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By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll's reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll's reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By P. S. Roller

P. S. ROLLER,* College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should be defined as the distance between an F line and a [?] line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and [?] lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. I between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz," This would require many data to prove, but no proof is given; any considera¬tion would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.,* Cambridge, Mass.¬Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids.5 Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg8 have ground

Jan 1, 1941

By W. L. Phillips

Nickel alloys containing approximately 0.5, 2.0, and 6.0 at. pct of Os, Pd, Ru, and Rh were Prepared by vacuum melting. Tension tests were carried out at 25°, 500°, 800°, and 1000°C; stress-rupture tests were carried out at 650° and 800°C. The room- and elevated-temperature tensile strength, as well as the stress-rupture life, increased for the same atomic percent in the order palladium, rhodium, ruthenium, osmium. The ductility decreased with increasing concentration or temperature for a given concentration. The results are discussed in terms of solid-solution theory. BOTH solid-solution strengthening and weakening have been observed in alloys. The simple rules which have been suggested to explain alloy strengthening are subject to several exceptions and deviations based on atom size and valency effects. The purpose of the present investigation was to extend the knowledge of the effect of solid-solution alloying on the mechanical properties of several Ni-Pt group metal alloys at room and elevated temperatures. The platinum group metals, osmium, ruthenium, rhodium, and palladium were chosen as the solute elements because of their different valencies and atom sizes. Nickel was chosen as the base material because of the large amount of previous literature available on nickel alloys. EXPERIMENTAL PROCEDURE Grade A Carbonyl nickel powder having the following composition: C, 0.07 pct; Fe, 0.013 pct; Mn, 0.0005 pct; Si, 0.016 pct; Mg, 0.0003 pct; S, 0.003 pct, was purchased from the International Nickel Co. The platinum-group metal powders were purchased from A. D. Mackay Co. The powders were weighed, cone-blended for 4 hr, and vacuum-melted into 1-in.-diam billets, approximately 2 in. long. The ingots were homogenized for 5 hr at 1800°F before being extruded into 1/4-in. rods at 2100°F. The alloy compositions are shown in Table I. Typical impurity values were not significantly different than that of the as-received nickel. All alloys were single phase. The lattice parameter of each alloy after the heat treatment described below is also included in Table I. Each alloy was annealed at 2200°F for 1 hr and air-quenched to comparable grain sizes (ASTM G.S. No. 4-5). The rods were then machined into test samples 0.160-in. diam and 0.750-in. gage length. Tension testing was carried out in an In-stron tension-testing machine at a strain rate of 0.02 in. per in. per min. An extensometer was used to determine the room-temperature yield stress. Stress-rupture testing was carried out in an Arc Weld stress-rupture unit. All testing was performed in air. EXPERIMENTAL RESULTS A) Room-Temperature Mechanical Properties. The 0.2 pct yield stress, ultimate tensile strength, and elongation for all alloys tested at room temperature are plotted as a function of atomic percent solute element in Fig. 1. The ultimate tensile strength for the same atomic percent increases in the order palladium, rhodium, ruthenium, osmium. The yield strength at low concentrations, -0.5 at. pct, increases in the order osmium, palladium, ruthenium, rhodium. At higher concentrations, 3.0 and 10.0 pct, the yield strength increases in the same order as the tensile strength. Both yield strength and tensile strength increase rapidly ini-

