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By A. W. Schlechten, C. M. Hsiao

The apparent vapor pressures of a number of metal sulphides were determined by measuring their rate of weight loss when they were heated under vacuum. The calculated pressures are due in some instances to the volatility of the sulphide and in others to the decomposition pressure. FIE direct reduction of metallic sulphides, as in the precipitation method for lead or antimony, is not a widely used process today. However, it might be employed for the production of a number of metals if the operation were carried out under reduced pressures. Two general procedures are possible; the reducing agent could form a stable nonvolatile sulphide from which the valuable metal could be removed by volatilization or liquation. The other approach would be to choose a reducing agent which would form a sulphide that could be volatilized away from the valuable metal. A vacuum operation would serve to protect the sulphides and metals from oxidation and would increase the evaporation rates. A related process is the separation of metallic sulphides by selective volatilization either at atmospheric pressure or under vacuum. This procedure is already used commercially for the elimination of lead and cadmium as PbS and CdS from zinc calcines; it might well have other applications. To predict such processes it is necessary to know the relative volatilities of the metallic sulphides and to know whether they volatilize as sulphides or whether the predominant weight loss is due to decomposition. Such data would also be of value in studying problems such as the use of sulphides for refractories, as described by Brewer,] or in the evaluation of the theory of ore deposition from the vapor state, as proposed by Brown.' Qualitative statements concerning the volatility of metallic sulphides can be found frequently in the literature and are well summarized by Mellor, but accurate determinations of rates of evaporation or vapor pressures are very scarce. Kelly" lists vapor pressure data only for PbS; his reference being to the work of Schenck and Albers,4 who measured the vapor pressure of PbS by a dynamic method between 850" and 995°C. More recently Veselovskii5 has determined the vapor pressures of the sulphides of antimony, lead, cadmium, and zinc at temperatures ranging from 360" to 1000°C using Knudsen's method. A second Russian worker, Pogorelyi,6 determined the vapor pressures of CdS and ZnS at temperatures from 900" to 1250°C. The results obtained by these workers are shown in subsequent graphs in comparison with the data of this paper. Brewer and coworkers1 have studied some of the metallic sulphides to determine their suitability as refractories in vacuum. Veselovskii's determinations on PbS checked well with those of Schenck and Albers, and his determinations of CdS check almost exactly with Pogo-relyi. For the vapor pressure of ZnS the data of Veselovskii and that of Pogorelyi are in fair agreement, as shown in Fig. 1, but it should be pointed out that Lumsden7 has discovered that the equation given by Veselovskii for the vapor pressure of ZnS: - 14,200 log P9.495 is in error by a factor of ten when compared to the experimental data. In contrast with the scarcity of data on vapor pressures, the decomposition pressures of many metal sulphides have been determined and are summarized by Smithells.8 Theoretical Considerations The experiments described in this paper consisted of determinations of the rate of weight loss of certain metallic sulphides under very low pressures at different temperatures. These data plus observation and analyses of the products reveal the mechanism of the weight loss and also provide a basis for the calculation of the vapor pressure or apparent vapor pressures of the sulphides.

Jan 1, 1953

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS C. H. MATHEWSON. Chairman PAUL D. MERICA, Vice-Chairman CHESTER A. FULTON CARROLL A. GARNER H. Y. WALKER FINANCE COMMITTEE OF THE BOARD OF DIRECTORS ERLE Y. DAVELER, Chairman WILBER JUDSON RUSSELL B. PAUL HENRY KRUMB, Consultant

Jan 1, 1943

CONTENTS PAGE Bronze Bearing Metals. By G. H. CLAMER 1729 Pennsylvania Railroad Anti-friction and Bell Metals. By F. M. WARING . . 1733 The Tin-plate Industry. By D. M. BUCK. Discussed by G. H. CLAMER, J. W. RICHARDS 1735 The Aluminum Bronze Industry. By W. M. CORSE 1738 Bronzes, Bearing Metals, and Solders. By G. K. BURGESS and R. W. WOODWARD. Discussed by G. H. CLAMER, R. T. ROBERTS 1742 Babbitts and Solder. By G. W. THOMPSON 1751 The Cadmium Supply Of the United States. By C. E. SIEBENTHAL. Discussed by M. L. LISSBERGER, C. W. HILL, F.- F. COLCORD . . .. . . . . 1752 Solder, Its Use and Abuse. By M. L. LISSBERGER 1759

Jan 12, 1918

By M. E. Wadsworth, W. H. Dresher, W. M. Fassell

HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 sphalerite,4 galena," and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,6 ho found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo++ in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,' only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By Earl S. Greiner, Eric R. Jette

