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By Hans Rumpf

INTRODUCTION Agglomeration is based on adhesion between particles. Production of agglomerates of specific strength, strain properties, size, porosity and structure necessitates the activation of the adhesive forces. To achieve this, it is important for us to know details of the various systems of adhesion. Reports on the work of our Institute for the investigation of systems of adhesion were published on various occasions. A reference to those publications is made in the following abstract, and the findings previously published are presented only to the extent necessary for a better understanding of more recent test results, or of changed ideas. 1. MECHANISMS OF ADHESION We must distinguish between various "mechanisms of adhesion". By "mechanism of adhesion" we understand the interaction between a particle and a substrate resulting from a clearly definable physical or physico-chemical process resulting in a definite mathematical interrelation- ship between the decisive variables.

Jan 1, 1977

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944

By Edward C. J. Urban

ESSENTIAL requirements for ensuring safe working atmospheres in underground metal mines are planned systems of ventilation and provision for effective distribution of sufficient volumes of air by auxiliary equipment. Investigators1 in the past have suggested that quantities of air supply ranging from 300 to 800 cu. ft. of air per minute per man underground are necessary, to establish adequate general ventilation. These fundamentals are just as important as the use of water in dust suppression, control of blasting, the use of personal protective equipment, frequent inspection of working areas and education of employees in good dust-prevention practice. During the past two years the necessity for direct control of the underground working environment has become particularly urgent. The increase in production rate, with two-shift and three-shift operation replacing the single shift, has complicated the problem of dealing with excessive concentrations of blasting fumes and gases, carbon dioxide and monoxide, heat and oxygen deficiency. Although previous industrial hygiene programs had given consideration to these factors, they were generally regarded by mine operators as secondary to the control of dust hazards. Today, blasting smoke in a mining area means delayed production because the miner cannot return to his work place after a short interval. Smoke on the haulage level means a safety hazard and exposure of the underground employees to excessive concentrations of atmospheric contaminants. Exposure to the moderately excessive concentrations of carbon dioxide and monoxide found in metal mines has caused physiological disturbances and a decreased capacity for work; deficiency of oxygen, in some cases to as low as 3 per cent, has resulted in fatalities. During the past 10 years the Saranac Laboratory2 has been associated with the iron mines in the Upper Peninsula of Michigan and Wisconsin in developing and maintaining an industrial hygiene and silicosis-prevention program. At present, about 35 underground iron-ore mines are operated full time in this area. With two exceptions, all of them are ventilated by main fan installations installed either on surface or underground. ,The types of mining used in these mines may be classified either as sublevel cave, radial top slice or sublevel stope, and the procedures commonly employed in the ventilation of these three types are described in Figs. 1 and 2. A number of different methods of mine ventilation had been in use in this area when the study was started. Natural ventilation had proved unsatisfactory. The wide variation between low air volumes during the summer months and higher volumes during winter led to unpredictable conditions that were difficult to control. In the majority of the mines two separate shafts or openings to surface are utilized in

