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By H. Eyring, J. W. Fredrickson

Many theories have been advanced to explain the phenomena of elastic and plastic deformation. The object of this report is to present a mechanism for deformation, not radically differing from existing theories, but embodying.certain principles and concepts of these theories. This proposed theory cannot be the complete answer to the age-old problem of deformation but it is believed that it will be a step further in the proper direction. The plastic properties of solids have recently been reviewed by Seitz and Read.' ZenerZ has reviewed and correlated the existing work on the anelasticity of metals. With these and others3'4'5 resent theories of deformation are well-known. Of the many theories now extant, those receiving most attention have been proffered by Griffith,6 Becker,l Smekal,8 Polanyilg Orowanlo and Taylor.'' Although differing quite widely in details, these theories are based more or less on a common principle of flaws or dislocations that exist in the crystal lattice. The effect of stress concentrations surrounding a flaw or crack has been treated most recently by Fisher and Hollomon.12 The various authors differ as to the exact nature of the flaws or dislocations, the causes of their appearance, or the manner in which they initiate slip. All of the theories agree that the number of dislocations increases with progressing deformation. It is universally agreed that the shearing process is not a simple gliding of ideally perfect atomic lattice planes. It is also agreed that the "macroscopic" process of gliding, or slip, is brought about by the spreading of a large number of locally initiated "glide steps" through the whole crystal. The occurrence of these "glide steps" is closely related to the presence of some kind of deviations from the "ideal" lattice structure, even in the undeformed crystal. These deviations are overcome ''one at a time," in a manner of speaking, due to some stress-concentrating effect.13 Proposed Theory Many solids show a continuously increasing deformation if subjected to a constant load of suitable magnitude in an extended range of temperature for a sufficient time. This deformation, or flow, may be said to be due, in general, to the tendency of the atoms or molecules in an elastically stressed body to readjust themselves in such a way that if the deformation were kept constant, a release of stress would take place. If rupture does not occur, this process of relaxation causes the rate of flow to obtain a final constant value, as shown in the curve (Fig I) obtained by Taylor and Quinney.14 In this state the release of stress by relaxation exactly counterbalances the increase due to the elastic strain on the test pieces.

Jan 1, 1949

By Willis R. Battles, William F. Cerini, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By William F. Cerini, Willis R. Battles, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By W. H. Gunniss

When the copper smelters were built, in Montana, all of the refractory products which were used in their construction were shipped in from Eastern factories. It was apparent that if a material suitable for the manufacture of these products could be found within the State, a saving of freight could be effected and a new industry built up. Prospecting for such materials was started and experiments were made with samples from numerous deposits. Considerable effort and funds were expended in an attempt to manufacture silica brick from Dillon quartz, a light colored sandstone that is found near Dillon, Mont., on the Oregon Shortline railroad. As a brick material the Dillon quartz was a failure, but it has proved very satisfactory as a silica cement. It is now being used in laying silica brick and for reverberatory furnace bottoms. A bed of quartzite that is particularly suited to the manufacture of high-grade silica brick was finally discovered at Browns Spur, 6 miles west of Anaconda. The material from this deposit is now being used in the manufacture of the Anaconda silica brick, which have gained a wide reputation for heat-resisting and lasting qualities. The analysis of an average sample of this quartz is: SiO2, 96.7; Fe2O3, 0.3; Al208, 2.5; CaO, 0.3 per cent. The very low percentage of fluxing ingredients makes this a most refractory material. All of the Anaconda silica brick are hand molded. Various types of brick machines have been tried, but the hand-mold process proved the best suited to the manufacture of silica brick from this material. The silica is first put through a jaw crusher and is then dumped into wet pans, where 4 per cent. of lime paste is added, to produce a bond. Without the lime the material would not be plastic enough to mold. After a few minutes' grinding in the wet pans the material is conveyed to the molder, who forces it into the molds by hand. The brick are then dumped on pallets and placed in the drier, where they are left. until dry enough to be set in the kilns. Some of the brick are re-pressed before being dried. They are burned about five days, in round down-draft kilns. It is not necessary to have as much heat in the kilns as the brick will be subjected to when in use in the furnaces. Montana refractories are used in smelters throughout the West. Prospecting for fire clays was also carried on. After experimenting with clays from several different deposits, it was found that a mixture of

Jan 1, 1914

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By H. H. Stout

IN the early fall of 1025, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500° to 1600°F. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F." Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me." The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after confer-ring as to ways and means, decided to go ahead with preliminary laboratory experi-ments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: I. Since brittle cathodes were often unin-tentionally produced, it seemed probable that the laws controlling this type of deposi-tion could be ascertained. 2. We had already proved the gas-clean-ing feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia Uni-versity for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrounded and heated by a resistance coil of Nichrome wire. Broken tough cathodes were used.

