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By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By Oliver Smalley

EXCEPT for the work of Guillet, who conducted a systematic investigation on the zinc-replacing value of nickel in brass, and extended his investigation with a view to developing commercial high zinc content nickel brasses, the author does not know of any systematic research on the subject. The most promising commercial alloys and their physical properties obtained by Guillet are given below: Maximum Elonga- Reduction Copper Zinc Nickel Stress, tion, of Area, Brinell Tons Per Per Cent. Per Cent. Sq. In. 55.0 41.0 5.0 24.4 46.5 94 Sand cast. 22.6 27.0 90 Chill cast. 56.7 39.74 3.35 30.0 43.0 51.7 97 Casting annealed 2 hr. at 750° C. 33.9 33.0 50.7 144 Cold-drawn bar. 55.15 42.3 2.24 29.8 33.0 116 Casting annealed 2 hr. at 750° C. 32.3 29.0 151 Cold-drawn bar. These test results scarcely justify the use of such quantities of so expensive a metal, and could have been obtained from ordinary commercial brass. For purposes of comparison, the physical properties of ordinary brasses, ranging from 70 per cent. to 50.1 per cent. Cu in both the cast and normalized1 conditions are included in Table 1. These incidentally furnish a useful standard of the properties of castings and of rolled, extruded and forged brass when correctly annealed. A close study of some of the well-known special brasses containing nickel reveals a series of alloys which bewilder by their complexity, and one can only hazard a guess at the function and commercial value of each of the many elements used.

Jan 10, 1925

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By G. G. Priest, B. E. Morgan

The production of oil and gas from wells is often seriously hindered by the compaction of solids in the perforations during the perforating process. To realize the full productive capacity of a well, it is necessary either to remove the plugging material from the perforations or to perforate in a manner which does not cause plugging of the perforations. The latter method can be accomplished by having a non-plugging fluid in the casing at the time the well is perforated. This paper describes the results of laboratory tests, perforating tests, and experimental field tests which demonstrate that certain emulsions serve effectively as non-plugging perforating fluids. The principal components of these emulsions are two liquids: an aqueous phase consisting of a solution of either sodium chloride or calcium chloride, and an oil phase consisting of diesel oil, tetrachloroethylene, or a combination of both. Small amounts of other agents which serve to stubilize the emulsions, to reduce the fluid loss, and to inhibit corrosion are also present. The density of the emulsions is controllable within the range of 7.5 to 12.5 lb/gal; no insoluble solids are present, the filtration rate is low, and the thermal stability is satisfactory at temperatures as high as 200°F. The corrosion of steel by these emulsions is negligible. Tests conducted under conditions which simulate the temperature and the pressure in an actual well demonstrate that these emulsions fulfill the requirements of a non-plugging perforating fluid. In addition, lirnited field experience furnishes evidence that these emulsions remain in position after they are spotted, that they are retained in the casing after the perforations are made, and that they are easily removed from the perforations when the well is opened for production. When the pressure in the borehole is greater than the formation pressure at the time a well is perforated, plugging of the perforations can be avoided by spotting an emulsion adjacent the interval to be perforated. This procedure should eliminate low well productivity caused by plugging the perforations. INTRODUCTION Nature of Problem The most widely used method for the completion of oil and gas wells is to set and cement casing through productive horizons, and then to obtain production by gun-perforating the section of casing opposite the desired interval. This method is gen- erally successful and it was thought at one time that those failures which did occur were due to insufficient penetration by the perforator. Despite recent improvements in perforators which assure ample penetration, unsatisfactory fluid production continues to be a problem. Evidently, the trouble comes from some other source. Recent results obtained by Allen and Worzel1 demonstrated that low fluid productivity may be caused by the perforating process and/or by the fluid in the wellbore at the time of shooting. They found that perforations are often completely plugged by debris from the perforator, pulverized sand from the formation, and compacted solids from the drilling mud when the pressure in the wellbore is greater than the pressure in the formation at the time of perforation. In some cases a differential pressure in excess of 400 psi was required to initiate flow into the well through these plugged perforations. The plugging of perforations by solids not only causes low productivity from wells, but it creates simultaneously other problems in the production of oil and gas. For example, when most of the perforations are plugged, high rates of flow must occur through the few perforations that are open. The resulting high pressure drop may cause production

