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By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By Henry Leidheiser, Melvin C. Jr. Hobson

The rate of formation of the intermetallic compound, indium antimonide, at the interface between iudium and antimony at 100°C is greatly increased when a composite electrode of indium electrode -posited on antimony is made the cathode in an electrolytic cell. The amount of indium antimonide formed during electrolytic treatment at constant potential appeared to he proportional to the square root of time, but the scatter of the data, particularly at long times, makes it impossible to state this conclzlsi1:ely. The rate constant for the electrochemical synthesis was estimated to he 1.5 x 10-12 sq cm per sec. A similar- set of experiments was conducted in the absence of an applied potential but under otherwise similar conditions. The rate constant lor the thermal synthesis was less than 2 x 10-14 sq cm per, sec, at least two orders of magnitude less than obtained during electrolytic treatment. In a series of electrochemical studies it was observed that intermetallic compounds formed on the surface of polarized electrodes.1'2 The possibility of using this technique for the electrochemical preparation of intermetallic compounds was investigated and subsequently applied to the synthesis of the semiconducting III-V compounds. Gallium antimonide, indium arsenide. indium antimonide, and indium bismuthide were successfully formed by electrodepositing the Group III element from a boiling acid solution onto an electrode made of the Group V element. The following kinetic studies were undertaken on indium antimonide to obtain quantitative information on the rate of formation of this representative III-V compound under a potential gradient. EXPERIMENTAL The electrolytic cell for these experiments was a modified, three-neck, round-bottom, 500-ml distillation flask. Sealed into the side of the flask was a Luggin probe which monitored the surface of the working electrode and extended out of the flask to a small reservoir containing a saturated calomel electrode. The counter electrode was platinum. The three electrodes were connected to a Wenking po-tentiostat which maintained a preselected constant potential near the surface of the working electrode with reference to a saturated calomel electrode. All potentials noted in this paper are with reference to a saturated calomel electrode at 45° ± 5°C. The potential and the current were both monitored using Sargent Model MR recorders. The antimony electrodes were cast in graphite molds to form spheres about 15 mm in diameter with a shank 6 mm in diameter and 10 mm long. A heavy copper wire (12B & S gage) was soldered to this shank. Collodion was applied for protection to the shank and the connecting part of the copper lead. A snug-fitting O-ring was slipped over the shank and the electrode was then fitted into a teflon holder such that only the spherical portion was exposed. The electrode surfaces were cleaned and chemically polished prior to assembly and introduction into the electrolyte by etching in a modified CP-4 solution (50 parts glacial acetic acid, 10 parts concentrated nitric acid, 2 parts 48 pct hydrofluoric acid). The electrolyte was 10-2 M In+3 in 1 MH2So4 and its temperature was held constant by refluxing. The reflux condenser was open to the atmosphere and no temperature correction was made for changes in barometric pressure. The indium concentration in the electrolyte was checked from time to time by the analytical method outlined below for the determination of the amount of indium antimonide formed electrochemically. A schematic of the recorded potential is shown in Fig. 1. At point A the antimony electrode was introduced into the cell and the open-circuit potential recorded. At point B the potentiostat, preset at the desired potential, was switched on. It was switched off at point C and the potential fell to the open-circuit value of the electrodeposited indium. The