The constitution of the iron-silicon alloys containing from 14 to 33.4 weight per cent silicon has been studied by a number of investigators, whose results have been reviewed in a monograph published by the Engineering Foundation1. In these previous researches, the solubility of silicon in iron was determined by thermal, microscopic or magnetic methods and the compound Fe3Si2 was reported to be stable at temperatures from 0 to approximately 1030' C. This paper describes the results of an X-ray investigation of the solubility of silicon in iron and gives data which prove that the Fe3Si2 phase is unstable below 825" C. In order to obtain the present results on the solubility of silicon in iron, the authors have utilized the lattice constants of the alpha-phase iron-silicon alloys given in a previous publication2, and also some additional data which will subsequently be described. Materials and Methods The alloys used in this investigation are listed in Table 1. They were prepared in 30 or 50-gram ingots by melting specially purified silicon and electrolytic or carbonyl iron in alundum crucibles under a pressure of less than 1 mm. of mercury. The purity of the silicon, electrolytic and carbonyl irons has been given by the authors in previous publications2, 5. The ingots were homogenized in vacuo at approximately 1000" C. for at least 96 hr. and then slowly cooled. The homogenized specimens were ground to powder in a hardened steel mortar. This powder was passed through a 150 or 200-mesh screen and sealed in evacuated quartz, Jena or Pyrex glass tubes and heat-treated as noted in the various tables. Specimens 23A, 24B, 33 and 35 and the specimens heated for one month at 700" C. were quenched by quickly removing the tubes from a horizontal tubular furnace and dropping them into water. The other specimens were quenched by means of a drop-quenching device, which has been described previously3.

Jan 1, 1937

By E. O. Chartkoff

IN 1926 one of the authors published researches on the determination and description of the iron-tungsten and iron-molybdenum systems,1 including the equilibrium diagrams. In 1929, further work was carried on, including the examination by X-rays, which is recorded here. Measurements were made of changes in lattice parameters in the solid solutions. Precipitation from the solid solution and the accompanying changes in hardness were studied as well as the formation of the intermetallic compound phases upon sintering a mixture of metal powders.

Jan 1, 1930

By Robert Glass Cleland

THE THIRD and most important item on the Phelps Dodge agenda for the development of new ore supplies involved the site of the company's initial venture into Arizona, the old mining camp of Morenci. By the purchase of the Arizona Copper Company's holdings in 1921, Phelps Dodge had obtained control of virtually the entire Morenci district, including town, public utilities, and, above all, the huge mineralized area that had once been divided between numerous competing companies. Because of this rigid concentration of ownership in the hands of one organization, Phelps Dodge was able to plan and successfully carry out a program of greater magnitude than any Arizona mining company had previously under- taken. The immense deposit of low-grade ore, usually referred to as the Clay Orebody, had been known to the mining companies of Morenci for many years. Pioneer exploratory work, both by the Arizona Copper Company and later by Phelps Dodge, revealed that the deposit, mostly of light-gray porphyry rock, lay under a hard capping from two hundred to five hundred feet thick. An intensive drilling

Jan 1, 1952

By F. Selig, E. J. Couch

The following points serve to supplement the interesting theoretical study on forward combustion by Thomas, and may be of some general interest. The mathematical model presented by the author can be viewed as a first approximation to the problem of calculating the vertical burned height profile resulting from ignition of the interval | z |<h/2 in a very thick formation. However, the assumption of a given minimum combustion temperature T, would give a better approximation to the vertical burned profile if the burning height were not constrained to stay within the ignited layer. This follows from the fact that both fuel and oxygen are present in the adjacent region, |z|>h/2, and for certain combinations of process variables the temperature is sufficiently high for complete combustion to occur. In this case, the vertical coverage will first become greater than the ignited interval before cutting back to zero as the extinction limit is approached as shown in Fig. 1. Such growth of vertical coverage is possible if the minimum combustion temperature is less than the initial source temperature (r = rj) at the edge (z = h/2) of the ignited interval. But this latter temperature is equal to one-half the source temperature for the case of infinite burned height.&apos;,&apos; Thus growth will occur initially if The fact that the vertical burned height can be greater than the ignited interval complicates the picture considerably, as can be seen by referring to Fig. 1. Here burning occurs in Region A, whereas none was possible in the original mathematical model. At the same time, there is no combustion in Region B, contrary to the assumption of burning in the entire layer |z|<h/2. This apparent inconsistency suggests that the vertical coverage derived from this simple model does not adequately represent the vertical height of the burned zone. A more compatible model will result from the actual stepwise calculation of the burning length (as a function of time) that would give rise to the specified combustion temperature. This problem can be more conveniently attacked by using the temperature distribution, given by the author&apos;s Eq. 12, expressed in the integrated form:

SAN FRANCISCO LOCAL SECTION Executive Committee G. HOWELL CLEVENGER, Chairman C. W. MERRILL, Pace-Chairman JAMES C. RAY, Secretary-Treasurer, 1235 Webster St., Palo Alto, Cal. F. W. BRADLEY ANDREW C. LAWSON Meets on the second Tuesday of each month Farewell Dinner to H. Foster Bain H. Foster Bain, Who has gone to London to assume the editorship of the Mining Magazine, was tendered a farewell dinner by the San Francisco Sections of the American Institute of Mining Engineers, the Mining and Metallurgical Society of America, and the Engineers&apos; Club, on the evening of Mar. 9, 1915, at the Hotel Bellevue, San Francisco, 85 members being present. George H. Clevenger acted as Toastmaster and the following toasts were responded to: Bain and the Mining Industry, E. H. Benjamin. Bain, the Geologist, A. C. Lawson. Bain, the Man, F. W. Bradley. Bain, the Friend, C. W. Merrill. Bain, the Schoolboy, C.. F. Tolman. The Frontispiece and Flow sheet from the souvenir program, designed by James C. Ray, Secretary of the Section, are reproduced herewith.

Jan 5, 1915

By V. Steve Reed, Ed L. Reed

The in situ leach mining process generates a waste stream that is high in sulfates, total dissolved solids, and radium 226. During the mining phase, the volume of the waste stream is relatively low and consists primarily of the bleed stream. During the restoration phase, larger volumes of waste water are generated. These waste streams require environrnentally sound disposal. The low net evaporation rate in the Coastal Bend area precludes pond evaporation as a feasible disposal alternative. Reverse osmosis is a practical method of reducing the volume of the waste water handled, but the concentrated waste stream from the reverse osmosis unit must be disposed properly. Deep well injection into highly saline reservoirs is considered a sound method of disposing of the liquid waste generated by in situ mining in the Gulf Coast uranium district. Thirteen injection wells have been permitted to serve the disposal needs of the leach mining industry in Texas. Of these 13, 11 have actually been drilled. Seven applications are pending. The injection zones for the permitted wells range from depths of 3050 to 6200 feet. Pressure limitations imposed on these wells range from 500 psi to 1350 psi. The following criteria are used to determine the desirability of a disposal well site: 1. A minimal number of nearby, improperly plugged borings which penetrate the disposal zone; 2. Minimal crustal disturbance; 3. Sufficient salinity of the water contained in the disposal zone; 4. Protection of oil and gas producing zones; and 5. Sand of sufficient permeability and areal extent to handle the desired volume without fracturing the reservoir. 1. Improperly plugged borings: During the early part of the century, oil wells, gas wells and test holes were drilled using cable tool equipment, often with a minimum amount of surface casing. Production casing, when it was set, was often partly removed when the holes were abandoned. Thus, wells drilled prior to 1940 frequently have less than 100 feet of surface casing and either no production casing or the upper part of the production casing removed. Additionally, these holes are often plugged only with mud. The close proximity of these holes to an injection well location are a concern in that they can provide an avenue for injection-depth fluids to migrate up the bore hole and jeopardize shallower fresh water reservoirs. Usually, where there are more than 6 or 8 poorly plugged borings in a 2 1/2 mile radius of the well site, it is preferable to examine deeper zones for disposal well potential. The deeper zones are especially attractive where the borings are not in a cluster, which renders monitoring more difficult. Often, even the deeper disposal zones are penetrated by a few improperly plugged borings. When this condition arises, the potential for leakage through the borings can be addressed in the following ways. a. Demonstration that the static head in the boring is higher than the anticipated increase in bottom hole pressure generated at the boring by the disposal well. A 100 psi differential between these two pressures is recommended. The calculated increased pressure at a boring caused by injection should be refined using annual bottom hole pressure measurements in the disposal well. Figure 1 illustrates an injection pressure map which can be overlain on the oil well map to determine the anticipated increase in pressure expected at each oil, gas or abandoned hole. b. Shallow ground water monitoring. A shallow monitor well is drilled next to the boring and both pressure and quality measurements are made periodically in the shallow well. c. Disposal zone monitoring. Recently there has been a tendency for regulators to require disposal depth monitor wells instead of shallow well monitoring. We consider disposal depth monitoring to be a less effective method of monitoring because it provides only indirect evidence of potential problems. Assumptions have to be made for the unplugged borings, such as mud weight, that are not addressed by the disposal zone monitoring program. There is little improvement with this system to that discussed in "a" above. A shallow zone monitoring program, however, yields direct evidence of a developing problem with an unplugged boring. Leakage by the boring will be detected quickly by an abnormal increase in pressure in the shallow well. Quality monitoring will detect upward migration of poor quality fluids. The pressure data provide an early warning of impending leakage; the quality monitoring will detect actual fluid migration.

