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By Edmund C. Pechin

I REGRET that I am unable to present this subject in definite form and detail. All I shall attempt at this meeting is to lay before you some curious facts, the bearings and explanations of which must be reserved for future consideration. I hope before the next meeting to have carried experiments far enough to furnish a more important contribution to the science of iron metallurgy. The Wickersham process consists in the introduction into the molten metal, as it runs from the furnace, of air from the hot blast. Mr. Samuel Wickersham is the originator of the plan, as applied in practice, although Mr. Martien had the idea a long time ago, and, I believe, .went to England about it. But at that time Mr. Bessemer was coming before the public with his invention, which engrossed the attention of iron-masters, and Mr. Martien accomplished nothing. The principal difficulty in our experiments at Dunbar was to get a practicable runner or trough, through which the molten metal should pass, and in which it should be exposed to the action of the blast. The runner we used was ten feet long, and perforated on the sides to permit the entrance of the air-currents. When we used a cast-iron and fire-clay runner, the heat was so great that before we were more than half done with a run, the lower part of the runner was melted, and we had a magnificent Fourth of July display of fireworks until the blast was shut off. We had to abandon fire clay. The runner with which we have had the best success ,is made of wrought-iron tubes, 2 1/2 inches in diameter, attached to a wrought-iron frame, and lined with a mixture of crushed conglomerate (quartz) and a little fire clay to give it cohesion. The wrought-iron shell curves inward over the upper edges, so as to catch and throw back into the current the flying sparks and particles of metal thrown out by ebullition. With this we have been able to run 12 to 14 tons at a heat with great ease. Mr. Wickersham has since prepared this material (pounded quartz) into a shaped brick or tile, with the necessary perforations for the passage of the air, which promises to answer every requirement for steady working. As regards the improvement in the quality of the iron, there seems to be no question. A large number of practical tests were made in

Jan 1, 1873

By Dwight H. Seely, Louis R. Records

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

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

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

Jan 1, 1951

By G. W. Neighbor, M. S. Abrahams

The actice slip plane in InSb is found to be of the {111} type by using the method of two-tmce anulysis. Measurements of the rotation of the tensile axis with increasing plastic shear strain indicate that the tnacroscopic slip direction is a <110>. Recrystal-lization is first observed at a sheav strain of about 70 pct for a crystal deformed at a temperatzcre of 473° C and at a shear strain rate of 2.90 times 10- %ecc-I; the dislocation density corresponding to this value of the strain is 1 x 108 em-&apos;. At a shear strain of about 170 pct, the recrystallization process is complete. This appears to be the fimt time re-crystallization has heen observed in a semiconductor. V HE operation of the {Hi} glide plane in Ge was first noted by Gallagher.&apos; This finding was confirmed by Treuting who also extended the result to Si. Using X-ray techniques, Treuting3 demonstrated that the macroscopic slip direction in Ge was of the <110> type. The choice of the (111) <110> slip system in Ge is exected since in the diamond-type structure the {Ill7 plane is the plane of highest density and the <110> direction is the direction of closest packing.4 There is little reason to expect that the glide elements of InSb are different from those of Ge, since the zinc-blende structure characteristic of InSb is quite similar to the structure of Ge. With regard to InSb, Allen5 has indicated that the glide plane is the {111} type. There appears to be no quantitative determination of the glide direction, however. The present work was undertaken to establish both the glide plane and glide direction in InSb and also to see if recrystallization occurs at large shear strains. EXPERIMENTAL PROCEDURE Mechanical Deformation. The single crystals of InSb used in this investigation were deformed in uni-axial tension. The tensile axis of the specimens was [145] and the periphery was bounded by (111) and (321) planes as shown in Fig. 1. The metallographi-cally polished specimens were deformed in a dynamic atmosphere of He, using an Instron machine. The tensile tests were performed at temperatures in the range of 300°C to the melting point (525OC) and at shear strain-rates varying between 1.94 X 104 sec-&apos; to 1.94 x 103 sec-&apos;. Additional details concerning the preparation and deformation of the specimens have been presented previously.&apos; Analysis of the Glide Elements. The traces of the active slip plane in both (111) and (321) planes were analyzed according to the usual method of two-trace analysis." The macroscopic slip direction was determined by measuring the rotation of the tensile axis as a function of plastic strain,8 These measurements were made from Laue back-reflection X-ray photographs. The X-ray beam was perpendicular to the (111) plane. A given crystal was used for only one measurement of the rotation of the tensile axis after it had been strained to a predetermined value. Therefore, care was taken at all times to insure that the X-ray beam was parallel to the [Ill ] direction of all the samples. RESULTS AND DISCUSSION Glide Plane. After 3.4 pct plastic shear-strain, at a temperature of 369°C and a shear strain-rate of 1.94 x 104 sec-&apos;, the slip traces on the (111) and (3.21) planes appear as in Figs. 2(a) and 2(b), respectively. The results of an analysis of these glide markings demonstrate that the slip plane is (111). The operation of this plane is expected on the basis of the orientation of the specimen, since glide on this plane and in the [I011 direction will result in

