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By AIME AIME

FRANK T. SISCO is a native of Lawrence, Kansas. He received his earlier education in Clinton, Iowa and his university training at the University of Illinois. His experience in the steel industry has included service in the chemical, testing, and metallurgical departments of the Illinois Steel Co., of South Chicago; the Hess Steel Corp., of Baltimore; the IJ. S. Naval Ordnance Plant at Charleston, W. Va.; and the American Steel and Wire Co., Waukegan, Ill. He severed for seven years as chief of the metallurgical laboratories of the U. S. Army Air Corps at Wright Field, Dayton, before coming to New York in 1930 to become metallurgist and editor of the Alloys of Iron Research, the position he now holds.

Jan 1, 1940

MAY 17-The last bit of verbal sod had hardly come to rest on the grave of the coal industry-which grave was being eagerly dug with typewriters and microphones by administration hangers-on and even an operator or two-when its leaders gathered for the 1950 Coal Convention of the AMC in Cincinnati on April 24. Surprisingly, mourning clothes were not being worn but the boys had on their diggers preparatory to digging their way out from under the muck. High costs created by wage and welfare demands, together with work stoppages, have caused markets to shrink, but even so, an optimistic air still prevailed as new techniques were disclosed at technical sessions. The administration, however, came in for its share of knocks.

Jan 6, 1950

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By D. Harker, E. Epremian

The constitution of the nickel-tungsten system has been studied by a number of investigators, the most recent of which are Ellinger and Sykes.1 On the basis of metallography, electrical resistivity and hardness measurements and some X ray diffraction work, they constructed a consitution diagram (Fig 1). Ellinger and Sykes report a0 for the alpha face-centered cubic phase (nickel saturated with tungsten) as 3.66?.‡ The gamma phase (tungsten saturated with nickel) is given as body-centered cubic, but no value of a. is recorded. At 43 pct tungsten by weight (approximately 20 at. pct) a beta phase is reported, but structure and lattice parameter are not known. Primarily on the basis of metallographic evidence, they conclude that beta is a new phase and rule out the possibility of formation of a superlattice since they- observe a new phase in the microstructure. Grube and Schlecht2 report an ordering reaction in a system similar to the Ni-W (Ni-Mo) and Harker3 has shown that NirMo forms a superlattice upon the pre-existing face-centered cubic lattice of the alpha phase. Elliniger arid Sykes observed a change in the diffraction pattern of a 4.3 pct W alloy upon aging and attributed it to the formation of a new phase. Thus, there appears to be some question as to the character of the beta phase reported by Ellinger and Sykes. The purpose of the present work is to determine precisely the structure and nature of the beta phase in the Ni-w system of X ray diffraction methods. Experimental Procedure One inch diameter ingots of 43.66 pct, 40.15 pct and 34.06 pct .tungsten by weight (19.8, 17.6 and 14.1 at. pct respectively) were melted and cast under vacuum from electrolytic nickel and pure wire filament grade tungsten. The ingots were soaked for 16 hr at 1300°C in a hydrogen atmosphere furnace, then swaged at this temperature and finally drawn to 0.020 in. diam wire. Some of the bar stock was retained in 1/2 in. diam rod for hardness and metallographic studies. Wire samples for diffraction work were sealed in evacuated quartz tubes and subjected to the various solution and aging heat treatments in a hydrogen furnace. X ray photograms were taken in a Debeye-Slierrer camera using copper K radiation filtered by nickel foil. Results X RAY DIFFRACTION The lattice parameters of the alpha and gamma phases at saturation were determined by an X ray photogram of the 19.8 at. pct W alloy after solution heat treatment at a temperature well within the alpha-gamma range above the peritectoid temperature (17 hr at 1150°C—oil quenched). The alpha phase was found to be face-centeted cubic with a. of 3.594 ± 0.001?, while the gamma phase was determined as body-centered cubic with a. of 3.158 ± 0.001?. Exactly the same phases and parameters were ohtained with the 17.6 at. pct W alloy for the same solution heat treatment. Thorough analysis was made of an X ray photogram of a 19.8 at. pct alloy sample in the quenched and aged condition (solution treated 1T hr at