Jan 1, 1940

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By E. A. Gulbransen, J. W. Hickman

THE physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,1 if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth' is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's5 oxidation measurements from 700° to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow W03 with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors' presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By M. T. Worley

This paper reports investigative work conducted to develop a method of estimating the groundwater influx from a homogeneous permeable formation into a vertical mine shaft during sinking. A method of analysis was developed using data obtained from pumping tests and a modification of the Theis non-equilibrium interpretation technique. Excess influx of groundwater into mine shafts has long been one of the more important problems encountered in the development of a mining property. Much work has been done on methods of preventing such influx and on pumping schemes to control inflow if preventive measures fail. The fundamental aspects of the problem, on the other hand, seem to have been neglected. The purpose of this paper is to review the fundamentals of groundwater flow and to propose a rapid method of analyzing hydrologic data in order to estimate influx from a homogeneous permeable formation into a mine shaft. Such an estimate of the quantity of water to be encountered is of value in planning grouting, pumping and other programs designed to control that influx. It is emphasized that the proposed method of analysis should be regarded only as a tool to be used in evaluating the problem before investing the capital necessary to begin development of a property. FUNDAMENTALS OF GROUNDWATER FLOW In order to effectively approach the problem of estimating influx into a mine shaft, a knowledge of the fundamentals of fluid flow through a porous medium is necessary. Darcy, in 1856, developed an empirical relationship to explain the flow of water through sand filters. This relationship V = k (dh/dl), is the basis for all other flow formulae. It has been shown that Darcy's relation is a solution of the Laplace equation and thus is analagous to other natural phenomena such as heat flow. Theis, using the analogy of heat flow by conduction, developed an expression for determining the transient or time-dependent groundwater flow through a homogeneous, isotropic medium. The resulting equation Was also derived by Jacob using hydrologic considerations alone.' The individual terms in the equation are described in Table I. It is important to understand the assumptions upon which this equation is based. 1) The medium through which the fluid flows is infinite in areal extent, homogeneous and isotropic. 2) The well into which the fluid discharges completely penetrates the medium. 3) The characteristics of the medium remain constant at all times. 4) The initial pressure surface is horizontal. 5) The confining media are impervious and horizontal. 6) Fluid is removed from storage instantaneously by a decline in pressure. 7) The diameter of the discharge well is infinitesimal with respect to the drainage radius of the medium.

Jan 1, 1962

By F. H. Turan, F. W. Jessen

The gel strength and viscosity of two different suspensions of fractionated montmorillonite clay were measured by using a Stormer viscosimeter and Farm V-G meter. The amount of sodium poly-phosphate (sodium bexametaphosphate, sodium tetraphosphate and sodium acid pyrophosphate) adsorbed by the clay particles was determined. A relationship seems to exist between the amount of polyphosphate adsorbed and the nature of the surface, edge or plate, assumed to be the principal sites for selective adsorption. Reduction in viscosity and gel strength was found to be directly related to the adsorption. Both chemical bonding and physical adsorption seem involved in defloccula-tion Some indication of the axial ratios of particles of .l- to .04-micron average size is possible though study of the adsorption mechanism. INTRODUCTION AND PURPOSE A knowledge of surface areas of clay particles in a suspension and a precise determination of phosphate adsorption should provide a basis for a better understanding of reduction in viscosity and gel strength caused by molecularly dehydrated phosphates. The purpose of this investigation was to study the adsorption of sodium polyphosphates on suspensions of fractionated sodium montmorillonite. Although there is considerable uncertainty regarding details of the structure of montmorillonite, a generally accepted one is that suggested by Hofmann, Endell and wi1m.l The structure shown in Fig. 1 is an idealized one, and Marshall2 has postulated that it is possible for several isomorphous replacements to occur. Thus, aluminum may replace silicon, in which case an exchangeable cation would go along with the aluminum to neutralize what would otherwise be a net negative charge on the structure. There is disagreement among various investigators as to the particle size and shape of montmorillonite clays. Marshall2 reported the following results for the mean lateral dimensions of a Putnam clay (montmorillonite)— 3,730 A° for particles having average diameters ranging from 500 to 1,000 A, and 750 A° for those with an average diameter less than 200 A. The latter particles were estimated at 50A°in thickness, which would correspond to a stack of five unit cell layers. On the other hand, Shaw3 has interpreted micrographs as indicating that particles of montmorillonite ire readilv broken down to the individual cell layers by dispersion in water. Brindley4 and Merings indicate the ultimate particles to be of the order of 300 A° in mean lateral dimension. Van Olphen6 suggested the thickness of particles at four to five unit cell layers. It was suggested also that this number tends to become smaller with increasing dilution. Recently, Kahn and Lewis7 determined the size of sodium montmorillonite particles in aqueous suspension from electro-optical bi-refringence decay curves. The