Jan 1, 1964

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By J. C. Scully

In June, 1965, Sanderson and scully5 reported at the Conference on Environment Sensitive Mechanical Properties of Materials at the Research Institute for Advanced Studies at Baltimore that thin foils of titanium could be prepared by chemical polishing in a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. The technique is simpler than that since reported by Rice and Orava. As-received annealed titanium (containing 0.8 pct Fe and 30 ppm H) in the form of sheet 0.05 cm thick is placed in the solution and moved up and down. The reaction is violent but suitable foils are obtained very easily and consistently. A typical micrograph is shown in Fig. 3. The small precipitates were not identified. Yamane and ueda6 observed many spotlike features which they referred to as small dislocation loops. While their spots may be due to the reaction of the warm foil with the air as suggested by Rice and Orava, the precipitates in Fig. 3 are also found when foils of titanium are prepared by electro-polishing at low temperatures and subsequently examined in the electron microscope without any inter- mediate warming. Furthermore, they are not a surface effect. It is necessary to add that alloys of titanium cannot be so easily thinned by the chemical polishing solution described above since it contaminates the a, phase with hydrogen and produces y hydride. These matters are described at length in a paper7 and their relevance to stress corrosion is considered elsewhere.'-* Author's Reply The authors are grateful to Dr. Scully for bringing to our attention his hitherto unpublished technique for thinning unalloyed titanium, and deeply regret the unintended apparent duplication. The chemical thinning solution (7 parts HNO3 and 3 parts HF, by volume) reported by us is the same as that with which, for some period in the past, we had experienced success in the preparation of foils from single and polycrystalline niobium. Its subsequent effective application to titanium was a logical step, which, clearly independently of Scully, was conceived by Mr. Rice, to whom full credit is due. A few comments are warranted concerning some of the details of the preceding Discussion. It is evident to the discerning reader that the two thinning techniques under consideration are chemically almost identical, and in that sense are equally "simple". The chemical aspect is, of course, the one of primary importance in both communications. Thereafter, the relative simplicity is dictated by the mechanics of the actual thinning operation selected by the individual investigator. Our standard dimpling, or dishing, procedure was chosen with a view toward providing, for the electron transparent areas of the sample, the maximum protection from extraneous deformation during handling. That the long, straight dislocations visible in Scully's electron micrograph of a seemingly recovered structure closely resemble handling dislocations would tend to indicate the merit of our adopted technique. Features similar to those which Scully has attributed to precipitates, without any apparent diffraction contrast confirmation, were not observed in any of our clean foils taken from annealed or deformed specimens. This was admittedly somewhat surprising since the 3700 ppm (nominal) Fe in the A-70 commercial-grade titanium examined should have given rise to TiFe precipitates. Presumably these existed but were un-resolvable. Curiously, Scully's "precipitate1' density is fairly high although the iron content quoted was less than one-fourth of that in our material. One is forced to conclude from the evidence that prior thermal and mechanical treatments are responsible for the two different types of structure observed.

Jan 1, 1968

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse-grained high-purity aluminum at temperatures approaching the melting point permitted the formulation of a theory of subgrain formation. Subgrain boundaries were found to be formed by two different processes: kinking and polygonization. Polygonization is considered as the main factor in subgrain formation. SINCE "slipless flow" was first discussed in detail by Hanson and Wheeler,' many studies have been undertaken to determine how metals deform at high temperatures. Several types of observations have been reported. Jenkins and Mellor,² working on the creep of mild steels and various grades of commercial irons, found metallographic evidence of a kind of substructure within the grains after deformation at high temperatures. Homes" observed after creep deformation of steel at high temperatures that the original X-ray spots were sharply divided into several small ones. The same phenomenon was reported by Hirst4 from his studies on lead and later by Crussard5 from his work on aluminum. The works of these investigators demonstrated beyond any doubt that the splitting of the X-ray spots was due to the fact that the grains underwent a division into subgrains during deformation at high temperatures. Since then, numerous experiments have been undertaken on aluminum in order to determine the mechanism of formation of subgrains. Research workers can be divided, for the purpose of discussion, into two different groups as regards thinking on subgrain formation. On one hand, based on the work on polygonization by Cahn,6 Guinier and Lacombe,7 Greenough and Smith," Crussard,10,11 and Servi, Norton, and Grant," it was concluded that subgrain formation was a consequence of the simultaneous effects, first, of inhomogeneous deformation which produced bending of the lattice, and second, polygonization. On the other hand, Wood and coworkers13-16 based their work on the results of an earlier report" which dealt with crystallite size and a fragmentation theory. It is interesting to note that while Greenough and Smith8 and Wood et al. performed similar experiments, their conclusions were quite different. Wood et al. did not recognize polygonization as a fundamental mechanism and said that aluminum, at the beginning of the deformation, fragmented immedi- ately into subgrains in order to permit deformation of the metal, the number of these subgrains being a function of strain rate and temperature. They concluded that deformation of grains occurred by flow along the subgrain boundaries. In view of the contradictory conclusions, it would appear that the data were not explicit enough to provide an unambiguous conclusion. It appears that the techniques by which most of the results were obtained, namely, X-ray work, were not enough by themselves to solve the problem. Another approach was needed. In the present research, therefore, an extensive metallographic study was planned to supplement the X-ray work. The importance of revealing the subgrain boundaries metallographically was realized, and this will explain the extensive development and use of etching techniques. In order that subgrains would be considerably larger and therefore more readily visible under a microscope, the creep experiments were performed at very high temperatures approaching the melting point of aluminum. Development of Experimental Technique Creep tests were run at constant load on high purity (99.995 pct) aluminum specimens having a very coarse grain size. None of the specimens was run to fracture. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled in the gage section to permit