Jan 1, 1958

By R. F. Mehl, R. W. Parcel

THE rate of the decomposition of austenite in eutectoid steels, forming only pearlite, may be expressed fundamentally in terms of the rate of nucleation and the rate of growth of pearlite nodules. This matter has received much attention in recent years. (The basic references are listed in ref. 1; references of particular import to the present work will be given separately.) Systematic data have been developed for plain carbon eutectoid steels.:! Although the physical factors affecting the rate of nucleation, N, in case of plain carbon steels have presumably been identified, they cannot as yet be evaluated quantitatively.' Several somewhat successful attempts, however, have been made to calculate the rate of growth, G. In the latter case the important factors determining the edgewise growth of pearlite have been assumed to be: 1—the interlamellar spacing; 2—the concentration extremes and concentration contours of carbon in austenite in front of the growing pearlite interface; and 3—the rate of diffusion of carbon in austenite.* The only systematic data on N and G for pearlite in alloy eutectoid steels are those for Co-steels;6 there are no data on alloy eutectoid steels in which the alloying element is known to decrease the rate of formation of pearlite, apart from a few scattering data reported earlier' for steels containing manganese. This paper reports a systematic study of N and G for eutectoid alloy steels containing molybdenum and nickel, respectively. In order to provide information of help in understanding the results, new data are presented on the effect of molybdenum on the interlamellar spacing of pearlite, So; data on the effect of nickel on So have already been published.' The alloys used were in five groups: 1—Pure Fe-C-Mo alloys (Table I) were supplied by the Climax Molybdenum Company of Michigan, Detroit. They were made from Armco ingot iron of standard analysis, Acheson graphite, and ferro-molybdenum, melted in silica-lined crucibles in a high frequency induction furnace. The ferromolyb-denum was added to the melted steel, followed in 5 min by 0.08 pct Al. The ingot as-cast measured 23/4x 31/4x10 in.; it was hot-forged at 1150°C to a bar 1 in. sq.

Jan 1, 1953

By J. A. Danko, C. D. Pears, L. D. Schmidt, J. P. McGee

This paper describes a pilot plant built on the campus of West Virginia University by the Federal Bureau of Mines station at Morgantown, West Virginia, for gasifying pulverized coal in a mixture of oxygen and steam at pressures in the gasifier up to 450 psig. The work upon which this report is based was done under a cooperative agreement between the Bureau of Mines and the West Virginia University. The goal of Bureau of Mines work at Morgantown is development of a low-cost process for producing mixtures of carbon monoxide and hydrogen for the modified Fischer-Tropsch synthetic-fuel plants, which may be shifted to produce hydrogen for coal-hydrogenation plants. Gasification with oxygen offers the inducement that the gas may be generated at the pressure at which the gas will be utilized in a gas-synthesis plant. Since the optimum pressure for the synthesis appears to be about 400 psig, the gas should be produced at approximately 450 psig to take care of pressure drops in the purification train and control valves. If the gas is generated at the pressure of utilization, only the oxygen need be compressed, not the raw synthesis gas. This means a saving in power of 5 hp per hour per 1000 cu ft (CO + H2), which is approximately a saving of 4 cents per gallon of gasoline. For example, consider a commercial plant generating 18,000,000 standard cubic feet per hour of raw gas that would produce approximately 10,000bbl of liquid product per stream-day. Assume that this gas would be 85 pd CO + H2 and that the oxygen required would be 320 cu ft per 1000 cu ft of CO + H2. The following estimate is based on a commercial centrifugal compressor. If the 18,000,000 std cu ft per hour of synthesis gas is compressed to 450 psig with 74 pd efficiency, 107,000 hp is required for compression. If the synthesis gas is generated at 450 psig pressure, only

Jan 1, 1953

By Walter Craft, John L. Lamont

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By J. B. Mudd

Introduction It is difficult to think of any activity on which mankind has been more dependent than mining, and certainly there is much evidence in almost every part of the world of old workings that clearly demonstrate that man from earliest times has dug and toiled to take from the earth precious stones, metals and materials that from time to time have been essential or of value to him. In step with social development and industrial and technological advances the tempo of mining activity, regulated only by the laws of supply and demand, has quickened and in this century has accelerated rapidly in keeping with its dramatic development. Indeed, the rate of change of events has been such that if it were to continue to accelerate as fast as it has over the past decade there is reason to wonder how the insatiable demands for metals and minerals are to be met in the years that lie ahead. Shallow mines containing high-grade ore deposits either have been or are being rapidly mined out and their place can only be taken in general by ore lying at greater depth, or by ore of low grade, situated for the most part in remote and in underdeveloped areas. The cost of exploration and development is rising at an alarming rate, with the result that the expenditure now required to bring a mine to production far exceeds anything previously contemplated. It is estimated that the total capital required to maintain existing operations and develop new ones during the next 5 years will be of the order of $50,000 million and of this, new capital to bring new mines to production will be of the order of $3,000 million. Today no single mining finance company can, from its own resources, find all the money for a major mining development, and as a consequence there has been a strong trend toward joint ventures and to the formation of multinational consortiums. International lending institutions already play an important part in financing many new mining projects and their participation provides the financial umbrella under which other lenders can invest with greater security. There is little doubt that to finance the costly ventures in the future, governments and international lending agencies, banks and finance

Jan 1, 1971

By R. F. Mehl, G. V. Smith

THE decomposition of austenite in steels, because of its immense practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1-3 Although much information has been acquired, a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings-pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. PEARLITE Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix .2-5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth.2.3 Mehl and Smith6 have attempted to determine the lattice relationships existing between the ferrite in pearlite and the parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible, however, to decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrongly, as Mehl and Smiths have pointed out, that the lamellae delineate the [210] planes of ferrite.* MARTENSITE It is known that martensite is a transitional constituent of body-centered tetrag-

