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By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By Henry M. Howe

Jan 1, 1908

By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

By Walter Harvey Weed

Introductory.............449 Summary oF Types............452 I. The Virgilina Type...........452 The Virgilina mines...........452 Location.............452 History.............453 The rocks of the district..........453 The veins.............454 Notes on the mines.... 458 The Holloway. 458; Yancey and Durgy. 465 ; Copper World. 467 ; Frazier. 467 ; Thomas. 467 ; Anaconda. 468; Blue Wing. 468; High Hill. 472; Dorothy.......474 II. The Gold Hill Type...........474 The Gold Hill mine...........475 Location.............475 History............• 475 Surface improvements.......... 476 The rocks............478 Vein.phenomena...........478 Character of the ore..........481 Origin of the ore...........481 Notes on the mine.workings.........482 Other occurrences of ore-deposits of the Gold Hill type.. .. 483 III. The Ducktown Type..........484 The Ducktown mines...........485 Other examples of the Ducktown type....... 494 Alabama mines...........494 North Carolina examples : Ore Knob.......496 Virginia examples..........497 IV. The Catoctin Type.. ......... 498 General characteristics,......... 498 The Linden district...........499 General distribution of the Catoctin type.......503 Introductory. In the early history of this country the existence of copper in the Appalachian region was well known. but no mining mas attempted until the discovery of the Ducktown deposits in

Jan 1, 1901

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By S. J. Kidder, G. C. McCartney

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By L. W. Holm

This study shows that in the presence of foam, gas and liquid flow separately through porous media representative of reservoir rock. These results were obtained by using tracer techniques to measure the flow of the gas and liquid comprising the foam. Foam does not flow through the porous medium as a body even when the liquid and gas are combined outside the system and injected as foam. Instead, the liquid and gas forming the foam separate as the foam films break and then re-form in the porous system. Liquid moves through the porous medium via the film network of the bubbles and gas moves progressively through the system by breaking and re-forming bubbles throughout the length of the flow path. The flow rates of the gas and liquid are a function of the number and strength of the films in the porous medium. There is no free flow of gas; i.e., no continuous gas phase. On the basis of these results, foam can be expected to improve a water flood or gas drive by decreasing the permeability of the reseruoir rock to a displacing liquid or gas. This improves the mobility ratio and thus the conformance of the flood. INTRODUCTION Foam is formed when gas and a solution of a surface active agent are injected into a porous medium either simultaneously or intermittently. During the past few years, several papers have been published on the subject of foam flow in Dorous media. Foam has been used successfully in the removal of capillary water blocks from producing formations.''2 The use of foam in gas storage reservoirs to reduce gas leaks and to increase storage capacity has been considered in recent years. Foam has also been investigated as an oil displacing agent,3-5 and as an agent to improve the mobility ratio in a waterflood.6-10 However, the mechanism by which the gas and liquid phases comprising the foam flow through a porous medium has nor been described adequately. Normally, when two immiscible phases (gas and liquid) flow concurrently through a porous medium, each phase follows separate paths or channels. At given saturations of the two phases, a certain number of channels are available to each phase, and as saturations change, the number and configuration of the channels available for each phase also change. The effective permeability of each phase is a function of the saturation of that phase only, and the flow of each phase can be described by Darcy's law. When foam is present, the effective permeability of the porous medium to each phase is greatly reduced compaced with permeabilities measured in the absence of foam.6,11-13 Based upon the observed flow of surfactant solutions and gas in capillaries, it has been concluded that the gas and liquid may flow separately or they may flow combined as foam. At least four mechanisms have been postulated to explain how fluids flow with foam present: 1. A large portion of the gas is trapped in the porous medium and a small fraction flows as free gas, following Darcy's law.9 2. The foam structure moves as a body; the rate of gas flow is the same as the rate of liquid flow. 6,13 3. Gas flows as a discontinuous phase by breaking and re-forming films. Liquid flows as a free phase.12 4. A portion of the liquid and gas move as a foam body while excess surfactant solution moves as a free phase.14 It also has been suggested that different flow mechanisms exist for high quality (dry) foams made from dilute surfactant solutions and for foams made from more concentrated solutions. Studies conducted on the flow of foam through capillaries have shown that a plug-type flow occurs and that foam flows as a body.6,15 Fried also has described the flow of foam through porous media as

