Search Documents

By Clyde E. Williams

MUCH has been said recently concerning the depletion of the Lake Superior iron ore re- serves. Estimates given indicate a total life of the present known reserves of twenty to thirty years. Some argue that there is no need to concern ourselves about the possible depletion of the Lake Superior iron ore supply because foreign ores can be brought in to this country at a lower price than rich agglomerated ore can be produced from the lean domestic ores. Some fear, as a result of this, a displacement of the steel business from present districts to the Atlantic seaboard. Others show that foreign ores will be brought to interior points via the projected Great Lakes-St. Lawrence waterway. Others believe that the South, given better freight rates, will extend its iron and steel market into northern territory.

Jan 1, 1931

By R. Hogg

Sintering is a process in which the pore structure of an agglomerated powder is modified. For many applications, it is desirable to be able to control the pore structure in order to optimize such properties as mechanical strength and reactivity (availability and accessibility of solid surfaces to reactant gases, for example). In general, these properties will be determined by the total porosity and the pore size distribution of the agglomerate. In the work described in this paper, a physically realistic mathematical model for the sintering process has been developed. The model is based on the usual assumption that the pore system in an agglomerate can be treated as a network of interconnecting, cylindrical pores of continuously varying size. It is further assumed that the total pore length is conserved during the course of the sintering process. Using standard expressions for the rate of shrinkage of an individual pore, the model can be used to predict the changes in total porosity and pore size distribution as sintering proceeds. Experimental pore size distributions, obtained by mercury intrusion porosimetry, for the sintering of oxides appear to be in general agreement with the predictions of the model.

Jan 1, 1977

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By C. E. Arnold

A BRIEF description of this installation was included in a recent paper by H. Kenyon Burch.1 The purpose of the present paper is to amplify Mr. Burch's description, as it is felt by the writer that the subject merits more than passing attention. In making a comparison between the common method of hoisting men in mine shafts, and elevator practice in high buildings, the former shows to great disadvantage both as regards safety measures and smoothness of operation. It is surprising that in view of the inducements offered, the step of applying the building equipment direct to the mine shaft has not been taken before, as in many respects the conditions of service are similar, and the objects to be attained are identical. Even without doing this, it is certain that safety to life and limb in the usual method of hoisting men underground can be greatly enhanced by the application to the mine hoist, of some of the features of the building elevator. In the case under consideration, the elevator cage runs in a vertical, concrete-lined shaft compartment 5 ft. 11 in. by 5 ft. 6 in. (1.8 by 1.68:m.) in section and 585 ft. (178 m.) deep, while the counterweight runs in the pipe and ladder compartment of a twin shaft 102 ft. (31 m.) distant. The section of the division of this compartment occupied by the counterweight measures 2 ft. 4 ¼ , in. by 3 ft. 10 ½ in. (0.72 by 1.18 m.), and the counterweight is made in the form of a small cage which. suffices to carry two men for the purpose of making inspections or repairs in the pipe and ladder way.

Jan 12, 1917

By J. F. Kemp

The use of nickel-steel has directed increasing interest of late towards the deposits of nickel, and at the same time the parallel advance in our knowledge of the basic igneous rocks has rendered these deposits a subject of important geological inquiry. Investigations have led to some views, more or less new, on the igneous origin of certain ores, which, though not universally accepted, have a growing number of adherents. In Europe, the mines in Norway have been especially suggestive subjects of study, and others somewhat less generally known have also added their testimony; while in this country the great economic importance and scientific interest of the developments in the Sudbury district of Canada, have furnished the principal texts for the discourses that have appeared among us. The purpose of the present paper is to set forth these views through the medium of one interesting ore-body, of which but little has been written ; and, by the description of another, to place in contrast two different geological associations in which nickeliferous pyrrhotite occurs, and to indicate a generalization, based upon these different geological characters, and justified by the experience so far gained. To Prof. J. H. L. Vogt, of Christiania, Norway, is due the chief credit for the revival of interest in the geology of nickel. His important contributions* of recent date have made generally available

Jan 1, 1895

By C. W. Mason

TIN has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphur. The notorious "tin disease," which Cohen1 has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white 0 tin to cubic gray a tin, has apparently encouraged the expectation that one or more addi-tional polymorphic modifications might exist. The search for confirma-tion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but for previous assumptions. The ball apparently was started rolling in 1880 by Trechmann,' who reported a new modification of tin (y tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be y tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller.3 Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,6 by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) and stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencer3 in 1921 examined the above evidence critically; he found similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on a second lot of crystals, not described crystallographically.)