Jan 1, 1965

By W. K. Hartley

INTRODUCTION AND HISTORY The Kimberley Division of De Beers Consolidated Mines Limited includes four underground mines in Kimberley viz. Dutoitspan, Bultfontein, De Beers and Wesselton Mine and two outside mines, viz. Finsch, an opencast operation and Koffie- fontein, an underground operation. Figure 1 is a map of the Kimberley district showing the location of these mines. Finsch is 150km west of Kimberley and Koffiefontein is 80km south of Kimberley. The head office of the De Beers Company is in Kimberley. The diamond sorting and trading companies for diamonds produced in South Africa are also in Kimberley. Diamonds were first discovered in the Kimberley area at Hopetown in 1866 on the banks of the Orange River. This, and later finds, triggered the start of the great "Diamond Rush". In 1870 the Jagersfontein (now closed) and Dutoitspan pipes were discovered, followed by those at Bultfontein, De Beers and Kimberley Mine (now closed) in 1871, Koffiefontein in 1880 and Wesselton in 1891. Finsch Mine was a more recent discovery in 1961. Finsch, due to go underground in 1986, and Koffiefontein, are fully self-contained with their own treatment plants, housing, services etc. The four Kimberley mines deliver ore by conveyor to a central treatment plant and use joint ser- vices. ,+lining is presently carried out mainly by Block Caving which has replaced the earlier Chambering method. De Beers Mine, on a limited scale, and Wesselton Mine have recently started to use Sub-Level Caving, and both Bultfontein and Du- toitspan are scheduled to use the same method at a later date. The combined ore tonnage produced by the Kimberley Mines is 17 400 tons per day, Koffiefontein 12 000 tons per day and Finsch Mine 17 000 tons per day. THE EVOLUTION OF MINING METHODS Initially, the open-cast mining was carried out to as great a depth as safety would permit. In the early stages of open-cast mining, the Kimberlite was removed in horizontal slices from levels 13m to 20m apart. The rock broken in the workings was raised to the surface by means of endless rope haulage inclines. As lower levels were attained these rope haulages were replaced by aerial hoists, inclined shaft haulages or inclined skip-ways. These methods were dependent upon the strength of the unsupported pipe walls, which became increasingly unstable with depth and a system was adopted whereby the ground mined in open excavations was tipped down passes to tunnels connecting with vertical hoisting shafts sunk in the country rock. As work in the open pit became more and more impracticable due to extensive falls of ground, this system was replaced by a combination of open-cast and underground mining, and eventually by wholly underground methods. Chambering With the advent of underground mining, a system known as "Chambering" (or "Inclined Chambering") was evolved. It was essentially a combination of shrinkage stoping and caving, whereby advantage was taken of the high pressure exerted by the loose rock that had accumulated in the open excavations due to the collapse of the pipe walls. This mining method was introduced around 1890 and was successfully employed, with little change, up to the early nineteen seventies. In this system each mine was served by a main hoisting shaft situated about 300m in the country rock. Main haulage cross cuts were driven from the shaft to the pipe at 200m (600ft) vertical intervals. A sub-vertical shaft, situated close to the pipe provided access to the working levels. Chamber levels were established from the sub-vertical shaft at 13m (40ft) intervals. See figure 2. On each of these levels successive 6,8m wide “cuts" were mined out across the pipe, from one rock contact to the other, and extended vertically to the footwall of the level above. Every 6,8m cut was made up of a chamber and a "back-pillart1, each approximately 3,401 wide. The chamber was mined by overhand shrinkage stoping. The levels were carried "en echelon", with each chamber on a level approximately three cuts ahead of the chamber on the level

Jan 1, 1981

By Charles E. Wait

HAVING had some experience in the use of gasoline-gas in a laboratory, I have been induced by frequent inquiry to present a few hints concerning it, which I hope may be of some value to those who are out of the reach of coal-gas, and who contemplate using this gas. While I will not delay to describe the method by which this gas is made, it may not be out of place to note that, unless frequent charges are put into the carburetter, the gas is variable in richness. This may be partially avoided, it is said, by repeatedly pumping from one cell in the carburetter to another. If a machine is in constant use for many months without re charging, the gas becomes rather poor for illuminating purposes ; but in this condition it may be burned in a Bunsen burner with advan tage. Could the gas be used always in this condition, no difficulty would be experienced, and it would be quite satisfactory for general laboratory purposes. Considerable annoyance, however, is experi enced whenever the machine is filled with gasoline. The Bunsen and other burners then produce a flame too smoky to be used with com fort, and, in fact, with most of them, a full supply of air; turned on at the base of the burner, will not suffice to completely burn off all the carbon. Finding it necessary to adopt some method by which I could get a flame free from unconsumed carbon, I adopted a plan which has in every way proved satisfactory. In addition to the pipe conveying the gas to the table, and ar ranged with a stopcock, there is brought to the table, within a fern inches of the gas-pipe, another pipe, conveying air direct from the pump. This pipe is also arranged with a stop-cock. The air- and gas-pipes are now connected with one pipe by a T joint; and to this last pipe is attached, by rubber tubing, the Bunsen or other burner. I have successfully used this simple system in connection with both small and large Bunsen burners, a burner with three tubes, arid a Fletcher burner; and recently I have added a new still to our equipment, and have been tising with it a Fletcher special high power burner No. 6, to which this system has been applied. With