Jan 1, 1962

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,&apos; and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson&apos; determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12&apos;13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer&apos;s personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company&apos;s office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893

By E. G. Spilsbury

AS a fresh illustration of the advances made in the past few years in the overhead-cable systems of hoisting and conveying, as applied to open-cut deep mining and quarrying, I would call attention to a further development of this system of transportation which has lately been put in operation i-n this State. A few miles above Williamsport, on the Susquehanna river, the Glen Union Lumber Company, of Pottsville, Pa., owned a large tract of valuable timber-

Jan 1, 1892

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By Forrest F. Craig

Both early and more recent1 laboratory measurements of gas-oil relative permeabilities were made by subjecting oil-saturated cores to external gas drives. In these runs it was generally assumed that the flowing gas/oil ratio was constant at every point throughout the core. Using this assumption, the resulting equation for the gas-oil relative permeability ratio becomes A where Q is the flow rate at the producing end of the system. This relative permeability was then specified for the average saturation of the core. The assumption and resulting equation fail to recognize that in an external drive, the oil flow rate varies from zero at the injection end to a maximum at the producing end. The assumption also fails to consider the existence of a saturation gradient during an external drive. This saturation gradient is due solely to non-steady-state flow. Some authors2,3,4 have used this erroneous method of calculating relative permeability ratios from external drives. Other authors5,6,7 have used relative permeability ratios in calculating expected field performance by external drive, using Equation (1) and making the incorrect assumption that the saturation is uniform within the driven portion of the reservoir. To find the correct relation between the relative permeability. ratio at the average saturation and the produced gas/oil ratio, the insertion in Equation (1) of a factor, F, to adjust it for oil velocity gradient has been considered. The equation then takes the form Assuming that the oil velocity is directly proportional to the distance from the injection point leads to the conclusion that, for a linear system, the average oil velocity is one-half that at the producing end. Thus, the average gas/oil ratio is twice the produced gas/oil ratio, and Equation (2) is transformed into However, here again the existence of a saturation gradient is not recognized. The produced gas/oil ratio is related to the relative permeability ratio at the saturation of the outlet end of the system. It can be shown quite readily that, if the true log k,/k, saturation relationship is linear over small ranges of saturation, then d log kjko Where aaxv and u2 are the average and outlet saturations, respectively. Examination of Equation (3) shows that the factor F cannot have a single value over the whole saturation range. Another method of dealing with external drives is that of Buckley and Leverett.&apos; Their method, which assumes no gas expansion and outlet end effects, considers fully the saturation gradient present due solely to the displacement mechanism during an external drive, and applies Equation (1) to each point along this gradient. The calculation of production history using relative permeability ratio is straightforward. However, the calculation of relative permeability ratios from production history by this method is impractical. In a recent paper, Welge,1 using an approach similar to that of Buckley and Leverett, presents a simplified method for determining the saturation at the producing end of the system. At thi; saturation, the relative permeability ratio calculated by Equation (1) applies exactly, after breakthrough of the stabilizej front. By this method, relative permeability ratios or production history may be calculated with equal ease. Use of this method as a laboratory tool in determination of relative permeability ratios by external drive requires the knowledge of the total injected fluid volume; in addition to the average saturation and producing ratio. As a preliminary test of this method of calculation, laborntory external gas drives were run on a 3% in. diameter, 11 in. long sample of Nellie Bly consolidated sandstone. This core sample had a permeability of 824 md and a porosity of 28.1 per cent. The driving fluid was air. Three different oils were used, having viscosities of 1.4, 9.8, and 125 cp, respectively. The runs were made under identical pressure differentials,