Jan 1, 1939

By Edward W. Parker

IF one is to place any credence at all in the reports published in the daily press, the subject of conservation has been a very lively topic of conversation during the past 60 days, and it does not appear that the temperature of the summer months has been in any way moderated by the discussion. It is a subject in which we are all vitally interested and to which, so far as our mineral resources are concerned, both the Institute and the Geological Survey have liberally contributed. The report of the National Conservation Commission, appointed by President Roosevelt, contains a series of papers on the conservation of mineral resources, all of which were prepared by members of the Geological Survey and were compiled largely from information previously collected by that Federal bureau in the performance of its regular duties. It is not the purpose of this paper to reiterate in extenso any of the material already published. The contributions of the Survey officials to the Commission's report have been published in a separate document as Bulletin No. 394. This docunient is for free distribution and may be obtained upon application to the Director of the Survey. In the preparation of this paper I desire merely to make a few suggestions regarding the possible necessity of some restraint upon or control of one branch of the mining industry with which I have been somewhat closely associated for the past 20 years-that of coal. Most of the members of the Institute are cognizant of the suits brought by the government against the anthracite-operators in Pennsylvania, or the combination of interests commonly known as the ? hard-coal trust." No defense of any illegal combination in restraint of trade is intended, but there are some facts which should not be lost sight of, and unfortu-\

Nov 1, 1909

By G. D. Tranter

THE importance of ladle and teeming practice and its relationship to the yield and quality of the product has focused considerable attention on this phase of open-hearth operation. Inherently bad steel cannot be perfected by manipulation during teeming, but through the proper handling of "off heats" serious losses, which in many cases arise, can be greatly minimized. Conversely, good steel can be ruined as a result of poor workmanship in the -pit, and rendered unsuitable for application to orders where exacting surface and physical requirements are essential. Sufficient evidence has been secured to warrant careful investigation of pit operations when an abnormal number of basic defects develop in the semifinished product or are found on the inspection table. This paper is written from the standpoint .of the problems involved in making satisfactory ingots for sheet rolling. Furthermore, since rimming steel is almost universally used for manufacture of sheet, the data presented herein refer particularly to that type of steel. Going back some 30 years in open-hearth .history, the word "pit" properly described the hole into which the ladle was lowered to receive the metal tapped from the furnace. The working space was necessarily limited, and the disposal of slag and metal overflowing the ladle or lost because of breakouts presented a serious problem. The equipment, of course, was rather crude in the light of present-day development. Often no ladle stands were provided, the ladle being hung on the crane beneath the runner. When delayed taps occurred, the ladle was often held in position for many hours, thus tying up pit operations and causing delays to adjacent furnaces. Because of crowded conditions, slag thimbles were not used and a network of cast-steel triangles and old tapping bars, placed before the heat was tapped, was the means for removing slag from the hole. Furnaces of different capacities were used

Jan 1, 1935

By Fred C., Bond

DETERMINATIONS of circulating load in a classifier operating in closed circuit with a grinding mill are usually made from screen analyses of the mill feed and classifier products. The percentage remaining on someone selected screen size must be used in the calculation, and, because of the wide variation in average particle size between the mill feed and classifier overflow, an accurate and representative result at the selected mesh is often difficult to obtain. To overcome this difficulty and reduce the time required in making the determination, I have devised a method which uses the liquid-solid relationship in the circuit rather than screen analyses. The quantities required for the calculation include only the usual dilution and feed tonnage measurements, which should be made regularly in the course of ordinary mill operation and, in addition, the amount of new water added to the classifier, or to the head of the mill with the new feed. If measurements are obtained on both of these quantities it is possible to check the calculated circulating load, and to calculate the percentage of moisture in the new feed to the mill; or, if the latter is known, to check the feed tonnage.

Jan 1, 1937

By Leonard D. Jaffe, Donald C. Buffum

THE importance of temper brittleness in alloy steels has long been realized in Europe, In the United States recognition of its importance has developed within the last several years. Many brittle failures encountered in parts made of alloy steel are undoubtedly attributable, wholly or in part, to temper brittleness. These failures have occurred particularly at low temperatures, under shock loading, and in the presence of notches, restraints and combined stresses. It has been almost universally accepted that plain carbon steels are not susceptible to temper brittleness. As a result, considerable effort has been expended in attempts to discover the manner in which alloying elements introduce temper brittleness. It is desired to raise the possibility that plain carbon steels are not only susceptible to temper brittleness, but are much more susceptible than alloy steels, in the sense that they embrittle much more rapidly. It is suggested that previous views, (that plain carbon steels are not susceptible), are based upon an erroneous interpretation of the experimental results. INTERPRETATION OF PREVIOUS DATA For many years the standard criterion for susceptibility of a steel to temper brittleness consisted of comparison of the energy absorption, in a notched-bar impact test at room temperature, of specimens that had received two heat treatments.1 One specimen (or group of specimens) was quenched, tempered, and quenched from the temper. The other specimen (or group) differed only in having received an embrittlement treatment, which might consist of a slow cool from the tempering temperature, or of an isothermal hold in the range 450-550°C subsequent to quenching from the temper. If the energy absorption of the specimen receiving the embrittlement treatment was lower than that of the specimen not given this treatment, it was said that the steel was susceptible to temper brittleness, If the energy absorptions were the same, it was said that the steel was not susceptible. Several investigators2,3 found that plain carbon steels showed negligible difference in energy absorption in such tests (at least when their manganese content was below 0.60 pct), and concluded that plain carbon steels are not susceptible to temper brittleness. Recently the deficiencies of the criterion mentioned above have been pointed out.4-6 The criterion now generally used for susceptibility to temper brittleness retains the heat treatments used in the earlier scheme, but instead of the notched-bar impact tests being made only at room temperature, they are made over a range of temperatures, covering the transition from ductile to brittle fracture, If the transition temperature of the specimens receiving the embrittlement treatment is higher than those