Jan 1, 1954

By E. C. W. Perryman

On electropolishing, high-purity Cu-Sn and Cu-Sn-P alloys with more than 5 to 9 pct Sn were found to contain many grain boundaries with a ridge-and-furrow profile. The effect was not eliminated by solution treatment and was present at the new boundaries in recrystallized material. It could be produced by diffusing tin into the 3 pct Sn alloy and it is concluded that the effect is due to enrichment of certain boundaries in tin, or possibly in an impurity present in the tin, in solid solution. IN the hot working of tin bronzes, especially those with moderately high tin contents, considerable difficulty is frequently encountered from intercrystal-line weakness, which results in cracking at the edges in sheet on strip rolling and in the unsupported regions of the rod in rod rolling.' These difficulties are not at all pronounced with up to 3 pct Sn, but at 5 pct Sn impose serious limitations and at higher tin contents, especially if the phosphorus content is also high, they may become very severe. In some work carried out at the laboratories of The British Non-Ferrous Metals Research Association it was found that a notable lack of ductility in tension at elevated temperatures, associated with intercrystal-line failure, was characteristic of tin bronzes even of relatively high purity. That the intercrystalline fracture is not due to a brittle or molten impurity phase at the grain boundaries was shown by the fact that the temperature at which intercrystalline fracture first occurred decreased with decrease of rate of straining. Tensile tests on some commercial tin bronzes, reported by Goetzel,² show a similar fall in ductility with increasing temperature. As no visual evidence had been obtained showing that the grain boundaries of the tin bronzes were different from those in copper, a more detailed microscopical examination was carried out, and the results of this are given in the present report. Several workers"' have observed that electrolytic polishing is a powerful tool for detecting small amounts of a second phase and in particular for detecting high solute concentrations, "equilibrium segregation," at grain boundaries. Since it had been found that the suggested solutions for electropolishing bronze and the standard solutions for brass and copper did not give satisfactory results it was first necessary to find a suitable electropolishing solution.' Experimental Procedure Materials Used: The cast and wrought materials used for this work were the same as those used for the mechanical tests referred to above. They comprised 3, 6, and 9 pct Sn alloys without phosphorus and the same three basic alloys with 0.03 and 0.4 pct P. A 5 pct Sn alloy without phosphorus, of similar purity, was also examined. The basis materials were Chempur tin, high purity 15 pct phosphor-copper and cathode copper, and spectrographic analyses are given in Table I. Treatment: The cathode copper was first melted under charcoal, degassed by plunging marble chips beneath the surface, and cast through a coal gas flame into sand molds to produce a number of small ingots which after machining were of a suitable size for subsequent vacuum melting. Chill cast bars of the alloys, approximately 1¼ in. in diameter, were then made by melting and casting in vacuo, the tern-

Jan 1, 1954

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.' Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer's number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By J. W. Whalen