Jan 1, 1886

By Phil Hulse

The Atlanta mine is located in east-central Nevada, approximately 360 km (225 miles) from Las Vegas. It lies in Lincoln County, 116 km (72 miles) south of Ely and 80 km (50 miles) northeast of Pioche. The property is currently operated by the Standard Slag Co. under a joint venture agreement with Bobcat Properties Inc, of Fort Lauderdale, Fla. Operations began in May 1975, and the mill is currently processing 109 000 to 122 500 t/y (120,000 to 135,000 stpy) of gold- and silver-bearing ore. Open-pit mining takes place in a breccia zone that occurs between Ordovician limestones and dolomites on the footwall and Tertiary rhyolites on the hanging wall. The quartz breccia ore is among the most abrasive in the world-shovel teeth must be replaced every week, 19-mm-thick (3/4-in.) steel chutes last about a month.

Jan 9, 1978

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md'ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,'-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-' Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.'-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By AIME AIME

A PAPER recently presented before the Anthracite Section of the A. I. M. E. by S. J. Phil- lips, Mine Inspector, Fifth Anthracite District, Department of Mines of Pennsylvania, covering the water hazards in the anthracite coal mines of the Lackawanna River Valley, was especially timely because the conditions there are duplicated to a large extent in the Wyoming Valley, which is traversed by the Susquehanna River with its many large tributary streams. Also, in the southern anthracite field, where there are a number of large creeks, similar pumping problems and mine water hazards will in time be presented if mining is continued to its conclusion.

Jan 1, 1936

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

Discussion of the paper of George K. Burgess, J. J. Crowe, H. S. Rawdon, and R. G. Waltenberg, Finishing Temperatures and Properties of Rails. By Albert Sauveur, R. Trimble, William R. Webster, P. H. Dudley, George B. Waterhouse, M. H. Wickhorst, James Aston, E. F. Kenney, A. W. Gibbs, W. A. Aiken, and G. K. Burgess . . 767 Discussion of the paper of Albert Sauveur, Manganese Steel and the Allotropic Theory. By G. K. Burgess and J. E. Stead 787 Discussion of the paper of J. V. Emmons, The Surface Decarbonization of Tool Steel. By Albert Sauveur, Bradley Stoughton, E. G. Spilsbury, Oliver W. Storey, H. O. Hofman, and J. V..Emmons 790 Discussion of the paper of Richard H. Rice, Turbo Blowers for Blast-Furnace Blowing. By S. G. Valentine, W. McA. Johnson, L. Iversen, J. E. Johnson, Jr., Karl Nibecker, W. Trinks, Otto Banner, H. S. Braman, Arthur G. McKee, and Richard H. Rice . . . 794 Discussion of the paper of J. K. Furst, The Plant of the Duplex Process for Making Steel. By W. McA. Johnson, Arthur G. McKee, Henry D. Hubard, and Bradley Stoughton . . 810 Discussion of the paper of E. C. Harder, The Iron Industry in Brazil. By I. C. White and E. C. Harder 813

Jan 4, 1915

By R. A. Bergman, C. J. B. Fincham

THERMODYNAMIC properties of many high-temperature systems containing sulfur, such as slags, metal sulfides, and solutions of sulfur in liquid metals, have been studied by means of equilibration with known gas mixtures.'" This method presupposes a complete and accurate knowledge of the thermodynamic data for all possible components of the gas phase at high temperatures. However, a survey of the data available up to 1952 on the thermodynamics of gaseous sulfur species and compounds, by Richardson and Jeffes,' showed that there was considerable uncertainty in the values of the free energies of formation of S, SO, HS, and CS. In many cases, this uncertainty made it impossible to decide whether or not these species would form a significant proportion of the sulfur present in the gas phase in any given system. After the review by Richardson and Jeffes had been published, St. Pierre and Chipman6 measured, by an indirect method, the free energy of formation of SO. This also enabled a clear choice to be made among the three possible spectroscopic values for the dissociation energy of S2 into atoms10 thereby determining the free energy of formation of S from S2, and fixing the free energy of formation of HS more accurately" The main purpose of the present investigation was to measure the free energy of formation of CS, which was still in considerable doubt. For example, at 1600°C, it could be estimated to be +6 +25 kcal per mole,* most of the uncertainty being in the * Based on the dissociation energles of CS6 and S2,5 the heat of sublimation of graphite, and, the assumption that the entropy of formation of CS is the same as that of CO. value of the dissociation energy." A secondary purpose of the investigation was to determine more accurately the equilibrium sulfur pressures over dilute solutions of sulfur in carbon-saturated liquid iron. General Method Dilute solutions of sulfur in liquid iron, saturated with carbon, were brought to equilibrium at 1600" and 1800°C, with known gas mixtures consisting, initially, of A and CS2. After equilibrium had been reached, the melts were quenched and analyzed for sulfur. In the high temperature region of the furnace, an equilibrium was set up between the various possible sulfur species and compounds in the gas phase; namely, CS2, CS, S2, and S. (It can be calculated that the amounts of S6 and S, are negligible at these temperatures:) Morris and Bueh17 and Kitchener, Bockris, and Libermana had previously studied the corresponding