Jan 1, 1969

By J. Sharshall Grasty, Thomas L. Watson

The users of barite in the United States derive their supply partly from the domestic production and partly from the imports from foreign countries. According to the Mineral Resource division of the U. S. Geological Survey, the domestic production of barite in 1913 was 45,298 short tons, valued at $156,275, or $3.45 a ton, and the imports of crude barite were 35,840 short tons, valued at $61,409, or $1.71 a ton. These figures clearly show a decided advantage in cost of the foreign over the domestic barite to users in the United States. The difference in cost is the only advantage to the consumer of foreign barite, for there are large reserves of the mineral in the United States of good grade. The production of many of the operating mines is capable of decided increase, and it is believed that the operating mines together with the large reserves of undeveloped deposits of barite are entirely adequate to meet the demands of the users in the United States. Deposits of barite are known in California, Idaho, Nevada, and Alaska, but most of them are undeveloped because there is, apparently, no market for the material in that region. The domestic production is derived from Missouri .and the Appalachian States, the greater part being obtained from Missouri. Following the outbreak of war in Europe many users of foreign barite in the United States have been forced to seek their supplies at home. It seems opportune at this time, therefore, that a general review be given of the barite industry in the Appalachian States, one of the two areas from which the domestic supply of the mineral is derived, and that attention be directed to the undeveloped deposits in the region. Briefly, then, this paper reviews the barite industry in the Appalachian States, and describes the occurrence, preparation, and uses of the mineral. General Character Barite, known commercially as barytes or heavy spar, is barium sulphate (Baso4), containing when pure BaO, 65.7 per cent., and S03, 34.3 per cent. The specific gravity is 4.3 to 4.6, and the hardness 2.5

Jan 1, 1915

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949

By Walter H. Bruckner, George B. Clark

SINCE the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained e1sewhere.l,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established concerning cavity liners: 1,2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as on the base diameter of the charge. Acute apex angles require thinner walls for optimum performance and more obtuse angles require thicker walls for the same base diameter. 2. Cones were more effective in forming a penetrating jet when the walls were tapered; i.e., the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical proper- ties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of Slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2. Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1947

By M. P. Tixier

In several log interpretation methods, water saturation is evaluated by use of the ratio of the readings of a short spacing resistivity device and a long spacing resistivity device plus information on the mud filtrate and connate water resistivities, which is often derivable from the SP. These methods are valid over a certain range of conditions, usually specified by moderate invasion and R.. greater than R,. Since these methods involve no explicit evaluation of the formation factor, F, the saturafiion so found may be used in the standard Archie equation to derive a computed formation factor which, as a check, may be compared with the formation factor known from other independent measurements. Discrepancies in the two values of formation factor generally indicate that the ratio method is not within its range of applicability. If the computed F is too low, the corresponding S, is too low; if the computed F is too great, the corresponding S, is too great. By means of this "porosity balance" check, and some knowledge of the probable conditions of invasion, the interpretation can often be improved. The poqosity balance check is discussed for the cases of the Induction-Electrical Log Interpretation Method, the Rocky Mountain Method, and the R.,/R, Method. For the first method, a discussion is also given for the case of shaly sands. INTRODUCTION Al though many logging tools are available to obtain a practical value of porosity, the only logging method reflecting the water saturation is electrical logging. Water saturation is commonly computed from electrical log data by means of the basic Archie formula, Where F is the formation factor, R, the resistivity of the formation water, and R, the true resistivity of the formation. One difficulty in this procedure is a possible error in the evaluation of R, from the logs— for example, in the case of very deep invasion. There is no possibility, inherent in the procedure, which would provide a check of the accuracy of R, and, hence, of the computed saturation. Other approaches have been proposed which are based essentially on the ratio of the readings made with two dzerent devices: one device, with a short radius of investigation, provides a value close to the resistivity of the invaded zone; the second device, with a long radius of investigation, gives a value close to the true resistivity of the bed. By these methods, the determination of saturation is made independently of any direct knowledge of the formation factor. Therefore, if the formation factor (or porosity) is known from other sources (core analysis, neutron log, MicroLog . . .), it becomes possible to take advantage of this additional information in order to check the value of saturation derived from these latter methods. Inasmuch as this proposed check procedure relies on a knowledge of the value of formation factor or porosity, it has been deemed appropriate to call this verification a porosity balance. The purpose of this paper is to discuss the principle and the application of the porosity balance, depending on the method of interpretation being used. Basis of the Method There are in existence three interpretation methods by means of which the water saturation can bc found without a knowledge of the formation factor (or porosity). As just stated, they are based on the fact that the ratio of the two resistivities (one measuring the resistivity close to the hole, the other measuring the resistivity far from the hole) is independent of the formation factor since it affects the two resistivity measurements in the same way. Chronologically, the resistivity ratio methods are: (1) the Rocky Mountain Method, which has been used since 1943 and was explained in a paper in 1949;' (2) the R../R, Method or Shaly Sand Method, presented in 1954, which permits the calculation of the water saturation in both clean and shaly sands2; and (3) the Induction-Electrical Log Method, presented in 1957 for the interpretation of the induction-electrical log combination." Each method requires certain definite conditions in order for the interpretation to be reliable. The porosity balance method will let us know whether these conditions are fulfilled. In clean formations we know that the fundamental Archie relation (Eq. 1) must always be verified. This relation can be rewritten:

By W. M. Weigel

Economic deposits of barite occur in Missouri in two main districts. The most important, the Southeastern or Washington County district, is in the southeastern part of the state, mostly in Washington County with a small extension into the northeastern part of St. Francois County. Roughly, it embraces nine townships or about 200,000 acres and accounts for from 80 to 90 per cent. of the state production. The Central district, is in the central part of the state, includes most of Morgan and Miller counties, and parts of Camden; Benton, Moniteau and Cole counties. The area embraced is much larger than the Washington County district, but the deposits are more infrequent. The location and general area covered by the two districts is shown in Fig. 1. There is another small area in southern Franklin County but so far its production has been of small consequence. It might be considered as a northward extension of the Washington County field. An, area in the central part of Hickory County has also produced a small amount. The outline of the districts as shown indicates the general area in which deposits have been found. The total area covered by deposits of barite is only a small part of this, as, in the Central district especially, there may be miles of supposedly barren areas between ore-bearing areas of an acre or two in extent. The date when barite was first mined in Missouri cannot be definit stated, but the industry probably dates back to about 1860. The occurrence of barite was known long before this, as it was encountered in the lead mines in Washington County and mentioned by several earlier writers." Missouri is reported as producing 8000 tons in 1882 so it is evident the industry was well under way in the seventies in order to have arrived at this substantial production. By 1893 Missouri production had increased so that it ranked with that of Virginia, then the largest producer it increased until in 1914 Missouri accounted for about 65 per cent. of the total United States output.

Jan 1, 1929

By A. E. Wheeler, H. Y. Eagle

The copper industry in the Province of Katanga, in the Belgian Congo, which is now controlled and operated by the Union Minére du Haut Katanga, had its inception many years ago in the vision of a Scotsman, Robert Williams, now Sir Robert Williams, Baronet. He it was who personally negotiated the mineral concession with King Leopold of Belgium, sent in the prospecting parties who located most of the present mines of the company, later arranged for the Belgian participation from which the present company was formed, and has been its active mentor ever since. The idea back of his efforts was the establishment of an industry on the Congo-Zambezi divide, of sufficient importance to draw up to it the head of the Cape to Cairo Railroad, the dream of Sir Cecil Rhodes, and the consummation of which he had left as a legacy to Mr. Williams, his successor. The reports of the prospecting expeditions showed that copper in profitable quantity was there, but many difficulties lay in the way of the establishment of the infant industry. The isolated location of the mines, various tribal wars, the Boer War, and many other factors contributed to making progress very slow. However, in spite of these difficulties the railroad was finally built and a blast-furnace plant erected at Lubumbashi, near Elisabethville, the capital of the Province. Operations of this plant were started in 1911, treating high-grade oxidized ores and producing pig copper by a reducing smelting. Production has been continuous since that time and the company has grown so that at present it ranks as the largest individual copper producer in the industry. It is a fitting monument to the foresight, optimism and driving force of its founder, and the progressive policies of his Belgian colleagues. In January, 1914, the Union Miniere du Haut Katanga engaged as its consulting engineer, Archer E. Wheeler, metallurgical engineer, at that time general superintendent of the Great Falls plant of the Anaconda Copper Mining Co. Mr. Wheeler was commissioned by the Board of Directors to proceed into Katanga, and make all necessary investigations to enable him to report on a comprehensive development program, and to recommend a scheme of treatment particularly for their low grade