The design, operation and evaluation of an instrumental method for the determination of fluid saturation in porous materials during multiphase flow studies is described. The presence of a magnetic tracer comprising approximately 20 per cent by weight of the aqueous phase is necessary in the utilization of this method. The results of two-phase relative permeability studies on two samples of porous media are presented. The realizable accuracy of the magnetic susceptibility apparatus in fluid saturation determination is estimated to be 2 saturation per cent. The response characteristics of the instrument, together with its simplicity of operation and maintenance are sufficient to recommend its use in routine laboratory studies. INTRODUCTION The problem of fluid saturation determination in laboratory multiphase flow studies characterizing oil recovery processes is one which has been given exhaustive study. Briefly the requirements which are considered essential for a method sewing this purpose are: (1) that the measurement be made external to the porous rock sample under study with no interruption of the fluid flow pattern, (2) the saturation indication must be independent of fluid distribution in the volume scanned by the measuring device, (3) the sensing element should have a small field of definition enabling several independent measurements to be made along the length of a core sample, and (4) the properties of the fluid phases should not be too greatly influenced by required tracer substances. Several methods of saturation determination have found acceptance as meeting most of the above requirements. These include resistivity,1 X-Ray absorption,2,3,4 radiotracers,5,6,7 and neutron8 diffraction The merits of these techniques have been discussed elsewhere in detail and will not be considered here. It may, however. be pointed out that the elaborate instrumentation required by the methods mentioned above, with the exception of the resistivity method (which is undesirable from other standpoints) encourages the development of methods of saturation determination which, while meeting the requirements listed, are simple to operate and maintain. It is the purpose of this paper to describe the instrumentation and evaluation of a technique for the determination of fluid saturation which combines relative simplicity with an accuracy and applicability comparable with methods now in practice. DESCRIPTION OF THE METHOD If the magnetic susceptibility of one of the fluid phases contained within a porous material is sufficiently greater than that of the remaining phases, the fluid content of the material with respect to that phase may be determined by an induction measurement. This may be accomplished by measuring the induced voltage in the secondary of a transformer which contains the porous sample and its interstitial fluids as a portion of the magnetic flux path. Since the fluids used in multiphase flow studies involving petroleum reservoir samples possess uniformly low magnetic susceptibilities, the use of a magnetic tracer in one of the fluid phases is required. In view of the relatively high paramagnetic susceptibility of salts of the transition elements, together with their high water solubility. these compounds become logical choices as tracer materials. Cobaltous chloride, having a specific magnetic susceptibility of 17.5 x 106 cgs electromagnetic units, was used as the tracer material throughout this work, in a concentration of approximately 20 per cent by weight in the aqueous phase. MAGNETIC SUSCEPTIBILITY APPARATUS Basically, the magnetic susceptibility apparatus consists of a transformer serving as the detecting head, a

Jan 1, 1955

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By R. E. Maringer, B. A. Wilcox, A. H. Clauer, J. H. Sovik

Internal friction measurements from 25° to 1100°C have been made on specimens machined from TD nickel bar. The use of miniature torsional pendulum specimens alloived damping measurements to be made on specimens whose axes were parallel to the original bar axis, at 45 deg to the bar axis, and at 90 deg to the bar axis. There was a marked difference in damping with varying specimen orientation, and this was related to the pronounced micro structural anisotropy of this material. Varying the microstructure by cold working plus re crystallization annealing also greatly affected the damping behavior. Recrystallization essentially removed the broad peak found at 400° to 650°C in as-received TD nickel, and in addition greatly lowered the background damping. DlSPERSION hardened metals such as SAP-type alloys (Al + AI2O3) and TD nickel (Ni + 2 pet ThO2) have been developed primarily to improve high temperature strength properties. There have been numerous damping studies on SAP-type alloys,1"9 and one of these6 showed that the damping capacity was greater than that of 99.5 pet pure Al from 25° to 600°C. Several preliminary observations on TD nickel10 and an experimental Ni-ThO2 alloy11 indicated that here, too, the damping capacity was quite high. A high damping capacity in TD nickel, combined with its relatively good high temperature creep strength, could provide an additional benefit for some high temperature structural applications. This work was undertaken to study the internal friction behavior of TD nickel bar over the temperature range 25° to 1100°C. In Ni-ThO2 and Ni-Cr-ThOz alloys, other properties such as steady-state creep rate,12 creep rupture life,12'13 modulus of elasticity,14 and ultimate tensile strength,14 are sensitive to orientation with respect to the primary working direction. Thus, in order to examine anisotropy effects in damping, studies were made on specimens machined with their axes parallel, at 45 deg, and transverse to the original bar axis. MATERIAL DESCRIPTION AND EXPERIMENTAL PROCEDURES The material used in this investigation was from the same £ in. diam TD nickel bar that has been studied previously.13'15 The structure typical of the as-received TD nickel is shown in Fig. 1, and additional details of the structure can be found in Refs. 13 and 15. Elongated grains are parallel to the bar axis and are about 10 to 15 u long and about 1 u in diam. This structure is very stable, since no recrys-tallization or grain growth occurred after annealing for 3 hr at 1300°C.13 The total ThO2 content was 2.3 vol pct and the particles ranged in diameter from 100 to 1000. The average particle diameter was 370Å and the mean planar center-to-center particle spacing was 2340Å. To examine the influence of grain and subgrain structure on damping, a section of TD nickel bar was swaged and drawn at room temperature from 1/2 in. diam bar to 0.040 in. diam wire (99.3 pct re-duction in area). The structure in Fig. 2 resulted after the wire was annealed for 3 hr at 1250°C. The recrystallized grains were much larger than the grains in as-received bar, but still showed considerable elongation in the direction of working. A high