Jan 1, 1952

By M. Hansen, C. C. Wang

THE 6 phase of the Cu-Sn system (Cu,Sn, = 32.53 pct Sn) was considered to be stable down to room temperature until Owen and Iball showed by X-ray analysis that it undergoes a eutectoid decomposition into the a and e phases at a temperature near 300°C. Their findings have been confirmed by other investigators,2-5 a11 of whom used X-ray diffraction studies of powdered specimens. The transformation temperature has been reported by various authors as lying between 300" and 380°C. To our knowledge, no microscopic evidence of the eutectoid reaction has been published, as yet. It was in connection with other work that longtime annealings at 300°C were conducted with alloys containing 22, 32.6, and 35 pct Sn (nominal compositions) prepared from electrolytic copper and electrolytic tin and cast in a small iron mold. The specimens were first annealed at 700°C for 5½ hr and quenched from 400 °C after cooling to, and annealing at, that temperature for 9½ hr. After this treatment the sample with 22 pct Sn was cold worked for 15 pct reduction in thickness; the 32.6 and 35 pct alloys were too brittle to be cold worked. The final anneal at 300°C was done in a sealed pyrex glass bulb for 63 days. Fig. 1 represents the microstructure of the annealed alloy with 22 pct Sn. It shows primary a solid-solution crystals in a matrix of the (a + 8)-eutectoid formed at 520 °C. The a crystals contain 8 inclusions which precipitated from a due to the decrease in the solubility of tin in copper with fall in temperature. The decomposition of the 8 phase into a (light) and E (dark) can clearly be seen in some areas of the (a + 8)-eutectoid matrix. However, the decomposition is far from being completed, even after the long-time anneal used. Figs. 2 and 3 depict the microstructures of the annealed 32.6 pct alloy, which was intended to consist entirely of 6 phase. Due to some loss in copper on melting, the composition is slightly higher in tin. Accordingly, the sample after quenching from 400 "C consisted of grains of the 8 phase with the e phase arranged along the grain boundaries and as a Wid-manstatten precipitate within the 6 grains. After an annealing time of 63 days, the eutectoid decomposition, 6 + a + e, is still in its early, initial state. The pearlitic type of eutectoid is nucleated at the c crystals, preferably those surrounding the grain boundaries of the 8 phase. The appearance of the (a + €)-eutectoid in the 35 pct Sn alloy was very similar to that shown in Figs. 2 and 3. Again, the eutectoid decomposition nucleated at the 6 phase and proceeded from there into the 8 areas. As is evident from Fig. 2, the rate of decomposition of the 6 phase at 300°C is extremely sluggish: In the representative area shown only about 5 pct of the 8 phase has undergone the eutectoid trans- formation after annealing for 63 days. On the other hand, Owen and Williams2 have reported that X-ray photographs of powdered samples with between 17.5 and 34 pct Sn did not show 8 lines after annealing for only five to seven days at 300°C. This is in accordance with the fact that the rate of reaction in powdered samples is higher than in massive specimens, as a result of the excess free energy of the powder (due to its greater surface area). The authors wish to express their thanks to C. A. Johnson for preparation of the micrographs.

