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By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous metals of certain classes recovered in the United States for the year 1924 to 1925 as shown in Table 1. The figures are tabulated simply to give the reader some idea of the scope of the secondary non-ferrous metal industry. Approximately 900,000 tons of an annual value of $244,000,000 were recovered in the year cited. In 1916 (again using the Mineral Resources of the United States as authority) the tonnage reclaimed was approximately 632,000 tons and the value, because of the high prices for metals prevailing at that time, amounted to $265,000,000. It is not the purpose of this paper to discuss smelting and refining operations or the feasibility of an organization, primarily engaged in some other activity, conducting smelting and refining operations to convert its own non-ferrous scrap metals and alloys. The classification and preparation of these non-ferrous materials is a preliminary step, regardless of what subsequent operations the material may pass through or where these operations may be conducted. For that reason the subject can be readily discussed without any reference to subsequent activities. Space must be provided, with suitable handling facilities, scales and the necessary storage bins where the material may be accumulated. The scope of the activity, the nature of the industry and the tonnage handled will determine, in a large measure, what preparation, if any, it may be desirable to give these scrap materials to put them in the best marketable condition. By preparation is meant largely what, for the want of a

Jan 1, 1928

By R. Fahn

Bentonites are best suited for the preparation of acid activated clays with efficient adsorption properties. They are weathering products of acid volcanic ashes and natural deposits are spread worldwide. The main constituent of bentonite is aluminum hydrosilicate montmorillonite with a high ability to swell. Physical and Chemical Properties of Montmorillonite The clay mineral montmorillonite is named after its place of discovery, near Montmorillon in southern France. The structure of this clay is shown in [Fig. 1]. The montmorillonite crystal consists of about 15-20 silicate plates. Each silicate plate is composed of three layers. The central one is formed by aluminum or by ferric hydrate octahedrons, the two outer ones consist of silicon dioxide tetrahedrons. In the presence of water, the montmorillonite crystal swells and water molecules become deposited between individual silicate layers. Two types of natural bentonites are known: the Western type, which is a natural sodium bentonite (high swelling grade), and the Southern type, an alkaline earth or calcium bentonite (low swelling grade). Southern bentonites have efficient adsorption properties of their own. They are called natural active earths or fullers earths. Acid Treatment of Bentonite Under the influence of a mineral acid, the exchangeable alkaline earth ions of bentonite are substituted by hydrogen ions. Moreover, depending on the acid concentration, temperature, pressure, and reaction time, a more or less pronounced leaching process takes place. Thereby Al-, Fe-, and Mg-ions are extracted from the octahedron layers. This results in a change in the crystalline structure of montmorillonite and in an increase of its specific surface area and porosity, as shown in [Fig. 2].