Jan 1, 1950

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.' Preliminary results on the rate of evaporation of zinc were described in a previous publication.' The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

By L. L. Gray, D. W. Reed, F. Morgan

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948

By F. Morgan, L. L. Gray, D. W. Reed

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2'4'5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.' Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By D. Turnbull, R. E. Cech

THE supercooling behavior of pure liquid metal droplets has been described.' The solidification behavior of small droplets of Cu-Ni alloys as a function of composition is described herein. The Cu-Ni system is of interest for such an investigation because the components are miscible in all proportions in both the liquid and solid state and the phase diagram of the system, Fig. 1, is a type often encountered in metal systems. It was noted by Van Riemsdyk2 and others that the nature of the "blick" of gold droplets during assaying is not perceptibly affected by the content of the platinum group metals that are soluble in both liquid and solid gold. With the exception of these very qualitative observations there appear to have been no prior investigations of the supercooling of alloy droplets. A series of nine alloys varying in composition by 10 pct (nominal weight) steps was made using certified OFHC copper, 99.996 pct purity, obtained from the American Brass Co., and electrolytic nickel pellets, 99.92 pct purity, obtained from the International Nickel Co. The alloys were melted and cast in vacuo in a high frequency induction furnace. Segregation was minimized by chill casting into 1-in. diam steel molds. Each alloy rod was homogenized at a temperature 50°C lower than the solidus for 100 hr in dry hydrogen. Samples for solidification experiments and chemical analysis were machined from the same portion of each rod and at a depth of in. from the rod surface. A Car-boloy tool was used in taking turnings to minimize contamination of sample by the cutting tool. As a check, a number of samples for microscopic observation were chipped from the ingot with a fragment of pyrex glass. The resultant data in all cases agreed, within experimental error, with the data obtained from machined turnings. A number of small particles, 30 to 50 micron diam, of a Cu-Ni alloy were placed in a quartz vial 1/32 in. diam x % in. long. This was inserted into a platinum ribbon heater and mounted in a high temperature microscope stage. The general procedure followed in inserting samples into the stage and measuring the temperature of melting and solidification was the same as described in an earlier paper.' A chromel-alumel thermocouple was used to study alloys of 88.93 pct Cu, 80.62 pct Cu, and 72.27 pct Cu. A platinum-10 pct rhodium thermocouple was used for the remainder of the alloys. Procedure The assembled high temperature microscope stage was first evacuated and the sample given a 2 min in situ treatment at 900 °C in dry hydrogen to remove surface oxides which might otherwise catalyze crystal nucleation. After this treatment the atmosphere was changed to purified helium and melting and solidification were observed microscopically. It was not possible to determine the solidus with certainty. However, the liquidus temperature was measured very accurately since the surface of the particle changed in appearance from coarse and uneven to smooth, mirror-like within a few degrees. The visually determined liquidus temperature was checked by finding the highest temperature to which the particle could be heated such that it did not supercool upon lowering the temperature. This temperature which checked within experimental error with that found by observing surface change was assumed to be characteristic of the thermody-namic liquidus. In order to minimize the effect of selective evaporation of copper from the alloy, samples were changed frequently and the droplets were heated no more than 50 °C in excess of the liquidus temperature T,. When the latter conditions were fulfilled, T, values were reproducible. After melting, the temperature was decreased slowly until the particles solidified. The sudden release of heat of fusion on solidification caused the