Jan 1, 1952

By J. Gurland

The effect of four different second-phase additions on the strength of composite alloys with a common matrix was investigated. The four compositions each consisted of 85 pct by volume of silver with additions of 15 pct of either tungsten, molybdenum, tungsten carbide, or nickel. These particular additives were chosen because of their low mutual solid solubilities with silver at room temperature, the alloys consisting essentially of a dispersion strengthened silver matrix in which the second phase is distributed randomly. Test specimens were prepared by a powder metallurgy procedure consisting of ball milling the mixed powders, compacting, and sintering at 920°C for 1 hr in hydrogen. The constituent powders were of CP quality and of particle size between 2 and 10 ?. The compacts were subsequently hot pressed at 1000 psi and 1400° in an Inconel die, coined at room temperature at 60,000 psi and finally annealed and outgassed in vacuum at 800°F. The microstructures of the alloys are shown in Fig. 1, and the microscopically observed porosity grade was A-2 or better as evaluated by ASTM Recommended Practice B 276-54. The properties of the sintered compacts are listed in Table I, and the load-deformation curves in bending are shown in Fig. 2. The samples, of rectangular cross section, were loaded at the center of 58 in. span, and the reported stress was calculated on the basis of linearly elastic behavior in order to allow the comparison of specimens of slightly different dimensions. It is apparent that the tungsten, molybdenum, and tungsten carbide alloys exhibit very similar deformation curves. The moduli of elasticity were determined from the slopes of the stress-deflection curves at small loads. The measured values agree quite well with those calculated by the strength of materials approximation proposed by Paul1 for the elastic constants of mixtures, the calculated values being 15.0, 15.0, 17.4, and 13.4 million psi, respectively, for the tungsten, molybdenum, tungsten carbide, and nickel combinations with silver. The strength of the Ag-Ni composition is appreciably lower than that of the other three alloys. The discrepancy between the two groups is accounted for by the following characteristics of deformation and failure which were observed microscopically during the tests: A) The deformation of the W, Mo, and WC alloys did not involve the second phase particles to any appreciable extent. Slip and fracture took place in the silver-rich matrix alone, although the fracture path generally skirted the particles by favoring the phase boundaries. The deformation proceeded according to the following sequence: 1) formation of small, discontinuous microcracks in areas of the matrix adjacent to a particle, 2) general slip in the matrix and extension of cracks, 3) failure of specimens by propagation of cracks through matrix. The near coincidence of the 3 load-deflection curves suggests that the nature of the second phase particles does not decisively influence the plastic behavior of composite alloys of this composition as long as the particles do not undergo any considerable deformation themselves. B) A markedly different behavior was exhibited by the Ag-Ni composition where the relatively low flow strength is associated with the low yield strength of the nickel grains. Slip in the nickel grains was first observed at a stress of approximately 10,000 psi, although failure, at a later stage, took place by the propagation of cracks through the matrix. The ductility of this aggregate, in which both components deform plastically, is appreciably greater than that of the elastic-plastic composites. In summary: 1) The measured values of the moduli of elasticity of the composite alloys under discussion are in good agreement with the "strength of materials" approximation proposed by Paul.&apos; 2) The overall plastic behavior of these particle-strengthened alloys is unaffected by the nature of the second phase particles, if the latter remain elastic. This work was supported by the Office of Naval Research. The experimental results are presented

Jan 1, 1962

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By Stephen Royce

[PAGE Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine (TP 2000 by JOHN W. VANDERWILT, Min. Tech., May 1946. Discussion by STEPHEN ROYCE and the Studies of the Design of Shaped Explosive Charges and Their Effect in Breaking Concrete Blocks (TP 2157 by GEORGE B. CLARK, Min. Tech. May 1947. Discussion by PHILIP B. BUCKY, V. H. CLARK, E. D. GARDNER, M. H. HAWKINS, H. L. WALKER, and the author) 2 See TP 2377, Min. Tech., May 1948 for discussion of San Manuel ProsPect (TP 2255 by H. J. STEELE and G. R. RUBLY, Min. Tech., Sept. 1947. Discussion by L. KENNETH WILSON, ELDRED D. WILSON and the authors)] Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine STEPHEN ROYCE•-It is interesting to note from B, Fig 2, how closely the subsidence limits approximate to the 60° angle of draw, which is so commonly found to rule in large scale rock subsidence. The tension cracks shown at B are commonly found in the initial stages of subsidence movement and spread like a halo about subsidence limits as movement extends. These tension cracks usually grow into escarpments later on. Apparently from the illustrations and description given, a system of vertical fractures is the predominating weakness in the wall rock at Climax, and therefore both tension cracks and escarpments are prevailingly vertical in attitude. The illustrations in Mr. Vanderwilt&apos;s article seem to conform to the general rule that yield by subsidence is heralded by tension cracks which foreshadow the appearance of the subsidence scarps which are both described in the paper and shown in Fig 2. The difference between the B side and the A side of Fig 2 is apparently caused mainly by the vertical fracturing which controls subsidence at Climax as compared to the relatively homogeneous rock formation at A upon which the original figure in Peele&apos;s Handbook was based. The draw at B is exactly 60°, while the draw at A is a little flatter. The influence of the vertical fractures explains the difference. The surprising feature is the relatively small deviation from the general 60° draw line, which is about the average of rock subsidence experience. The influence of local fracture systems, faults and bedding in controlling subsidence all the way from extremely low angles of draw to vertical is rather fully discussed in the Peele&apos;s Handbook article referred to. The more illustrations of subsidence there are published the better will be our knowledge. The general principles are pretty well established. The wide local differences reflect the effect of local conditions. This paper is a very valuable contribution to the subject, and for the benefit of the mining industry, it is to be hoped that there will be many more such clear and concise presentations. Particularly block caving is apt to be of greatly increasing importance in the future of a mining industry that must meet high labor costs. More examples of block caving from small scale to large scale operations like those at Climax will serve a vital need. JOHN W. VANDERWILT (author&apos;s reply)-I would like to thank Mr. Royce for his discussion; however, in his comments the meaning of subsidence, draw and tension cracks is not entirely clear. As used in my discussion of subsidence at Climax, subsidence refers to movements involving appreciable downward displacement. Tension cracks indicate only