Jan 1, 1983

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By C. T. Liu, J. Gurland

The deformation behavior in tension of spheroidized carbon steels was studied at room temperature as a function of carbon content, 0.065 to 1.46 wt Pct, and carbide particle size, 0.88 to 2.77 p. It was found that the Hall-Petch strength-grain size relation is directly applicable to the yield and flow stresses of the two lower-carbon steels , 0.065 and 0.30 pct C. The strength data for the medium- and high-carbon steels, 0.55 to 1.46 pct C, also satisfied the Hall-Petch relation, provided that these data are based upon the particle spacing. Beyond 4 pct strain, the flow stress data of all the steels studied could be represented by the same Hall-Petch relation with dinerent spacings for grain boundary and particle strengthening. The behavior of the higher-carbon steels was consistent with the postulated formation of a dislocation cell network during processing and initial deformation (up to 4 pct strain). The cell size was assumed to be equal to the planar particle spacing. The true stress at the ultimate tensile strength was also found to be a function of the particle spacing. At a given temperature and strain rate, the yield and flow stresses of carbon steels depend on the type and dimensions of the microstructure. Starting with the work of Gensamer et al. in 1942,' experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2'3 and the carbide particle spacing;1'4'5 on this basis, two different strengthening mechanisms have been developed to apply to steels of low and high carbon contents, respectively. In polycrystalline iron and mild steels the grain boundaries are regarded as the major structural barriers to slip. The relation between strength and grain size is generally represented by the Hall-Petch equation which is based on a linear proportionality between strength and the inverse square root of the average grain size.2'3y677 However, Gensamer et al.' and Roberts et related the yield strength of medium -and high-carbon steels to the carbide particle spacing alone, and they found a linear relation between the logarithm of the mean free path in the ferrite and the yield strength in both spheroidized and pearlitic steels. By means of the electron microscope, Turkalo and LOW' extended the study to finer structures; they concluded that the logarithmic relation is not valid for the entire range of microstructures unless grain boundaries are also included in the measurement of the mean free path. For the specific case of spheroidized steels, Ansell and aenel' found that the yield strength data,4'5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T'ysong found that the same data fit the 0rowanl0 relation if a planar inter-particle spacing is used. Recently Kossowsky and ~rown" studied the strength of prestrained spheroidized steels, 0.48 and 0.95 pct C, and concluded that the strength due to the carbide dispersions varies linearly with the reciprocal of the square root of the mean free path between carbide particles and dislocation networks. Such networks were first observed by Turkalo." The conclusion common to all these studies is that the available slip distance in the ferrite is the most important variable in determining strendh. Previous work on carbon steels is restricted to limited composition and strain ranges. The mechanism which governs the flow properties is not clearly understood, and, in particular, little is known about the composition dependence of the transition between grain boundary strengthening and particle hardening. The purpose of the present work is to investigate the strengthening mechanism in spheroidized steels over a wide range of carbon content, 0.065 to 1.46 wt pct, and plastic strain, yielding to necking. The spheroidized structure was chosen because of its relative simplicity and the relative ease of control and measurement of the structural parameters. The experimental work is limited to tensile testing at room temperature at constant extension rate. The effects of the carbide particles on the fracture behavior of spheroidized steels are discussed elsewhere.13 EXPERIMENTAL PROCEDURE Eight different grades of vacuum-cast carbon steels were supplied in the form of forged and rolled plate by the Applied Research Laboratory of the U.S. Steel Corp. The compositions furnished with these steels are given in Table I; the carbon content ranges from 0.065 to 1.46 wt pct, or from 1.0 to 22.3 vol pct of carbide. The steel plates were cut transversely into rods a little larger than the test specimens, 1 in. gage length, i in. diam. The rods were austenitized in air (enriched with CO by a consumable carbon-rich muffle) at 50° C above theA, orA., temperature for 2 hr and then quenched in oil with vigorous stirring. The as-quenched rods were tempered in two stages in order to obtain the desired distributions and sizes of carbide particles. The rods were first tempered at 460° C for 10 hr and then at 700" C for periods ranging from 4 hr to 3 days, in vacuum. After final machining, all specimens were vacuum-annealed again at 650°C for 1 hr in order to relieve residual stresses. The tension tests were carried out in two steps. The initial part of the load-strain curve, up to about 2 pct strain, was determined on a Riehle testing machine with an extensometer of small strain range, 4 pct strain, in order to obtain the yield and initial flow piopertiesi As soon as the first part of the test was finished, the specimen was placed in an Instron testing machine equipped with a strain gage extensometer with a maximum strain range of 50 pct. The load-strain curve to fracture was

Jan 1, 1969

THE Geophysics Education Committee has devoted several years to a consideration of the problem of training geophysicists. Past reports have dealt largely with fact finding and with the discussion of particular aspects of geophysical education. In the present report it is proposed to review the subject more comprehensively. This involves the question of what educational qualifications the geophysicist of the highest professional standards should possess, and the related question of what changes must be effected in existing educational institutions in order that prospective professional geophysicists may obtain instruction of the desired quality. The type of geophysicist here contemplated is one familiar with what is known already in the several branches of earth physics, and capable not only of following contemporary progress in any of these branches, but of contributing to that progress in a research capacity. Geophysics in its broadest sense, as has been emphasized repeatedly by this Committee, is the study of the physics of the earth and of terrestrial processes. This includes both the static and the dynamic characteristics of the gaseous, the liquid, and the solid portions of the earth, as well as its gravitational, thermal, and magnetic and electrical manifestations. Some branches of earth physics have been cultivated but slightly; others have reached an advanced state of development. Those branches whose development is sufficient to warrant explicit recognition in the form of organized Sections of the American Geophysical Union are: geodesy, seismology, tectonophysics, and volcanology, dealing with the rock constituents of the earth; oceanography and hydrology with the aqueous constituents; meteorology with the atmospheric constituents; and terrestrial electricity and magnetism with the electromagnetic manifestations. At present, instruction on the professional level in any of these branches of earth physics can be obtained in but few universities in North America. In most institutions where such instruction is undertaken different subjects are given in different and independent departments. Geodesy and hydrology are taught, if at all, as a part of civil engineering. The nearest approach to volcanology and tectonophysics ordinarily is represented by petrology and structural geology given