Jan 1, 1958

By Victor A. Phillips

A series of strips of a Ni-12.7 at. pct A1 alloy were Prepared containing cubical y'(NisAl) precipitates with edge lengths from 60 to 500A. A particle-free solution-tveated strip was included for cornparison. They weve cold-rolled 95 pct and the effects of particle size on the isochronal (1/2 hr) annealing behavior between 300° and 950°C studied (by hardness and light and electron microscopy). It ulas inferred that the particles deformed with the lnatvix becoming lamellae which remained coherent. Comparison with published data fov pure nickel showed that aluminum greatly re-tavded softening and recrystallization, but it made little difference whether or not particles were present. The presence of pakticles led to a heterogeneous distribution of precipitates after annealing at 700" to 750°C. Recovery was not detected. Recrystallization occurred by the growth of new grains into unrecrys-tallized material. In a previous study by the author,' the growth of Ll2-type ordered yl(Ni3Al) precipitates was followed in Ni-12.7 at. pct A1 alloy as a function of aging at 600" and 700°C. The particles were showo to be cubical in shape in all sizes from 50 to 3000A and remained coherent. This work was used as a guide in preparing the starting structures for the present study of the effect of these particles on the annealing behavior of heavily cold-rolled strip. Another question of present interest was whether dislocation and particle hardening were additive, since the structures before rolling ranged from solution-treated to peak-aged to overaged. Also, precipitation might occur on annealing after cold-rolling. Reference may be made to other papers2"5 for previous work in this relatively unexplored field and only some recent work will be mentioned her:. phillips2 studied the effect of deformable 0 to 590A-diam cobalt particles on a Cu-3.23 pct Co alloy rolled 95 pct and found that the particles, which rolled out into thin lamellae, impeded softening and recrystallization. Tanner and servi3 likewise studied the annealing of cold-swaged Cu-2 pct Co alloy containing 150A-diam particles and found impeding effects. Haessner et a1.,4 on the other hand, found that incoherent 2-p-diam non-deformable particles of B4C (0.04 vol pct) tended to increase the rate of recrystallization of copper rolled up to 95 pct reduction. They attributed this to the formation of new grains at the particle interfaces. Humphreys and artin' found that nondeformable silica particles in copper rolled to 30 pct reduction accelerated recrystallization if the particle spacing was large and retarded it if the spacing was smaller. Haessner et a1 4 also studied a rolled Ni-Cr-A1 alloy; however, the particles of y'(Ni3Al)-type precipitate were not put in before rolling, but separated during the isothermal annealing at 750°C. No previous work appears to have been carried out on the effect of y' (Ni3A1) particles on the annealing of Ni-A1 alloy. Hornbogen and ICreye7 redetermined the solubility c of aluminum in nickel as a function of temperature T and showed that it was given by c = 32.6 exp(-1940/RT). This relation gives aluminum solubilities of 15.1, 14.2, 12.0, and 10.7 at. pct at 1000°, 900°, 700°, and 600°C, respectively. The phase precipitated from the nickel-rich solid solution is fcc y1 (Ni3A1) which has a Cu3Au -type ordered structure8 and remains ordered up to 1000°C.B EXPERIMENTAL PROCEDURE The alloy used was identical with that used before. Chemical analysis showed 6.27 wt pct (12.71 at. pct) Al, the principle impurities being 0.065 pct Fe, 0.022 pct Co, 0.020 pct Cu, and 0.004 pct C. Bar stock of 1 in. diam was cold-swaged to % in. diam, cold-rolled to 0.300-in.-thick strip, and annealed at 900°C in dry hydrogen. It was cold-rolled to 0.100-in. thickness and solution-treated for 1 hr at 1000°C while sealed in a quartz tube in argon, quenching in iced brine with the aid of a device to snap off the nose of the tube. Lineal analysis gave an average grain size of 0.055 mm. Pieces of strip were aged at 700°C in vacuo for 30 min, 51/4 hr, and 1 week to produce nominal average particle widths of 60, 150, and 500A, respectively, as known from the previous work.' The average diamond pyramid hardness was determined. The heat-treated strips were rolled from 0.100 to 0.005 in., a reduction of 95 pct, and the rolled strips stored at about -5°C. Small pieces were annealed within 1 week for 30 min at temperatures from 300° to 950° ±2°C in a horizontal vacuum furnace. Strips were withdrawn into a cooling zone, giving an estimated initial cooling rate from 950°C of about 50°C per sec. Average diamond pyramid hardnesses were determined on a lightly electropolished spot on the surface of each strip using 300-g load. Each point on the softening curves represents a separate annealed specimen. Sections containing the rolling direction were examined by optical metallography. Selected specimens were electrothinned to the center plane' and examined by transmission at 100 kv in a Siemens Elmiskop I electron microscope. It is well-known that changes in the structure tend to occur when a deformed strip is electrothinned below a thickness of a few hundred angstroms, although this is less serious with a material such as nickel which has a high melting point, and also is apt to be less serious when particles are present. Observations were nevertheless confined to thicker regions of the foils with estimated thicknesses over 1000A. No changes were observed due to beam exposure.