Jan 1, 1943

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944

By J. Geertsma

The relationship between porosity and the speed of propagation of acoustic waves in fluid-saturated porous rocks as measured by the Sonic log and by ultrasonic tecbniques is analyzed. Biot's continuum theory 1 is used to explain the difference in acoustic wave propagation between a dry and a liquid-saturated porous material. The porosity is a variable in this theory. However, the acoustic wave propagation in the dry rock depends too on porosity, and this dependence is not predicted by the theory. Frequently in dry sandstones, a nearly linear relationship between reciprocal acoustic wave velocity and porosity is observed in the low-porosity range. The physics behind this behavior is outlined. An empirical relationship of the form, 1/v = A + F, applies accordingly for many porous dry rocks, provided the porosity is the only variable. The presence of a liquid in the pores changes the value of B, and this change is found to be in agreement with the Biot theory. The time-average relation introduced some years ago2 results in an equation of the same type — 1/V = F/Vf + (1 - F)/Vr — but is not based on a sound physical picture. Still, this relation sometimes predicts approximately correct A and B values. Carbonate rocks with their complicated pore structures sometimes show a different relationship between wave velocity and porosity, unfavorable for log interpretation. Examples are presented. The simultaneous presence of calcite, dolomite and anhydrite, with their different grain densities and matrix compressibilities, complicates acoustic-log interpretation in carbonate rocks still further. Other complicating effects of acoustic-log interpretation are discussed. They are related to the influence of shale streaks and natural fractures on the average wave velocity observed by the logging tool and to the effect of adsorption phenomena on wave propagation in unstressed rocks particularly in sandstones. INTRODUCTION The velocity of propagation of sound waves in porous sediments as a function of depth is a quantity frequently measured. Velocity loggers of various d-sign may be used, for which velocity is defined as the. distance between a wave generator and a wave detector (one-receiver system) or the distance between two wave detectors (two-receiver system), divided by the shortest time required for a vibrational pulse to cross this distance. Velocity loggers ale used to assist in seismic prospecting, to differentiate between the various types of sedimentary rock layers, and also to determine rock porosity and pore fluid content. This paper is especially concerned with the relation between velocity and porosity and the effect of the pore fluid. Most velocity-log interpretation in terms of porosity is based on a formula advocated by Wyllie, et al,2 suggested earlier by Hughes and Jones,3 and known as the "time-average relation". This formula app1ies for a model consisting of a layered system of parallel alternating slices of a solid and a liquid, crossed by the wave path perpendicular to the interfacrbs. This must be an unsuitable model for the derivation of wave propagation properties of liquid-saturated porous media. It suggests that only rock matrix and fluid properties influence the wave velocity. The surprising fact, nevertheless, is that applications of this formula to clean sandstones under specific conditions (sufficient effective stress) results in porosity predictions which are close to reality. Other authors, such as Gassmann,4 White and Sengbush,5 Brandt,6 and Hicks and Berry,7 make use of more realistic models to arrive at a wave velocity formula for porous sediments. Their models consist of various liquid-saturated packings of frictionless spherical grains and are, therefore, also highly idealized. A number of experimental results obtained in the laboratory can be better explained with these model theories than by the time-average relation. A study of a general character, not depending a priori on a special model of the porous structure, was still lacking.

By J. N. Chew, C. A. Connally

A correlation is presented for predicting the viscosity of gas-saturated crude oils under reservoir conditions. It is based on the dead oil viscosity and the solution GOR. The correlation was developed from a study which showed that at a fixed solution GOR, the relation between the gas-saturated oil viscosities and the correrponding dead oil viscosities is a straight line on logarithmic coordinates. Data from 457 crude oil samples from the major producing areas of the U. S., Canada and South America were used. The best straight lines through the data were fitted by the method of least squares with a digital computer. The correlation is presented in the form of an equation and also in a convenient gra-phical form. INTRODUCTION The viscosity of gas-saturated crude oils under reservoir conditions is an important physical property used in reservoir engineering calculations. Many difficulties are inherent in the sampling of gas-saturated oils and in the laboratory measurement of their viscosities. Therefore, it is frequently neither possible nor convenient to obtain measured values, so the viscosity must be estimated from other, more readily available data. This paper presents a correlation for predicting the viscosity of gas-saturated crude oils. The correlation is based on the amount of gas in solution and the viscosity of the dead oil at the temperature of interest. A previous correlation of these variables was presented by Beal. In comparison, the correlation presented here extends to a higher GOR and to a lower dead oil viscosity. Over the range of variables covered by both, this correlation is based on approximately 11 times as many oil samples. DEVELOPMENT OF CORRELATION A study was made of the variables or parameters which could be used to relate the viscosity of a gas-saturated oil to its dead oil viscosity. Preference was given to those variables which are easily and commonly measured in the field or in the laboratory. It was found that either the differential liquid formation volume factor or the solution GOR of the gas-saturated oil could be used as a correlating parameter. The solution GOR was se- lected for the correlation because of its simplicity and availability. In an attempt to refine the correlation by introducing a second parameter, the following additional variables were tested: differential liquid formation volume factor at the reservoir bubble point, the formation volume factor at the saturation pressure for the GOR of interest, reservoir temperature, viscosity of C+ fraction at 100°F and atmospheric pressure, weighted average gravity of gas in solution, oil gravity, reservoir bubble point pressure, saturation pressure at the selected GOR and reservoir temperature, and gas mol fraction. None of these improved the correlation to any significant extent. It was found that at any fixed solution GOR, the relation between the gas-saturated oil viscosities and the corresponding dead oil viscosities is a straight line on logarithmic coordinates, for the range of variables investigated. This straight-line relationship was used for the correlation. Viscosity data on a total of 457 crude oil samples were used. The data were obtained with rolling ball-type viscometers. The samples came from all of the important producing areas of the U. S., as well as from Canada and South America. Their geographical distribution is shown in Table 1. The ranges of properties represented by these samples are as follows: For each crude oil sample the viscosity of the liquid phase from each step of a differential liberation was plotted against its solution GOR on semi-logarithmic paper. A smooth curve was drawn through the points and values of viscosity in centipoises were read from