Jan 1, 1944

Correspondent. Must be able, by virtue of, connection, to forward; daily ands weekly, reports, outlining, conditions affecting economics of. industries, particularly the metallurgical, and chemical, industries. New. York, City. R-1982. Sales Lubrication. Engineer. Preferably with experience, as chief marines engineer familiar with internal-combustion; engines and, with, automobile trade. Must be good salesman, of goody appearance and be able to meet people. Middle West. Salary $27.00: to start. R71984.

Jan 12, 1919

By E. D. Fields, R. W. Sayers, M. C. Tippett

The Duval Corp. porphyry copper deposits at Copper Canyon and Copper Basin, though widely separated, form an econornic unit requiring integrated exploitation. Contrasts in mineralization, host rocks, and mode of occurrence present unique mining and milling problems. Mixed oxide-sulfide ore is treated in extensive dump leaching facilities in both areas. Complex Cu-Au-Ag ore is treated in a 4000-tpd mill at Copper Canyon. In both areas, hypogene metallization occurs within large aureoles of metamoiphism and hydrothennal alteration related to quartz monzonite intrusions of mid-Tertiary age. Supergene processes fitrther altered the rocks and enriched the hypogene protore. At Copper Canyon, hypogene copper and iron sulfides with gold and silver occur in fractures, as partial replacement of favorable beds, and as disseminations in Paleozoic sedimentary rocks. The lower part of the Pennsylvanian Battle formation was a particularly favorable host. Metallization occurs to a lesser extent in quartz monzonite. Metal zoning is well-developed. The deposits at Copper Basin consist principally of supergene copper minerals in arenites of the Cambrian Harmony formation. Oxidation of hypogene copper and iron sulfides in tactite zones has formed at least two commercial deposits; intersections of fractures with favorable beds exerted important ore controls. Recently, the Copper Canyon and Copper Basin properties of Duval Corp. have been added to the list of porphyry copper mines in Nevada, marking the first new copper open pit in this state in 15 years. The properties are situated in the Battle Mountain

Jan 1, 1970

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,' and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By Earl W. Palmer, Cyril Stanley Smith

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By Cyril Stanley Smith, Earl W. Palmer

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By B. Trafton, H. L. Hartman

An earlier paper1 introduced a rapid solution for mine ventilation network problems, employing the digital computer. In this paper, refinements and additions to the computer program which expand its scope of application and a solution to a ventilation network having a coal-mine configuration are presented. The revised program-written in FORTRAN for the IBM 7074 computer in Penn State's Computation Center-is applicable to any mine ventilation network employing natural splitting and having its fan located externally. It accomplishes the following: 1) Distributes an assumed total quantity of air flow among all airways of the network, performing iterations until an acceptable level of error is attained and the flow in each airway is known. 2) Computes the pressure drop (head loss) in all airways and the overall network and mine head losses. 3) Determines the operating point for the mine and a given fan, adjusting all air flows and head losses to the actual values. The basis of analysis used is the Hardy Cross method of successive approximation for solution of any fluid network, explained in detail in the earlier article. In brief, corrections to assumed air flows are computed for all the loops of a network; following distribution to the airways of each loop, the process is repeated until acceptable accuracy is attained. When a hand or desk-calculator solution is used, there is advantage to close approximation of the actual flows in the original assumption of air-flow distribution in the network. Since publication of the previous paper, in which assumption of initial quantities was also necessary in the computer solution, the program has been modified to make the first distribution itself, assigning the total quantity to one specified path in a split and then proceeding to correct the flows. The number of iterations required for a high-accuracy solution is little affected, at least in networks of few loops, 10 to 15 being sufficient to reduce the error to 1 pct or less. The principal limitation of the original program was that it contained no provision for handling a fan. Further, it did not determine the overall head loss in the network and was not designed for multiple parallel openings, such as occur in coal mines. The revised program was written to overcome these disadvantages and also to print out the adjusted flows for all airways, corrected for the system operating point. At the present time, the program can handle only an external fan. The procedure employed in solving a ventilation network is now as follows: 1) Input data consisting of airway characteristics and loop designation along with assumed direction of flow, for each branch of the network and any trunk airways, are fed into the computer. 2) Employing the resistance relationship, where R is resistance, K is friction factor, P is perimeter, L is length, A is area, and n is number of airways (where multiple intakes and returns are employed); values are computed for all airways. 3) An arbitrary, continuous route of flow through the circuit—from beginning to end—is selected and the path identified by airway numbers and read in. 4) Based on a total assumed quantity of flow Q (usually 100,000 cfm.) the computer employs the procedure described in the previous article in distributing quantities of flow among all the airways until a satisfactory level of accuracy has been attained (in the current program, the machine is turned off when the cumulative corrective error in cfm, is reduced to five times the number of airways). 5) Airway head losses H are calculated by the relation H = R Q2 and cumulated along the original designated flow route to find the overall head loss for the network. Trunk airways are then included to obtain the mine head.