Jan 1, 1952

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By S. Weinig, E. S. Machlin

IN a previous study of the grain boundary stress relaxation phenomenon,' the authors had arrived at the conclusion that two successive steps were involved in the complete relaxation of stress at a grain boundary. These two steps were grain boundary migration and grain boundary slip. It was further suggested that the slower of these two processes is rate controlling. In an attempt to ascertain the validity of the above, a study of grain growth kinetics on the same alloys used for the previous study was undertaken. Separate wire specimens, 0.030 in. diam, in the same as-deformed state (99 pct reduction in area) as in the previous investigation were heated to the various temperatures for a sequence of times. The compositions used and the temperatures of testing are summarized in Table I. A statistical determination of grain size was then made on each specimen, using the average length of traverse between boundaries as a measure of the grain size. Examples of typical results obtained are shown in Figs. '1 and 2. The grain growth law D = ktn was found to fit most of the data. Using this relation, values of the grain growth exponent n were calculated and the inter -esting dependence of n on solute content shown in Figs. 3 and 4 was then obtained. Also, it was found that the constant K which was obtained from extrapolation is roughly independent of solute content. (K is uncertain to within ±25 pct.) An estimate of the activation energy for grain growth was made using the technique of Burke? This method utilizes the plot of the reciprocal of time necessary for the grain size to increase from a definite starting size Do, to a final size D, for each isothermal heat treatment. The slope of this curve corresponds to the heat of activation for the process. In Fig. 5 the rate of grain growth is plotted against the reciprocal of absolute temperature. The activation energies were obtained from these curves and are summarized in Fig. 6. Discussion It is interesting to note that the same saturation in the variability with concentration has been found for the grain growth exponent n in this research as was found in the previous researches on both grain boundary stress relaxationa and internal friction of dislocation origin." The significant feature is that saturation in the variation of these properties has been found to occur at about the same level of solute concentration, namely, between 0.1 and 0.5 atomic pct. The only characteristic common to these different quantities is that solute adsorption at grain boundaries and dislocation can take place and affect these values in a similar fashion. Thus, it is concluded that the grain growth exponent n depends upon solute adsorption at the grain boundaries. It appears, therefore, that theoretical considerations leading to the contrary conclusions5,6 have not treated the real process by which solute atoms exert their effect on grain growth. Prior to the analysis of the observed activation energies, certain of the aspects of the aforementioned grain boundary stress relaxation investigation will be briefly reviewed. It was found that with the addition of solute atoms the grain boundary stress relaxation peak (internal friction vs temperature) decreased in intensity. Simultaneously a second peak was observed which increased with increasing solute atoms. Both of these peaks were shown to be the result of grain boundary stress relaxation. They have been termed, respectively, poire peak and solute peak. It was suggested that the solute peak was dependent upon grain boundary migration, whereas the pure peak was a manifestation of grain boundry slip. Activation energies for both peaks were obtained as a function of Solute content. The value of the activation energy in the temperature range corresponding to the solute peak was

Jan 1, 1958

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

Discussion of the paper of W. H. Gunniss, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 81, September, 1913, pp. 2309 to 2310. PROF. J. W. RICHARDS, South Bethlehem, Pa. :-In regard to the physical nature of quartz for making silica brick, is the coarse-grained preferable ? E. P. MATHEWSON, Anaconda, Mont. :-A dense quartz is preferable. The quartzite is the actual material used by the Anaconda Company. The sandstone referred to, the foreign quartz, was a very pure sandstone and bad hardly any impurities in it, and the brick made from that particular material, while apparently beautiful while coming out of the kiln, and true, immediately on heating in the furnace buffed up half an inch and were cracked open.

Jan 11, 1913

IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman .A. A. STEVENSON, Vice-Chairman HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. Guilliaem Aertsen, Robert W. Hunt, .-E: Gybbon Spilsbury, John Birkinbine, J. E. Johnson, Jr., J. S. Unger, William H. Blauvelt, William Kelly, Felix A. Vogel, Charles A. Buck, Charles Kirchhoff, Leonard Waldo, James Gayley, Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, William R. Webster, Henry M. Howe, C. F. W. Rys, Frederick W. Wood. Manuscripts of the following papers on iron and steel for the February -meeting have been received and accepted: Albert Sauveur, Notes on Heating and Cooling Curves of Professor Carpenter's Electrolytic Iron. H. M. Howe and A. G. Levy, Notes; on the Plastic Deformation of Steel during Overstrain.

Jan 2, 1914

THE task of the smith who works in iron is very laborious, indeed far more so than that of the coppersmith just described. For he also handles heavy weights continually, and stands constantly erect be- fore the fire of the forge, since the hardness of the iron cannot be softened except by means of heating and boiling it well. In this place he continually moves his body, now thrusting the iron into the heart of the fire with large thick tongs, now removing it to look at it and to put sand, tuff, or other earth over it, now putting on fresh charcoal, now moistening and slowing down the fire, and now cleaning it. Finally, while the iron is hot

Jan 1, 1942