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By R. T. DeHoff

A new approach to the measurement of the size distribution of particulate structures imbedded in opaque bodies is developed. The method is based upon the assumption of a general two-parameter distribution curve, and the estimation of these two parameters from three well-known counting measurements made upon metallogvaphic sections. The total number of particles in the system is also a product of the analysis. Application of the method with the assumption of the logarithmiconorma1 disfribution function is developed in detail. A complete description of the geometry of a particulate structure requires the determination of the size distribution of particles. The problem of estimating the size distribution of particles of a particular phase in a multiphase system, or the grain-size distribution in a homogeneous system, has been approached by many investigators.'-'0 All of the solutions proposed by these investigators share the following characteristics. a) A minimum of several hundred particle sections in the microstructure must be examined, and some characteristic dimension recorded, such as area,3'5 intercept length,6"9 or diameter.1'2'4'10 b) The resulting data must undergo a series of fairly complex calculations to generate the empirical histogram which describes the size distribution in three dimensions. c) In order to manipulate the result, the histogram must be fitted to some assumed mathematical formula, using the attendant statistical procedures. d) With two notable exceptions,8,10 the particles must be spherical. The measurements and calculations involved are in general very tedious and time-consuming, with the logical result that much effort has been expended in the development of equipment which will perform these tasks automatically and semiautomati-cally.9,11-15 considerable success has been achieved in this area, but the equipment is in general expensive, and usually places stringent requirements On the quality of microstructure which can be reliably analyzed. In laboratories which do not possess such equip- ment, the analysis of geometry is usually limited to measuring total properties of the microstructures, such as volume fraction and interfacial area, because the measurements required are much simpler to make. The determination of size distributions rarely is undertaken. The development which is presented in this paper permits the estimation of size distributions of three-dimensional structures from the same simple counting measurements which are required to determine the surface area and volume fraction of the particulate structure, and one other counting measurement. The basic approach that is used is to assume a general mathematical form for the distribution, which is described by two parameters (as the normal distribution is described by assigning values to the mean and the standard deviation), and then estimate these two parameters from the results of the counting measurements. The introduction of a third counting measurement also permits the evaluation of the number of particles per unit volume, Nv.

Jan 1, 1965

By M. D. Hassialis

THE claim is made in a number of patents1,2,3,4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S¬R[=]-R’ (where x = r,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using Biphenyl sulphide, ditolyl disulphide and dinapthyl disulphide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed was that of Moses, Hess, and Perkins. A sample of ore weighing 500 grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a 2-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8: 1. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of 12: 1. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. CONTACT-ANGLE TESTS In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcocite, chalcopyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By W. T. Isbell, Carleton C. Long