Jan 1, 1948

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during '"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term ''productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during '"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term ''productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943

By R. Taggart, J. W. Barton, G. R. Purdy, J. G. Parr

The constitution and mechanical properties of heat-treated alloys containing up to 10 pct* Ni in Ti have been investigated. The effects of quenching and of various isothermal treatments ale described, and C-curves are presented. The production of the precipitated and the martensitic hexagonal phases on quenching is discussed. MARGOLIN, Ence, and Nielsenl have determined the titanium-nickel phase diagram. A study of the transformations in gas-quenched and tempered powder specimens was made by Polonis and Parr.' Some isothermal transformation work was carried out by Margolin and ~unshah, who determined transformation curves for 4 and 6 wt pct alloys, while Robinson et al.investigated the formation of the w phase in a quenched and tempered alloy, Margolin and Bunshah showed that while a martensitic transformation could be obtained on quench- ing thin sections of a 4 wt pct alloy, a 6 wt pct alloy precipitated a nonmartensitic phase. The present investigation was undertaken to obtain more information on the transformations in quenched, quenched and tempered, and isothermally transformed lump specimens of alloys containing up to 10 pct Ni. Isothermal transformation curves have been determined for 7 and 10 pct alloys and cooling curves have been obtained for quenched alloys containing up to 7 pct Ni. The mechanical properties of 2, 5, and 10 pct alloys were studied, with the object of relating properties to microstructures. EXPERIMENTAL METHODS Alloys containing up to 10 pct Ni were prepared from sponge titanium and spectrographic standard nickel by levitation-melting and chill-casting in a split copper mold. The 5 and 10 pet alloys were prepared from sponge Ti having an as-melted hardness of 115 Vpn. The other alloys were made from a sec-

Jan 1, 1961

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By John T. Norton, R. E. Hiller

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

Jan 1, 1932

By John Hall

SOME months ago one of the authors was asked to write a paper on the heat treatment of steel castings that would be more comprehensive than other matter lie had published; this is an attempt to present in condensed form the results of experimental work and actual practice carried out for the most part in 1907, 1908; and 1909. It is not a laboratory research and the work done was carried out for the express purpose of putting in practice the processes discovered as fast as possible. Most of the tests are the result of commercial practice and not of bars annealed in our laboratory; most of the micrographs were made for our own records and not for publication. Certain of the micrographs, therefore, are not as clear as we may wish but they were good enough for our purpose at the time they were made. The tests and micrographs are selected from several thousands in our files. All of these micrographs are magnified 60 diameters. These experiments were conducted almost entirely on steel made in a 3-ton bottom-blown converter, and most of the steel illustrated analyzes about 0.05 in phosphorus and sulfur. Unfortunately, a certain number of specimens are shown of which we do not have the complete analysis, but in most cases in which the phosphorus and sulfur vary much from the figure just given that fact is noted. For purposes of comparison, we have included a certain number of micrographs and tests of steel made in the electric furnace, some of which were from specimens made in other shops and some in our own shop, and some tests of acid open-hearth and tropenas steel.

Jan 9, 1919

By R. S. Archer

IN the microscopic examination of aircraft-engine parts made of heat-treated alloy steels, the writer has been forcibly impressed by the failure of the usual etching processes to disclose any but gross defects in heat treatment. It seemed particularly desirable to bring out the grain size of the steel, which is indicated in the ordinary etching processes chiefly by the change in orientation of structure from grain to grain. After various attempts, a fairly successful method has been found, which is here presented in the hope that it may be of use to those who have occasion to examine these steels in the heat-treated condition. The specimens worked with have been mostly chrome-nickel steels heat treated (that is, hardened and tempered) to a Brinell hardness of around 300. A few experiments with other specimens will be referred to later. Briefly, the method employed consists in etching the steel about 10 min. in a fresh solution of picric acid in ethyl alcohol, and then rubbing off the smudge of carbonaceous matter on moist broadcloth. Different samples of almost identical analysis; heat treatment, and physical properties (including resistance to impact) respond quite differently to this treatment. In some, the grain boundaries are developed quite readily, while iii others, especially ill those whose grain is unusually fine or in which the final hardening heat, has not quite obliterated the previous crystallization, the results are more obscure. The exact time of etching to secure the best results also differs for various samples, and the greatest success is usually attained by a process of "tinkering." Such a process is illustrated in a series of micrographs, the first six of which were taken at a magnification of 300 diameters.

Jan 1, 1919

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968