Jan 1, 1964

By R. W. Fountain, W. D. Forgeng

A new constitutional diagram is presented for the cobalt-rich end of the cobalt-titaniurn system. The modifications result from the presence of a new, intermediate, fcc phase, ?, the existence and homogeneity limits of which were established by metallo-graphic and X-ray studies of alloys containing from about 3 to 30 pct Ti. The precipitation of the ? phase from supersaturated solid solution was studied by hardness and electrical resistivity measzsrements, and two distinct stages in the process were observed. COBALT forms the base for a number of precipitation -hardenable alloy systems which may be divided into two distinct categories of practical interest, a) those hardened by intermetallic compounds and b) those hardened by carbide formation. The precipitation of intermetallic compounds from solid solution in cobalt-rich alloys has, however, received very little attention. Although the phase diagrams for some binary systems capable of precipitation have been determined,' there is an almost complete lack of data on the property changes associated with the precipitation, and even less information on the kinetics of the reactions or morphology of the products. More information is available on the precipitation of carbides because of the practical significance in superalloys. A survey of cobalt binary phase diagrams suggested that the cobalt-titanium alloys might provide interesting and useful precipitation-hardenable alloys. The equilibrium diagram as proposed by Wallbaum2 is shown in Fig. 1. Köster and wagner3 have indicated that the maximum solubility of titanium in cobalt is about 10 pct at the eutectic temperature (1135oC), and this decreases to about 7.2 pct at room temperature. The temperature of the allotropic transformation in cobalt is lowered by the addition of titanium, about 5 pct being sufficient to retain the high-temperature fcc modification to room temperature. Wallbaum and Witte 4,5 have indicated that the precipitating phase in alloys containing up to about 29 pct Ti is Co2Ti, a hexagonal Laves phase of the MgNi, type. With slightly higher titanium contents, they also report a cubic modification of Co2Ti of the MgCu2-type Laves phase. Duwez and Taylor6 confirmed the existence of the hexagonal (MgNi2) modification but not the cubic (MgCuz) modification of Co2Ti and suggested that existence of the cubic form may have resulted from impurities in Wallbaum's alloys. In their work on Laves-type phases, Elliott and Rostoker 7 reported the cubic modification of Co,Ti, but did not confirm the existence of the hexagonal modification. However, Dwight8 in a discussion of the work of Eliott and Rostoker again showed the existence of both modifications of Co2Ti, a result which was confirmed at that time by Elliott and Rostoker. As a result of a study on the iron-cobalt-titanium system, Köster and Gellers suggested the existence of a Co3Ti phase isomorphous with Fe3Ti. Witte and Wallbaum,' however, established the fact that no compound, Fe3Ti, exists in the iron-titanium system, and in a later publication, wallbaum2 stated that Kitster and Geller's reasoning was not valid, and no compound, Co3Ti, exists. This conclusion was later acknowledged by Köster.10 Preliminary experiments by the present authors to determine the precipitation-hardening characteristics of the cobalt-rich, cobalt-titanium alloys re-