Zinc recovery from lead blast-furnace slags has heretofore been an indirect process, involving, first, the fuming off and collecting of an impure zinc oxide, and second, the reduction of the zinc portion of this oxide to metal either by electrolytic or pyrolytic means. (In a variation of this process, blue powder is the intermediate product rather than zinc oxide fume.) In 1940, W. T. Isbell proposed that molten slag from the lead blast furnace or stock-pile slag melted down in a blast or cupola-type furnace be charged directly into an airtight container (i.e., furnace) provided with means to heat further the slag by passage of electric current and means to introduce the carbon (coke) necessary to reduce the ZnO constituent of the slag to zinc as a zinc vapor and CO. He also proposed that the zinc vapors so obtained be condensed in a Weaton-Najariant internal condenser directly connected to the proposed furnace. It was thought that the Weaton-Najarian condenser could liquefy zinc vapor from lean mixtures of vapor and noncondensable gases. Such condensers have been in commercial use! since 1936 at Josephtown smelter, where the source of zinc vapor is a column of coke and zinc-bearing sinter electrically heated (charge resistor). Condenser output when supplied with vapor-gas mixtures containing approximately 45 per cent zinc and 55 per cent noncondensable gases, varies from 18 to 30 tons of slab zinc per day per condenser, depending upon the heat-transfer area (length) of the condenser and the volume of vapor (furnace size) fed to it. Lead-smelting operations at the St. Joseph Lead Company's plant at Hercu-laneum, Mo., produce a slag containing 12 to 16 per cent zinc. For several years this slag has been stock-piled with the object of recovering the zinc values if and when a commercial method was invented. Evaluation of the possibilities of the proposed method was made by pilot-plant operation at Josephtown. The first plant, designed in 1940 and operated in early 1941, consisted of a single-phase, two-electrode furnace. The evolved vapors were burned. Electrical characteiistics of the molten slag, power requirements, coke requirements, and extent of zinc elimination indicated the feasibility of the proposed method. In the latter part of 1941 a second pilot furnace was constructed, to which "was attached a small (6 ft. long) Weaton-Najarian condenser in order to develop an over-all picture of zinc-in-slag to zinc-in-slabs. This furnace was operated in the early part of 1942 and yielded such promising results that a decision was made to design- and construct a commercial furnace. Feed for the pilot-plant furnaces was granulated slag. A suitable deduction (300 to 350 kw-hr. per ton slag) was calculated in estimating power require-

Jan 1, 1944

By F. C. von der Weid

THE mining district of São Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineração de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis-the ore to be concentrated being mostly of a very high grade. MINERALIZATION AND ORES The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60° and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Macabú), the São Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and São Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in São Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydrothermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and

Jan 1, 1946

By M. G. Driessen

For a number of years the cyclone, familiar to Americans as a dust collector, has been used as a thickener of suspensions at one of the coal-preparation plants of the Netherland State Mines in Limburg. The plant treats nut-size coal at 120 tons an hour in a heavy-medium washer. The diluted medium from the rinsing screens is thickened in cyclones. More recently the cyclone has been adapted to act as a coal cleaner. The principle of the cyclone thickener is the same as that of the cyclones used in industry for catching dust or fine particles suspended in the air or in gases. Generally the latter are more efficient in this respect—the smallest particles that can be caught with reasonable efficiency are considerably smaller than with the cyclone thickeners. The reason is obvious; the ratio of specific gravities between the dust particles in a gas and the gas itself is about 800 times larger than the ratio between, for instance, the specific gravities of shale particles and water. The ratio of the velocities of fall of shale particles (? = 2.5)† in air and in water is as follows: In the range of Stokes: ?air = 93?water In the range of Allen: Wair = 49Wwater In the range of Newton-Rittinger: ?air = 36.6?water The same ratios apply for the velocities in the centrifugal field, from which it follows that it is especially difficult to catch the very fine suspension particles in a liquid. The efficiency of a cyclone thickener depends mainly on the circumferential velocity of the liquid at its innermost radius, because here the centrifugal forces are the highest. However, these velocities cannot easily be calculated, as the flow is three-dimensional, and thus the axial components cannot be neglected .(p. 252, condition 3). We believe that at first a spiral tangential motion along the cyclone wall is created, which causes the inner vortex ascending from the apex of the cyclone (Fig I). At the same time the inner vortex is strengthened by the individual vortices in horizontal planes, and thus a part of the total flow can find another and perhaps quicker way to the outlet. In any case, the exact motion, not only of the fluid but especially of the suspended particles, is so difficult that we have to refer to the experiments to find the exact behavior of this kind of apparatus. Method of Judging PerforMance of Coal Washer Geologists, rather than mechanical en-gineers, would be able to describe the separating or stratifying effect in nature, but even a bather on the shore lying on the soft sand near the sea wonders why all the small sand grains have approximately the same size. A child playing on the border of the river could easily

Jan 1, 1949

By R. S. Busk, E. G. Bobalek

THE relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.1,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittlement of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.3 To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Recently it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate microporosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.1 Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H2, solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice .2 For true equilibrium values of solubility, therefore, the pressure at the metal surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1946