Jan 1, 1947

OFFICERS OF THE WOMAN&apos;S AUXILIARY AIME President-Mrs Robert D Coombs, 375 Paramus Road, Paramus, N J First Vice-President-Mrs W McG Peirce, Troy Court 73 F, New England Avenue, Sum¬mit, N J Second Vice-President-Mrs Andrew E Beer, Richardson Avenue, Sea Cliff, Long Island, N Y Third Vice-President-Mrs Ira T Hook, 494 Norton Parkway, New Haven, Conn Fourth Vice-President-Mrs John R Kenney, 427 W Wrightwood Avenue, Chicago 14, Ill Fifth Vice-President-Mrs Alfonso Ballon, Montero Rosas 115, Barranco, Lima, Peru Recording Secretary-Mrs Arnold H Miller, 601 West 115th St, New York 25, N Y Assistant Recording Secretary-Mrs R J Mechin, 66 East 79th Street, New York 21, N Y Corresponding Secretary-Mrs Theodore Nagel, 76 Remsen St, Brooklyn 1, N Y Treasurer-Mrs Robert W Rowen, 116 East 68th St, New York 21, N Y Assistant Treasurer-Mrs Samuel H Dolbear, 11 Broadway, New York 4, N Y Assistant Treasurer-Mrs H A Kursell, 12 Murray Hill Road, Scarsdale, N Y

Jan 1, 1956

By Mark J. Klein, Robert A. Haggins

The pesence of a small amount of oxygen was found to cause significant grain growth restraint in 99.99 pct Ag. This behavior does not seem to be due to the presence of an oxide dispersion, but instead, to be related to the existence of minute amounts of oxygen m solid solution. In the amounts necessary to cause the observed effects it was found that oxygen migrates with extreme rapidity, probably along extended structural imperfections, such as dislocations and grain boundaries. A number of years ago, hastton&apos; observed that the presence of small amounts of oxygen caused a retardation of grain growth in silver. He attributed this behavior to the formation of a fine dispersion of oxide particles by the internal oxidation of trace impurities. More recently, wood2 also found that oxygen caused grain growth restraint in copper. Experiments using both copper and a dilute solution of aluminum in copper led to the conclusion that the effects observed in copper were due to oxygen in solid solution, rather than an oxide dispersion. During the course of a study of the influence of several solutes on the recrystallization of Silver, the presence of minute amounts of oxygen was found to exert a very significant influence on grain growth. The experiments reported here were undertaken to determine whether the grain growth restraint observed in silver due to the presence of oxygen is related to oxygen in solution or to an oxide dispersion. Because of the difficulty in measurement and control of the very small oxygen concentrations causing the observed effects no attempt was made to treat the data in a quantitative manner. EXPERIMENTAL PROCEDURE AND RESULTS Silver of 99.99 pct purity was melted and cast into slabs in a vacuum of better than 0.1 p. These slabs were reduced 50 pct by cold rolling to a thickness of approximately 2.5 mm. Samples cut from this material were annealed in vacuum for a series of different times at 803°C. Another group of samples was similarly annealed in air. This temperature is well above the recrystallization range for silver of this purity (150" to 200°C). The mean grain diameter of these samples was measured, both in the center and near the edge, using the line-intel-cept method, and is shown as a function of annealing time in Fig. 1. The grain size in the centers of the samples annealed in air was found to be larger than that of the surface regions, while the grain growth behavior of the edge and center regions annealed in a vacuum was approximately the same. he edge measurements were taken at a distance of 0.2 mm from the surface.) A few samples were annealed in nitrogen. Their behavior was identical to that of the vacuum-annealed samples. Samples annealed in oxygen had approximately the same grain growth behavior as those annealed in air, leading to the conclusion that this behaviouer is due to oxygen. The microstructure of a sample annealed in air at 803" for. 30 minutes is shown in Fig. 2. The smaller grain size near the surface is characteristic of the iir-annealed specimens. Possible causes of this grain growth restraint in the air-annealed specimen are the formation of an im-

Jan 1, 1962

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By R. A. Anderson, T. E. Tietz, J. E. Dorn