Jan 1, 1970

By I. R. Kramer

I. R. Kramer (Martin Co.)—In a recent paper Nakada and Chalmers24 reported some observations of effects of surface conditions on the stress-strain curves of aluminum and gold single crystals. It is of interest to compare these observations with the results published previously in this journal and to comment on their general conclusions. In brief, Nakada and Chalmers concluded that the removal of the surface layer of a prestrained specimen lowered the stress-strain curve for aluminum but not that for gold. Further, they concluded that the surface work hardening of aluminum is confined to a depth not more than l0-3 cm. In our results25 published previously, it was pointed out that when prestrained specimens of aluminum and gold were polished to reduce the thickness upon reloading the initial flow stress decreased markedly. Further if a sufficient amount of metal was removed, the yield point failed to appear. With continued application of the load the stress-strain curve became coincident with that of the virgin crystal. We have found this behavior in some 100 determinations to hold consistently for gold, aluminum, and copper in both single and poly-crystalline specimens. The amount of strain required before the curves coincided depends upon the amount of metal removed but it is usually less than 0.01. This type of behavior is the same as that reported for metarecovery by other investigators.29 For aluminum specimens which have been prestrained and then heated to temperatures above 50°C we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen. With respect to Ref. 24 the curves for aluminum are always below that of the virgin curves, while those for gold become coincident. This observation indicates at least for aluminum that the specimens must have been heated to a temperature high enough to cause recovery by an alteration of the internal dislocations. In addition, a recovery would be expected because of the removal of the surface work-hardened layer. Nakada27 had reported that, with his particular apparatus in which a perchloric acid polishing solution was used, the temperature of the specimen increased 65°C. The curves presented in Ref. 24 for gold do not permit one to detect the initial flow stress upon reloading after the surface-removal treatment. In fact, contrary to the method used by Nakada and Chalmers, the change in the stress-strain curve produced by a surface-removal treatment cannot be described in terms of a decrease in stress at strains much higher than that at the initial flow stress because of the coincidence of the curves at the higher strain values. With regard to the depth of the work-hardened surface layer, our data show for aluminum single crystals (7.5 by 0.3 by 0.3 cm) that the initial flow stress remained constant after 12 x 10-3 cm had been removed from the thickness. This depth was independent of the prior strain. For gold crystals this depth is somewhere between 10 x 10-3 and 20 x 10-3 cm. Y. Nakada (author's reply)— Kramer states,28 "for aluminum specimens which have been prestrained and then heated to temperatures above 50°C, we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen." However, Cherian et a1.26 discovered that aluminum polycrystals annealed at 32" and 100°C showed the metarecovery behavior. They showed that the orthorecovery behavior did not appear until the crystals were annealed at 150°C. Kramer suggests28 that the drop in the flow stress of aluminum crystals after the surface removal by electropolishing24 may be due to the recovery caused by the temperature rise which may occur during the electropolishing.27 However, as indirectly stated in Ref. 24, the current density used in these electro -polishing experiments was 0.15 amp per sq cm. According to ref. 27, this current density should cause a temperature rise of only 40°C. This may cause the metarecovery but not the orthorecovery. Furthermore, as stated explicitly in Ref. 24, the surface removal was accomplished by chemical etching as well as by electropolishing. The results were the same for both electropolishing and etching. During the etching, the specimen temperature did not rise above 35°C. Some aluminum crystals were placed in water at 35° C for 30 min. These crystals did not show the decrease in flow stress. Therefore, it is quite clear that the flow-stress drop after the surface removal is not caused by a high-temperature recovery. However, as Kramer points out,28 it is quite possible that the internal dislocation structure may have been altered because of the removal of the highly work-hardened surface layer. However, how much this rearrangement contributes toward the flow-stress decrease is not known at present.