Jan 1, 1980

By George H. Anderson

A CHAPTER of appealing interest was added to the industrial history of the Southwest early in June, when the War Production Board gave final approval to the erection of a blast furnace, a battery of coke ovens, an ore-beneficiation plant, and other facilities for the production of pig iron in northeastern Texas, just north of the East Texas oil field. For many years the people of Texas and adjoining states have cherished the ambition and desire that eventually an iron and steel industry drawing upon local mineral resources would be established to serve Southwestern markets. The existence in this vicinity of valuable deposits of iron ore, limestone, and coking coal has been known in a general way for many years, and efforts have been made from time to time to use them in the production of iron. The present development promises to bring to realization the dreams of the men who have visualized what the establishment of this basic industry would mean to the region.

Jan 1, 1942

By K. S. Krishnam, A. G. Guy

VOLUME 6 of the Transactions of the Baikov Institute of Metallurgy, Moscow, is devoted to the subject of "the experimental and theoretical study of the physical characteristics of dilute solid solutions,11 and summarizes work that has been done largely in the years 1958-9. In view of the attention that Soviet investigators have given to this subject, it seemed useful to carry out an independent experimental investigation in an effort to judge the scientific basis and practical significance of this field of study. The present note is a preliminary report of this investigation. The first property studied by the Soviet group was X-ray spectra of solid-solution alloys.&apos; An anomaly observed at low concentrations (--0.05 at. pct) of the alloying element led to the theory that each impurity atom in a transition-metal base alloy is the center of a "block" of affected atoms with a radius of about 10"7 cm. This theory was further developed in a later paper.2 By this time similar anomalies had been found in diffusion coefficients3 and in thermal expansion.4 The entire development up to 1959 was reviewed in a comprehensive paper, and further theoretical ideas were also published at this time. Finally, the volume mentioned above was published in 19607 giving new experimental data on anomalies in optical properties and Hall constant, and a new theoretical treatment also appeared.&apos; Although western scientists have done both theoretical work, summarized recently by Friedel,9 and considerable experimental work on dilute solid solutions, there is little support for the marked anomalies reported in the Soviet papers. Of the physical properties studied by the Soviet investigators, thermal expansion was chosen for the present investigation because of the relative ease of obtaining the necessary precision of measurement. A Leitz dilatometer was used for this purpose, and a special technique involving interchanging of the two specimens being compared permitted a precision of 0.05 x X in average thermal expansion over the range 27° to 600°C. The specimens were heated and cooled in vacuum or in a protective atmosphere at a rate of 50 °C per hr. Ferrovac E iron was used as the comparison specimen and in every case had a coefficient of expansion higher than (or equal to) that of the alloy. Since unintentional impurities are an important factor in studies of dilute alloys, special attention was given to the purity of the iron and the alloys used. The alloys were the same of those used by Abrahamson10 and by Michalak," and their preparation is described in these references. Chemical analyses of the Ferrovac E iron and of typical Fe-W and Fe-Mo alloys are given in Table I. The purity of the iron and alloys is undoubtedly higher than in the

Jan 1, 1962

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm&apos; sec-&apos;. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3&apos; has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