Jan 1, 1942

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.&apos; During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Perry G. Harrison

The first autlientic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is. said to have worked out his process. Jacobil in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein&apos;s process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeS04 + (NH4)2SO4. Lenz2 described some properties of electrolytically precipitated iron. He used Klein&apos;s bath, FeS0, + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By Oscar A. Glaeser

THE mine and plant of the United Verde Copper Co., located in Yav-api County, at Jerome, Arizona, have been described in various technical publications and, therefore, a brief outline of its essential features will suffice. The orebodies are of the schist replacement type, the main sulfide mass being a large lens-shaped body approximately 7 acres in cross-sectional area. In general, the mineralization is found along the iron-schist contact, with the orebodies extending about 1000 ft. along this contact and varying from a few feet to 250 ft. in width. The mine is located on a mountain slope and has openings into it on three horizons, as follows: 1. Raises and ore passes open vertically into the shovel pit. These extend down to the 1000-ft. level, where they terminate as loading bins in the Hopewell adit. The main fan intake air shaft, which also extends vertically down to the 1000-ft. level, has its surface opening on the hillside at the extreme north end of the shovel pit, and the main mine air return exhausts through a raise at the extreme south end of the shovel pit. 2. The 500-ft. level adit. 3. The Hopewell adit on the 1000-ft. level. The mine has a vertical downward extent of 2000 ft. below the 1000-ft. level. Underground operations are carried on through two main shafts, both of which are wholly underground. Shaft 5 is the ore-hoisting shaft. It has three compartments and extends from the 800 to the 3150-ft. level. Shaft 6 is the service shaft, and is used for lowering and hoisting men and material. It has a large cage compartment and three smaller compartments for counterweights, ladderway, and pipe and power lines. This shaft extends from the 500 to the 2550-ft. level, and is now being extended to the 3000-ft. level. An air shaft for the downward movement of fresh air from the fan has been provided, and extends to the 2550-ft. level at this time. Work has been started to extend this air shaft to the 3000-ft. level. A return airway for vitiated mine air, in the form of raises and short connecting drifts, extends downward to the 2100-ft. level. The underground mining operations extend from the 300 to the 3000-ft. level. There are about 45 stopes in active operation on the 17 levels

Jan 1, 1929

By I. Nilsson, G. Sundkvist, A. Danielsson

A spectrochemical method of slag analysis is descibed which utilizes fusion of the sample with a flux, then cooling and crushing to put all samples into a common form. The powder, is then fed onto adhesive tape and passed through a spark by means of a special device to provide very reproducible discharge conditions. Combined with a direct-reading optical emission instrument, this system provides speed and accuracy of antilysis heretofore unobtainable for. slag samples by any other method. THERE are many suggested methods for spectro-chemical analysis of slags. The most important are fusion-pellet methods and solution methods. In our company the fusion-pellet method has been used earlier, and is described by Lounamaa. W. H. Tingle and C. K. Matocha have made refinements of the pellet method.&apos; A Committee of the British Iron and Steel Research Association has investigated different methods of spectrochemical analysis of slags. Its purpose was to formulate a method which would give the complete analysis in 30 min with an accuracy of ±3 pct. The committee recommends a solution technique, which was thought to correspond best to their requirements. The method to be described is a fusion-tape method. The sample is isoformed by fusion and grinding. The powder is analyzed with the tape technique. The tape machine and some of its applications are described earlier.4&apos;5 The powder to be analyzed is continuously fed onto a moving adhesive tape, which passes through the spark gap. The sparks break through the tape and vaporize and excite the material to be analyzed. The most outstanding feature of the tape machine is its very high reproducibility. The concept of isoformation has been introduced earlier.= It means a pretreatment of the samples to make them uniform from the spectralanalytical point of view, i.e., cancelling systematic differences between the samples. The purpose of the isoformation is to reduce the influence of particle size, as well as chemical and mineral composition. Before describing the isoformation by fusion plus grinding, which is the purpose of this paper, a few words will be said about two other types of isoformations, i.e., grinding with buffer and ion exchange plus grinding as they have been considered during the application of the tape technique for slag analysis. Grinding with buffer might be a sufficient isoformation in some special cases, where the mineral composition is defined. The time of grinding must, however, be rather long, at least 5 to 10 min, even when using such an efficient mill as the Swing Mill from Messrs. Siebtechnik, Mühlheim, Germany. This type of isoformation is not recommended due to its limitations and due to the fact that the gain in time compared with the fusion technique is almost negligible. The principle of ion exchange plus grinding and some of its applications have been described.5 The following elements of interest in slag analysis can be determined in this way: Na, K, Cu, Mg, Ca, Ba, Zn, Pb, Al, Cr, Mn, Fe, Co, Ni. The very important element Si, however, cannot be analyzed with this method. Although the ion exchange isoformation for slag analysis cannot be looked upon as a routine method, it can be used for

Jan 1, 1962

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942