By J. R. Long, E. T. Hayes, D. C. Root, R. S. Dean

The U. S. Bureau of Mines has recently reported on the development of a process for preparing pure ductile titanium in substantial quantities1 and on the physical properties that may be attained in the metal, when consolidated by powder metallurgy methods and fabricated by certain hot and cold-working procedures.2 The high physical properties (Table I), combined with excellent corrosion resistance and light weight, will lead no doubt to appropriatc applications of the metal. In any application, methods of joining will be of considerable importance. The relatively high activity of the metal toward the common gases raises the question of weldability and conditions that might be required for successful welding. Since hydrogen, oxygen, and nitrogen embrittle the metal, it should be protected from these gases at elevated temperatures. This was demonstrated by a few preliminary trials of arc, gas, and resistance welding. In these trials only the resistance method proved to be immediately- applicable. While atomic: hydrogen welding of titanium may be successful in some instances, a considerable amount of development work will be required to prove its worth. In addition, it would be suited only to small assemblies that could be heated subsequently in a high vacuum to remove embrittling hydrogen. Heli-are methods likewise would be limited to small assemblies, which could be completely protected by a helium atmosphere. It was quite apparent that titanium required more protection than was afforded by the normal flow of helium gas used for welding magnesium and aluminum. The hot metal is attacked by oxygen and nitrogen, and the rapid diffusion of the oxide into the metal prevents the formation of a protective coating and requires the helium atmosphere to be maintained until the weld has cooled nearly to room temperature. The preliminary work indicated that titanium could be successfully spot-welded without deterioration of the metal and that the microstructures of the welds were normal, exhibiting good bonding, and no oxidation. The high resistivity of titanium (53 microhms per cu. cm.) suggested that it would behave somewhat like stainless steel and allow considerable latitude in the several welding variables. The results reported here are intended to give a general picture of the effects of varying welding current, welding time, and tip pressure on single spot welds made on several different thicknesses of titanium sheet. The work was undertaken to demonstrate the feasibility of welding titanium rather than as an exhaustive study of spot welding. There are, therefore, a number of factors that will require further investigation to establish the specific controls required for actual applications.

Jan 1, 1947

By L. K. Oliver, Marshall

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By J. R. Long, R. S. Dean, D. C. Root, E. T. Hayes

The U. S. Bureau of Mines has recently reported on the development of a process for preparing pure ductile titanium in substantial quantities1 and on the physical properties that may be attained in the metal, when consolidated by powder metallurgy methods and fabricated by certain hot and cold-working procedures.2 The high physical properties (Table I), combined with excellent corrosion resistance and light weight, will lead no doubt to appropriatc applications of the metal. In any application, methods of joining will be of considerable importance. The relatively high activity of the metal toward the common gases raises the question of weldability and conditions that might be required for successful welding. Since hydrogen, oxygen, and nitrogen embrittle the metal, it should be protected from these gases at elevated temperatures. This was demonstrated by a few preliminary trials of arc, gas, and resistance welding. In these trials only the resistance method proved to be immediately- applicable. While atomic: hydrogen welding of titanium may be successful in some instances, a considerable amount of development work will be required to prove its worth. In addition, it would be suited only to small assemblies that could be heated subsequently in a high vacuum to remove embrittling hydrogen. Heli-are methods likewise would be limited to small assemblies, which could be completely protected by a helium atmosphere. It was quite apparent that titanium required more protection than was afforded by the normal flow of helium gas used for welding magnesium and aluminum. The hot metal is attacked by oxygen and nitrogen, and the rapid diffusion of the oxide into the metal prevents the formation of a protective coating and requires the helium atmosphere to be maintained until the weld has cooled nearly to room temperature. The preliminary work indicated that titanium could be successfully spot-welded without deterioration of the metal and that the microstructures of the welds were normal, exhibiting good bonding, and no oxidation. The high resistivity of titanium (53 microhms per cu. cm.) suggested that it would behave somewhat like stainless steel and allow considerable latitude in the several welding variables. The results reported here are intended to give a general picture of the effects of varying welding current, welding time, and tip pressure on single spot welds made on several different thicknesses of titanium sheet. The work was undertaken to demonstrate the feasibility of welding titanium rather than as an exhaustive study of spot welding. There are, therefore, a number of factors that will require further investigation to establish the specific controls required for actual applications.