Recent investigations1,2,3,4 have conclusively shown that the strain hardened state of metals depends upon the temperature and strain rate of pre-straining as well as on the total plastic strain. A typical example of the effect of temperature of prestraining on the work hardening of metals is reproduced in Fig 1. When pure aluminum is strained at liquid nitrogen temperature the upper solid stress-strain curve (OFGH) is obtained. But when pure aluminum is prestrained to e2 = 0.153 at atmospheric temperature and the test is then completed at liquid nitrogen temperature, the curve OBCD results. Thus a prestrain E2 = 0.153 at atmospheric temperature gives a flow stress C when continued at liquid nitrogen temperature, whereas a higher flow stress G results when the specimen is strained exclusively at liquid nitrogen temperature to the same strain E2. Consequently the metal strain hardens more rapidly at the lower temperature. Obviously the strain alone is not a measure of the strain hardened state in metals. Inspection of Fig 1 reveals that the flow stress at C is identical with that at F. This fact suggests that a strain E2 = 0.153 at atmospheric temperature induces the same work hardened state as a strain E1 = 0.058 at liquid nitrogen temperature. But this concept of equivalent strains is also in error. If curve CD is shifted to the left so that point C falls on F, point D becomes D&apos;. Inspection of the curves reveals that the rate of increase of stress with strain at C is greater than the rate of increase of stress with strain at F even though the flow stresses are identical. Consequently C and F do not represent identical work hardened states. It therefore becomes important to ascer- tain how the strain hardened states at C and F might differ from each other. In a more recent report1 it was shown that straining at higher rates of strain increases the amount of strain hardening in a manner quite analogous to straining at lower temperatures. These observations suggested that the flow stress is not only a function of the strain but also a function of the strain rate-temperature history of straining, perhaps in accord with the Zener- ?H Hollomon parameter p = Ee /RT (where

Jan 1, 1950

By Louis A. Panek

THE purpose of this paper is to present a method of designing safe and economical arch structures that are to be constructed of concrete or directly of original earth materials. The experimental data used to illustrate the design method are taken from Bucky and Fentress,1,2 and the application of the ideas presented by them is extended by obtaining an additional set of curves from which arch structures may be designed. This design method is based upon the following principles of similitude: A scalar model made of the same material as that of the full sized structure will behave similarly to its prototype if the density of the model is increased in the same proportion as its linear scale is decreased. Let R represent the scale or model ratio, namely, the ratio of a prototype linear dimension to the corresponding model linear dimension. The effect of increased density may be obtained by rotating the model in a centrifuge at a speed such that the centrifugal field exerts on the model an accelerative force R times the accelerative force of gravity. Under these conditions; (I) model unit stresses are equal to corresponding prototype unit stresses, (2) the ratio of the prototype deformation at a given point to the model deformation at a similar point is equal to the scale ratio, R, and (3) the model and the prototype will behave similarly within and beyond the elastic limits of strain. According to the above relations, such models can be used to solve the following problems: I. The dimensions of the most economical safe arch structure for a given load. 2. The maximum safe roof span underground for given geologic conditions. The procedure is described briefly as follows. Tests are made by rotating in a centrifuge a number of models that repIesent a variety of prototype loads and dimensions. From the experimental data, curves are plotted to show the relations between these loads and dimensions. The curves are used to solve directly the problems stated above. Structural design is based upon the working (safe) stress of the material of construction, which is established by applying a factor of safety to the experimentally determined ultimate strength of the material. In conformity with this principle, each model is gradually loaded until failure occurs. A safety factor is then applied to the results. If a safety factor of 4 is used, a given model at failure represents a safe prototype, the linear dimensions of which are equal to one-fourth the model ratio at failure times the corresponding model dimensions. The safe model ratio is computed from the following formula: [Safe R = (rl 47r2n2r _ 7r2n2r~r~ \4/ gg in which: n = centrifuge revolutions per second at model failure; r = radius of rotation of the model in feet; g = 32.2 ft/sect.]

Jan 1, 1947

R. B. Sosman, * Kearny, N. J.—Mr. Sweetser brought out that in certain blastfurnace slag compositions a change of one or two tenths of a per cent may be quite significant. That is true not only of blast-furnace slags but of other compositions as well. We have all been up against the necessity of having to plot out equilibrium diagrams of this kind on a big enough scale so that we could actually use them, the

Jan 1, 1935

R. B. Sosman, * Kearny, N. J.—Mr. Sweetser brought out that in certain blastfurnace slag compositions a change of one or two tenths of a per cent may be quite significant. That is true not only of blast-furnace slags but of other compositions as well. We have all been up against the necessity of having to plot out equilibrium diagrams of this kind on a big enough scale so that we could actually use them, the

Jan 1, 1935