly normal. Owing to the sharpness of the distribution curves, the usual method of obtaining the mean or median was inaccurate, and was not used; instead the mean (also the median), calculated on the assumption of a normal distribution, was used to locate the center point of each distribution and proved satisfactory. The effect of polarity becomes very apparent in the plate-type separator where frictional charges play a very important part when using highly resistive minerals such as zircon. With rutile, a comparatively conductive mineral, polarity of the electrode has little effect. On the other hand, the magnitude of the voltage has a far greater effect on conductive than on resistive minerals. Shiou-Chuan Sun (authors' reply)—Thanks are extended to Drs. Ralston and Fraas for their keen interest in this paper. Their questions concerning coal dust,

Jan 1, 1951

By Norman Weiss

Most papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sul-phidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthate by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridan and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1919 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1949

By D. S. Sanders, E. W. Witcomb

FLOTATION tests, from which the flowsheet for the concentrator was determined, were made in a pilot mill at Chuquicamata and later comparative testing of full size flotation cells was done at the Andes Copper Mining Co. concentrator in Potrerillos. The principal sulphide copper mineral is chalcocite with varying amounts of covellite, enargite, and chalcopyrite. The oxidized portion is principally antlerite, a green basic copper sulphate. The gangue minerals include quartz, sericite, pyrite, feldspars and kaolin. Chuquicamata pit ores have proved to be hard grinding. The results of the flotation and metallurgical work prove that good extraction and concentrate grade can be obtained under a rather wide range of conditions. Metallurgy In general the metallurgy of the ore requires a fairly close control of the grind to the primary rougher flotation and of the regrind of the primary rougher concentrate before cleaning. Regrinding is necessary to reduce the insoluble content of the final concentrate since a large part of the middling combinations are between the copper and silica minerals. The alkalinity of the pulps can vary between wide limits and control of the percent solids gives the desired grind. Alkalinity Control Arroyo Salado water is supplied to the concentrator head tanks. It contains about 5000 ppm of salts but test work shows no deleterious effect. Actually this water permits a decrease of as much as 1 lb of lime per ton of ore as compared to San Pedro water, which is used for leaching oxide ore. About one quarter of the water flow through the concentrator will be new water from the reservoir. The remainder will be reclaimed from the thickeners. For primary grinding and rougher flotation, new and reclaimed water are combined in the head tanks. To avoid erratic results, only new water is used in the regrind system. Milk of lime is added to the rod mill feed chute to obtain the maximum benefit of mixing with the ore. This protects the equipment from corrosion due to entrained acids and soluble copper salts. Lime consumption is 3 to 5 lb per ton of ore. Grinding and Flotation The six bin gates over each belt feeder are opened in controlled combination and sequence to keep a live bed of ore in the bin to prevent arching and to obtain mixing. The milk of lime added ahead of the rod mill is regulated to suit rougher flotation requirements. The primary promoter reagent, Aerofloat 238, is added to the 10-mesh discharge of the rod mill as it is laundered to the ball mill scoop box. The classifier overflow is regulated to produce a grind of about 12 to 15 pct +65 mesh and 60 pct -200 mesh. A secondary promoter Z-4 (aml zanthate) and the pine oil frother are added in the overflow launder where a pH of 10 to 11 is maintained. Comparatively heavy beds of froth on the

Jan 1, 1952

By Norman Weiss

MOST papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in.small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sulphidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthatc by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridann and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1918 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1947

The meeting of the Institute at St. Louis brought together many members of the Women's Auxiliary, and Mrs. Philip N. Moore, who was nominated as the Director for the St. Louis Section, took the occasion formally to inaugurate the organization in that district. A meeting was held at the Planters Hotel, anti after discussion as to, the aims and objects of the. Auxiliary, officers were nominated for the' Section; the meeting then adjourned for two days, to he resumed in Joplin.. Here a very successful meeting was held, at which the Vice-Chairman, Secretary, and Treasurer were elected. A great deal of interest was arouse under the able directorship of Mrs. Moore the St. Louis Section is likely to become a large and active organization. The president of the Women's Auxiliary, in opening the meetings, told the ladies present of the inauguration of-the-Society in February, 1917, and of the work which had been accomplished up to date. She told how the Society devotes itself to patriotic and humanitarian work along lines acceptable and interesting to the Mining Engineer, standing always alongside and behind the men of the profession. The Central Welfare Committee of the organization has three Sub-Committees: Foreign Relief, Emergency, and Americanization, and under one or other of those heads most of the work of the' Society has been done. Mr. Hoover was responsible for the inception of the Foreign Relief Committee, as its first work was the collection of funds for the supplementary meals for the Belgian Children. Under the energetic administration of Mrs. H. Knox, this sub-committee raised $12,100 in the period between the February meeting and the Declaration of war by the United States, when our government took over the entire duty of feeding starving Belgium. The organization of the Belgian Relief Committee, as it was styled, still remains, but the members are now asked to take up the question of relief in France. The President, Mrs. S. J. Jennings suggested at the St. Louis meetings that one way of working for the foreign relief alight be that all the members of the Auxiliary should, during the period of the war, forego all giving' and receiving of Christmas presents, except those they have been accustomed to give to the poor or in charity, and those they would give to the men in the services of the United States; that the money usually spent on the Christmas gifts should be put into a fund to be sent abroad for the fatherless children of France, as a gift from the families of the Institute. A good deal of discussion followed this proposal, as some of the ladies felt that children should have their Christmas gifts as usual. The Director of the Section emphasized the truth that the Christmas spirit was the .spirit of giving and sacrifice, and that no sacri-

Jan 1, 1918

By H. H. Evinger, M. Muskat

A method has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-prcssure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. Introduction The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical prop-crties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.' Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of o to Ioo bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* Q ? u log r?/r? where k is the sand permeability, h its thickness, µ the liquid viscosity, ?p the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius re, and r? is the well radius. This gives the productivity factor: f= Q/kh?p ? 2p/µ log re/r? f=Q/ kh?p ? 2p/µ log re/r? which will have a numerical value for a

Jan 1, 1942

By M. Muskat, H. H. Evinger

A method has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-prcssure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. Introduction The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical prop-crties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.' Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of o to Ioo bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* Q ? u log r?/r? where k is the sand permeability, h its thickness, µ the liquid viscosity, ?p the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius re, and r? is the well radius. This gives the productivity factor: f= Q/kh?p ? 2p/µ log re/r? f=Q/ kh?p ? 2p/µ log re/r? which will have a numerical value for a

Jan 1, 1942