Jan 1, 1960

By G. R. Speich, R. A. Oriani

The rate of coarsening (Ostwald ripening) of copper precipitate Particles in an a-iron matrix has been studied in three Fe-Cu alloys containing 2.3, 4.0, and 5.4 wt pct Cu in the temperature range 730° to 830°C. The kinetics of Ostwald ripening ohevs the law as deduced by Lifshitz and Wagner so that matrix diffusion controls the process. The equilibrium shape of the particles is that of rods with hemispherical caps, and is due to the BOTH Lifshitz and slyozov and wagner3 have recently solved the complex problem of determining the rate of coarsening of an assembly of precipitate particles. Both workers, although using somewhat different mathematical approaches, arrive at the same equation for the relation between the mean radius 7 of a distribution of spherical particles and the bulk solubility co, diffusivity D in the matrix, large anisotropy in the copper/a iron interfacial free energy (y,/y, = 4). A Lifshitz -Wagner equation, modified for both the nonsphericity of the diffusion field and the reformulation of the Gibbs-Thomson equation for the case of nonsphencal particles, is derived. Using the modified equation, the calculated values of the mean radius are smaller than those observed by a factor of about one -half. absolute temperature T, gas constant R, surface free energy y of the precipitate/matrix interface, and the time t of aging: where V, is the molar volume of the precipitate and v is a stoichiometric factor. Wagner's treatment is restricted to the case of spherical particles growing in a liquid matrix where strain energy is not a factor. Lifshitz and slyozov have discussed the effect of anisotropic particle shapes and internal strains on the rate of coarsening. Oriani4

Jan 1, 1965

By Raymond E. Byler

THE challenge of unprecedented need for more metals to meet present-day re-armament and domestic requirements is being met with minerals beneficiation projects of great number and variety, and with new and improved methods, techniques, and. equipment. Iron Range Developments Much attention has been given during the year to the tremendous program for beneficiation of taconites and intermediate iron ores which is progressing through large pilot-plant tests preparatory to full-scale production operations. The greatest activity has been directed toward concentration of magnetic taconites on the Mesabi Range. The Reserve Mining Co. has let $75 million in construction contracts for the 2 ½ million-ton-per-yr project (concentrates) at Beaver Bay, Minn., and is building a 300,000-ton-per-yr pilot plant to prove up the magnetic separation and pelletizing operations. Oliver Iron Mining Co. has a pilot plant under construction near Mountain Iron for concentrating magnetic taconites, and is operating experimentally a sintering and nodulizing plant on fine ore screenings and concentrates at Virginia to fully develop agglomeration technique. The Erie Mining Co. plant at Aurora continues its production of concentrates from magnetic taconites which was begun three years ago. No plans have been announced to treat the Mesabi Range nonmagnetic taconites, but F. D. Devaney, Pickands Mather and Co., is studying a new process for magnetically roasting lean ores to make them amenable to low-intensity magnetic concentration. W. R. Van Slyke, Cleveland-Cliffs Iron Co., calls attention to several noteworthy developments in the field of intermediate ores, perhaps the most significant of which has been the first commercial operation of a Dutch State Mines (DSM) cyclone plant at the Buckeye mine of the M. A. Hanna Co. The plant concentrates the +1/4 in. fraction by means of conventional heavy-media treatment after suitable crushing, screening, and washing. The -1/4 in. +65 mesh material is treated in two 12-in. cyclones, the -65 mesh fraction being sent to tailing storage. The plant is operating successfully on feed rates up to 120 tons per hr, and indicates that successful treatment of the fine fractions of Mesabi intermediate ores is imminent. Another commercial-size DSM plant was placed in operation late in the year by Cleveland-Cliffs at the Holman mine, and two additional ones are expected to be in operation next year. Various other methods are also in use at different plants for treatment of the fine fractions, including classification, abrasion milling followed by classification, jigging, and Humphrey spirals. Where it can be economically justified, it seems at present that heavy-media treatment of the -1/4 in. fine fraction will also come into increasing use on the intermediate ores. During 1951 a one-unit, heavy-media plant to treat hematitic crude ore was erected at the Ohio mine on the Marquette Range by Cleveland-Cliffs and plans for another plant at Humboldt to produce 2000 tons of concentrates annually is contemplated, as is also the construction of a plant for agglomera-

Jan 1, 1952

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

The decomposition of austenite in steels, because of its immerse 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 wrong!:!, as Mehl and Smith6 have pointed out, that the lamellae delineate the {2I0} planes of ferrite.* Martensite It is known that martensite is a transiti0nal constituent of body-centered tetragonal lattice,' and that it forms suddenly

Jan 1, 1942

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

The decomposition of austenite in steels, because of its immerse 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 wrong!:!, as Mehl and Smith6 have pointed out, that the lamellae delineate the {2I0} planes of ferrite.* Martensite It is known that martensite is a transiti0nal constituent of body-centered tetragonal lattice,' and that it forms suddenly

Jan 1, 1942