The amount of coal used in the Colonies before the Revolutionary War was very small, and few records of it can be found, these all being in the Public Records Office in London. The exports and imports for the years 1768 to 1772, inclusive, are shown in Table 3, which apparently do not include the early shipments from the Virginia field. For the three years 1769 to 1771, the imports from Great Britain-their only source-totalled 17,943 tons, or an average of 5,981 tons per year. If the shipments from Richmond for the same period were available, this average would probably not exceed 6,800 tons per year. In Table 4 the shipments of coal from the James River ports for the period 1758 to 1769 are shown. A few of them are re-exports of coal brought from England, but the great majority are undoubtedly of coal produced in Virginia, and the movement was partly to West Indian ports but mainly to Atlantic ports from Baltimore to Portsmouth, N. H. (Piscataway). In Table 5 the data in Tables 3 and 4 are combined, the exports being deducted, and this summarizes all the available data on the amount of coal consumed in the Colonies before the separation from England. As has already been stated there has been a tremendous amount of work done in the Richmond field over a long period of time, many mines were opened and in some cases operated for years, and practically no accurate data remain or have been published to show what was done. There are undoubtedly manuscripts still remaining that will contribute to much of the knowledge of this field, and it is well worth the while of the proper state authorities to collect all the information that can be found anywhere, to enable the future development of these coal deposits to benefit by the record of what was done in the past. Table 22 shows all the methods of shipment from this field, and all of the data available about tonnages moved over each of them. The shipments by the Chesterfield and Clover Hill Railroads are largely duplicated in some of the other columns, but allowance has been made for this in the estimated totals. In addition to the difficulties experienced with similar data for the other states, these Virginia records have one peculiarly their own; it was the custom to allow 5 pecks to the bushel of coal at the pit and only 4 pecks at the docks or at vessel side. In most of the figures it is not stated to which point they apply, and a considerable error may exist due to this cause, although certainly it does not apply to all of them. The notes show the sources of the figures used, and while it is probable that the totals are lower than the actual amounts produced, the data given are the most complete that can now be assembled.

Jan 1, 1942

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck&apos;s work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck&apos;s outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."&apos; We were not however very successful in getting values for Schenck&apos;s "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck&apos;s work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

By A. S. Yue

Small-angle tilt boundaries have been observed in a lamellar eutectic structure. These boundaries are morphologically similar to a theoretical till boundary originally proposed by Burgers. The production of a small-angle tilt boundary in the lamellar eutectic structure is attributed to the formation of an indentation on a planar solid-liquid interface during growth. Constitutional supercooling due to the accumulation of impurity atoms ahead of the interface is primarily responsible for the generation of an indentation. The distance between two faults of like sign, designated as lamellar fault distance, is calculated by the Burgers equation for small-angle boundaries. It was found that the lamellar fault distance decreases exponentially and the tilt angle increases exponentially with freezing rate. SMALL-ANGLE tilt boundaries have been observed in many crystals in the as-grown states by etching techniques. However, a detailed substantial proof for revealing the presence of dislocations in the form of etch-pits was recently accomplished by Vogel. These boundaries are described as an array of dislocations of like sign. The angle of tilt associated with a boundary is treated theoretically by Burgers3 and is given by 0 = b/D for small tilt-angle where b is the Burgers vector of the dislocations and D is their average spacing. During the course of experimentation on the solidi fication of the lamellar Mg-32 wt pct Al eutectic a microstructure which was strikingly similar to a dislocation tilt boundary was observed. An example of the type of microstructure is given in Fig. 1, which shows a combination of transverse and top sections of the lamellar eutectic structure. The lamellae of the top section on one side of the apparent tilt angle are not parallel with those on the other side. Consequently, some lamellae must be terminated somewhere. Fig. 1 shows that the termination of lamellae is analogous to a dislocation tilt boundary in a crystal lattice originally proposed by Burgers. This work represents a closer look at such structures. The factors governing the production of the small-angle tilt boundary are discussed in terms of the freezing condition and impurity distribution in the melt. The effect of freezing rate on the distance between two faults, designated as lamellar fault distance, and the tilt angle is also described. In addition, the lamellar fault distance is determined by means of the Burgers equation for small-angle tilt boundary. EXPERIMENTAL PROCEDURE The slightly impure Mg-32 wt pct Al eutectic rods, 5/8 in. in diam and 12 in. long, were made from 99.99 wt pct Al and 99.98 wt pct Mg and were cast in a high-purity graphite mold. Some of these rods were purified by zone-refining the eutectic using direct-radiation helical-coil furnaces5 A molten zone about 2 in. long was passed through the cast rods at a speed of 5.3 x 104 cm per sec for ten passes of the molten zone. Before the freezing experiment was begun, 2-1/2 in. of the material from the head and tail ends of the zone-refined eutectic were removed from the rod to eliminate any impurity. The freezing experiments were carried out under controlled conditions,8 using a protective atmosphere of purified argon. At the end of each run, observation of the tilt boundary was made throughout the entire length of the rod with a light microscope on the top, longitudinal, and transverse sections (three mutually perpendicular sections) of the lamellar eutectic solid. The experimental data used for the determination of interlamellar spacing and tilt angle were taken from the middle portion of

Jan 1, 1964

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970