Jan 1, 1947

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By C. D. Demond

IN reverberatory smelting, fuel is the chief item of expense, as it commonly is in processes using large percentages of it. Hence the most suitable supply is eagerly sought; that is, the supply which, in the end, yields the greatest net profit. The better grades are not infrequently bought, even at an advanced price, because they are apt to be decidedly more economical. High price, of itself, however, is no merit, for freight is generally the largest part of the cost of fuel, and the nearby supply may yield as high efficiency as that from a greater distance. If a poorer grade is reasonably good, and if its cost is low enough to more than offset the decreased technical efficiency, it is of course the more suitable. Any smelting, operation depends for both efficiency and economy on raising the furnace atmosphere considerably above the "critical" temperature; that is, above the temperature at which smelting is completed. If this temperature is not exceeded, smelting stops, no matter how much coal is burned; and the real value of a fuel depends on the number of degrees that the temperature is continuously kept above this point. For example, if one fuel maintains 2,500° F. and another only 2,100° F., while the "critical" temperature is 2,000° F., the first is worth at least five times as much as the second, although the increase above atmospheric temperature is only one-fifth more in one case than in the other. This "margin of temperature" above the smelting point is much more significant than the total number of heat units developed from the fuel. The case is parallel to that of water flowing from a pipe. The reservoir may contain a billion gallons of water; but, even though the fluid has come to the nozzle, not a drop will run out, where it can be of practical use, unless the level in the reservoir is higher than the nozzle; and the speed and volume of flow depend on how much higher the level is in the reservoir than at this point. If the temperature inn a furnace is not above the critical level there will be no slag to flow over the skimming plate, even though there are enough heat units to bring an unlimited quantity of charge up to the point of slag formation; and just as the value of a water supply for the purpose of putting out a fire depends largely on the effective head, so the difficulties of furnace management

Jan 8, 1914

By Marshall, L. K. Oliver

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By Paul J. Fopiano

SOME relationships between the flow characteristics of iron single crystals of 99.9 pct purity and the behavior of imperfections have been investigated. X-ray rocking-curve measurements and etch-pit counts were made as a function of plastic strain, and compared to the stress-strain curve obtained on a modified Polyani tensile machine. Crystals grown from rolled strips of vacuum-melted iron by the strain-anneal method1 had a high preference for a (110) longitudinal direction and a (211) face normal. The tensile specimens were prepared from 2 by i by 0.040 in. single crystals having a gage area of 3 by \ in. Rocking-curve measurements were carried out with a highly perfect germanium monochromating crystal in which the dazz spacing was matched to that of the dZl1 in the ir0n.l Well-collimated CuKal radiation was used throughout. These procedures practically eliminated errors due to geometrical and wavelength resolution. Inasmuch as the rocking-curve half breadth may vary markedly from point to point in the specimen being irradiated, the crystals were strained in place by mounting a hydraulic loading device on the double-crystal spectrometer. The rocking curves were taken after each increment of strain in the unloaded condition, since no observable difference was found in the rocking-curves between the loaded and unloaded states. The rocking-curve half breadths of the as-grown specimens were in the range 90 to 120 sec of arc when the beam irradiated an area of about -£ by -& in. on the specimen. DeMarco and weiss3 have shown that, for a well-colli- mated X-ray beam, irradiating about 10"! sq in. of the very same material, half breadths within 10 pct of the Darwin natural half breadth were observed. Since the rocking-curve specimens were stressed by the load-unload technique, the strain achieved at any given stress depended on the time of holding because of low-temperature creep. Fig. 1 shows the rocking-curve half breadth (also area/peak height) as a function of plastic strain for a relatively short holding time (2 to 5 min) at each stress level. For strains less than 0.1 pct the rocking-curve breadth is essentially constant; it is only for larger strains that there occurs a significant increase in this breadth. Where the holding times at each stress level were longer (by well over an order of magnitude) there occurs a significant increase in the rocking-curve breadth only after plastic strains of the order of 0.6 pct had been introduced into the specimen. This observation is related to the time dependence of creep phenomena and emphasizes the difficulty in comparing data obtained by two such different straining methods. Etch-pit results were obtained using a 2 pct nital etch on specimens strained in the range of 0 to 1 pct. Prior to etching, all specimens were annealed for 3 hr at 150°C, the carbon content being sufficient to decorate the dislocations for strains of at least 1 p~t.~ The data points were all taken from parts of the same single crystal which had been strained with short holding times at stress in increments of strain of the order of tenths of 1 pct. The (211) plane is particularly difficult to etch-pit in vacuum-melted iron and therefore it is felt that these values are as much as an order of magnitude low. Fig. 2 shows the etch-pit density as a function of plastic strain. The smooth curve passing through the data points is not meant to infer a quantitative correlation with the rocking-curve data. What is of interest, however, is the change in etch-pit density in the region of 0.2 pct plastic strain. The first three increments in strain (points 2,3, and 4) did not produce a measurable change in the etch-pit density while subsequent increments did produce a measurable change. While the absolute values of these results do not appear to be cor-