Jan 1, 1934

By I. R. Kramer

Studies of the effect of size of the specimen on the change of slopes of Stages I and 11 by surface removal showed that the change of Stage I was independent of size with respect to the polishing rate; however, the change in the slope of Stage 11 with polishing rate increased directly in proportion to the surface area. The removal of the surface during the test affected the plastic deformation characteristics of gold, aluminum, and zinc single crystals and polycrystalline aluminum. The apparent activation energy of aluminum was found to be decreased markedly by removing the surface during the deformation process. In previous papers1-3 it was shown that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing during tensile deformation, it was found that the slopes of Stages I, II, and III were decreased and the extents of Stages I and II were increased when the rate of metal removal was increased. By removing a sufficient amount of the surface layer after a specimen had been deformed into the Stage I region, upon reloading, the flow stress was the same as the original critical resolved shear stress and the extent of Stage I was the same as if the specimen had not been deformed previously. The slope of Stage I was decreased 50 pct and that of Stage 11 decreased 25 pct when the rate of metal removal was 50 X 10"5 ipm. These data show that in Stage I the work hardening is controlled almost entirely by the surface conditions, while in Stages 11 and III both surface conditions and internal obstacles to dislocation motion are important. It appears that during the egress of dislocations from the crystal, a fraction of them becomes stuck or trapped in the surface regions and a layer of a high dislocation concentration is formed. This layer would not only impede the motion of dislocations, but would provide a barrier against which dislocations may pile up. In this case, there will be a stress, opposite to that of the applied stress, imposed on the dislocation source and dislocations moving in the region beyond this layer. It has been found convenient to refer to this layer as a "debris" layer. The "debris" layer may be similar to the dislocation tangle observed by thin-film electron microscope techniques.4 Reported in this paper are the results of studies on the effects of removing the surface during plastic deformation on aluminum crystals of various sizes. The effects of the surface on the yield point behavior of gold and high-purity aluminum crystals as well as the creep behavior were also determined. The effects of surface removal on polycrystalline aluminum (1100-0 and 7075-T6) are also reported. EXPERIMENTAL PROCEDURE For those portions of the investigation involving creep and tensile specimens, single crystals, having a 3-in. gage length and a nominal 1/8-in. sq cross section, were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The single crystals were prepared from materials which had initial purities of 99.997, 99.999, 99.999, and 99.999 pct for Al, Cu, Zn, and Au, respectively. The aluminum specimens for the size effect studies were prepared through the use of a three-tier mold in which crystals having a cross section of 1/8, 1/4, and 1/2 in. were grown from a common seed. The mold design was arranged so that one 1/2-in. crystal, two 1/4-in. crystals, and four 1/8-in, crystals of the same orientation could be cast. With this technique, it was possible to obtain only one set of crystals with the same orientation. Because of this limitation, it was not possible to determine both the changes of extent and slope of the various stages since a large number of crystals of the same orientation would have been required. Instead, only the change of slope as a function of the rate of metal removal was studied by abruptly altering the current density of the electrolytic polishing bath at various strains within the regions of Stages I and 11. The experimental techniques used for the tensile studies were essentially the same as those used previously.1,3 The specimens were deformed in a 200-lb Instron tensile machine, usually at a rate of 10-5 sec-5. A methyl alcohol-nitric acid solution was used as the polishing bath for aluminum. The temperature was maintained constant within ±0.l°C by means of a water bath. The tensile machine was

Jan 1, 1963