Jan 1, 1965

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors' conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors' article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.'); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors' reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

By E. Klar, A. B. Michael

Differences in the electrical conductivities of copper powder sintered under reducing, selectively oxidizing, and neutral atmospheres are related to impurities in solution or as precipitated oxides. The precipitation of impurities as oxides during sintering in nitrogen is proposed for maximizing the conductivity of sintered copper. Conductivity equations for two-phase systems are summarized. Selected equations are applied to porous sintered copper and composite structures. A recent review of the influence of impurities on the electrical conductivity of copper by Gregory et al.1 emphasized that an impurity in solid solution has a much more pronounced effect on reducing the electrical conductivity than when present partly or wholly as a second phase. When impurities in solid solution can be precipitated as oxides, the copper is purified with respect to these elements and the conductivity is increased. Cast and wrought copper, therefore, frequently contain an intentional residual oxygen concentration to oxidize and precipitate impurities less noble than copper. Copper powders generally also contain impurities which can contribute to a reduction in the electrical conductivity of the sintered material. The most deleterious impurities commonly found in commercial copper powders which markedly decrease the electrical conductivity when in solid solution but which can be precipitated as oxides include iron, tin, antimony, arsenic, cobalt, and nickel. In addition to impurities, porosity in sintered copper also contributes to a reduction in the electrical conductivity. The work reported herein discusses the influence of impurities, sintering atmospheres, and porosity on the electrical conductivity of sintered copper. These are important factors for controlling the electrical conductivity of materials such as sintered copper electrical contacts. Several publications on the electrical conductivity of sintered copper and composite materials with random pores or obstacles have incorrectly considered the conductivity to be proportional to the volume fraction of conducting material. However, analyses and equations have been proposed, the earliest of which is perhaps Lord Raleigh's of 1892,' which more accurately describe the conductivity of two-phase systems. These equations which in many cases allow one to closely estimate the electrical conductivity of porous sintered materials and two-phase composites will be reviewed and related to the measured electrical conductivity of sintered copper, copper-graphite. and Ag-W composites. INFLUENCE OF IMPURITIES AND OXIDIZING, REDUCING, AND NEUTRAL ATMOSPHERES Zone-Melted and Leveled Copper. The electrical conductivities of an electrolytic copper and a lower-purity compacting grade of copper powder after consecutive treatments in reducing or selectively oxidizing atmospheres are compared in Fig. 1. The powder and drillings from the electrolytic copper ingot were melted and solidified in a graphite crucible under hydrogen. The vertical zone leveling technique of multiple passes in opposite directions was used to obtain a uniform distribution of impurities. The electrical conductivity was measured on machined specimens 3 by 0.10 in. diam of the zone-leveled material and after the same specimens were consecutively treated as follows: 1) heating in hydrogen at 1600°F for 3 hr; 2) heating in air in a sealed tube so that 0.04 pct 0 was introduced; heating was started at 1000°F for 1 hr and continued at 1800°F for 8 hr; the stepwise diffusion treatment was used to avoid loss of copper due to evaporation of copper oxide at higher temperatures; and 3) final heating in hydrogen at 1600°F for 3 hr. A L&N Kelvin Bridge, type 4306, and a test fixture with knife edges 2 in. apart were used to measure the room-temperature conductivity with an estimated accuracy of ±0.5 pct. In all cases the conductivity of the electrolytic copper was approximately 100 pct of IACS. The conductivity of the impure copper was 80 pct of IACS both in the cast state and after heating in hydrogen. However, after the heating in air, the conductivity of the impure material was 100 pct IACS. After again heating in hydrogen, the electrical conductivity decreased to 60 pct of IACS. This decrease is attributed both to the dissolution of impurities and observed intergranular cracks due to the phenomenon of hydrogen embrittle-ment in copper. These data show that the electrical conductivity of commercial copper as represented by a compacting type powder can be increased significantly by the precipitation of impurities as oxides through heat treatment in an oxidizing atmosphere. Sintered Copper Powder. A commercial compacting type of copper powder pressed to various densities was sintered either in nitrogen, dissociated ammonia, or dissociated ammonia followed by a selectively oxidizing atmosphere of air in sealed Vycor tubes so that 0.06 pct O was added to the material. The electrical conductivity was measured perpendicular to the pressing direction on as-sintered specimens of approximately 3 by 0.25 by 0.15 in. The fully dense material was obtained by zone melting and leveling

Jan 1, 1969