Jan 1, 1967

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By Oscar E. Harder, H. A. Grove

It is now just a quarter of a century since Fred W. Taylor§(23) pub-lished his classical paper On the Art of Cutting Metals, describing his researches in which he, in cooperation with Maunsel White, had developed what is essentially the modern method of heat-treatring high-speed steels. Regarding this research, Dr. Sauveur,(22) in his address on Steel Wizards, Past and Present, at the annual banquet of the American Society for Steel Treating in Philadelphia in 1920 said, "The discovery of high-speed steel, or if you prefer, of the treatment imparting high-speed properties to certain steels by Taylor and Maunsel White I am inclined to consider as our one epoch-making contribution to the metallurgy of steel." It was at about that same time (1900) that Taylor exhibited high-speed steels, heat-treated by the improved process, at the World's Exposition in Paris and attracted much attention by showing that the steels would operate at such feeds and speeds that the tips of the tools were visibly red hot. This observation must have started metallurgists to wondering regarding the relative hardness of the various steels at red-heat temperatures. Considerable work has indeed been done in an effort to measure the hardness of high-speed steels and related materials in the red-heat range, using various methods. The result's, however, have been only partly satisfactory, owing to experimental difficulties. The present investigation had as it's immediate inception an address by J. V. Emmons, of the Cleveland Twist Drill Co., to the Columbus Chapter of the American Society for Steel Treating in 1931, in which he deplored the fact that comparatively little was known with regard to the hardness of high-speed steels at elevated temperatures, in spite

Jan 1, 1933

By W. M. Weigel

Salt production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been cstimated only by geophysical methods. The diameter of the salt core varies from less than 1/2 mile to over 2 miles. Only domes where the salt is comparatively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use. Fig. 1 shows the location of the domes so far developed for commercial salt and brine. Nos. 1, 2, 4, 7, 8, 9 and 10 are in the Gulf Coastal field,

Jan 1, 1938

By W. M. Weigel

Salt production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been cstimated only by geophysical methods. The diameter of the salt core varies from less than 1/2 mile to over 2 miles. Only domes where the salt is comparatively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use. Fig. 1 shows the location of the domes so far developed for commercial salt and brine. Nos. 1, 2, 4, 7, 8, 9 and 10 are in the Gulf Coastal field,

Jan 1, 1938

By John T. Norton, R. E. Hiller

The tremendous increase in the use of metals that have been prcpared by the various cold-working processes during recent years has greatly stimulated the investigation of problems concerned with the fundamental nature of these processes. It has been observed in practice that different methods of bringing about the same dimension changes in a sample result in a rather wide range of properties. Cold working reduces the ductility of a metal, or what is perhaps more nearly correct, its "working capacity," and naturally the manufacturer wishes to produce an article that has as large a working capacity as possible, and to produce it with the smallest number of operations. It has also been known for some time that cold deformation produces a parallel alignment of the crystal grains of a metal, and that the type of this preferred orientation depends to some extent at least upon particular processes employed in the deformation. The present investigation has for its purpose the study of the relations between the various factors of a cold-working process and the preferred orientation of the metjal crystals resulting from this deformation. The work is chiefly confined to a study of cold-drawn seamless tubing. Preparation of Samples The tubing samples used in this investigation were made of steel having a carbon content of 0.10 to 0.20 per cent, and were drawn on a standard type of draw bench. In order to obtain the large reductions, the annealed stock was coated with lead, for purposes of lubrication. The reductions of area stated refer to reduction from the annealed condition without intermediate heat treatment. The cold work was done as nearly as possible at room temperature. The samples of wire and strip used for purposes of comparison were of steel of approximately the same carbon content and were prepared in the manner indicated. X-ray Method of Investigation The condition of preferred orientation in cold-worked samples is best investigated by the X-ray method that employs a small circular beam of * Assoriate Professor of Physics of Metals, Massachusetts Institute of Technology. t Graduate Student, Department of Metallurgy, Massarhusetts Institute of Technology.

Jan 1, 1932

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970