Jan 1, 1968

By A. M. Gaudin

UNTIL recently little attention has been paid to the effect of particle size on flotation. This has been especially true of material finer than 200 mesh.1 Particles of different sizes must behave differently in a flotation circuit; increased information along this line would be of practical use as well as of theoretical interest. The object of this study has been to determine what effect particle size has on floatability. The problem has been approached in two ways. One method consisted in a study of samples of the final products of several mills. These samples were sized and each size-product was analyzed for its important constituents. Bakelite briquettes2 of some of the products were made and studied under the microscope. This investigation is being continued, with particular reference to quantitative microscopic analysis of intermediate products of flotation plants. M In the other method of study, mixtures of pure minerals were ground to different degrees of fineness and floated. The products were then sized and analyzed. A study of the behavior of mixtures of pure sized minerals would have been illuminating, but after trial it was considered impractical on account of the tediousness of the large amount of elutriation required and the fact that the mineral particles would oxidize while being sized, preparatory to flotation. Broadly speaking, the following conclusions have been reached: 1. Results obtained by the two methods of study are in agreement. 2. The usual notion about the relative ease of flotation of very fine particles does not agree with the facts: 3. There is a time sequence of flotation with regard to particle size, the medium coarse particles floating first. 4. No successful method of floating extremely fine pulps has been found. 5. Recovery is optimum in a certain well-defined size range. 6. Selection is optimum in another well-defined size range.

Jan 1, 1931

By E. I. Larsen, F. R. Hensel

According to statements by Guertler1 Smith and Hamilton were the first to study the copper-titanium alloys, but owing to the presence of large amounts of impurities their data are inconclusive. M. A. Hunter and I. W. Bacon later investigated the electrical conductivity and the temperature coefficients at room temperature. The present writers reported their results2 in November, 1930. Recently Kroll published data on copper-titanium alloys3 which agree closely with those obtained by the authors. Material Tested The titanium used was in the form of square sintered rods, the analysis of which runs as follows: titanium, 95.4 per cent; silicon, 0.7; iron,l.8; aluminum, 1.4; copper, 0.1; manganese, 0.05. The ingots were prepared in a high-frequency induction furnace in air atmosphere. Their analyses are given in Table 1. Up to 5 per cent titanium the alloys could be forged. Above that amount they were red short and broke up easily. Owing to their rapid absorption of nitrogen and oxygen from the air, the alloys with the higher amounts of titanium tend to form surface films which greatly increase the casting difficulties, especially when small masses of metal are handled. It was, however, possible to prepare sound ingots up to 25 per cent titanium. Thermal and X-ray Investigation The cooling curves of some of the alloys are plotted in Fig. 1, and R tentative diagram constructed from these data is given in Fig. 2. From this it is evident that the solid solubility of copper for titanium is approxi-mately 4 to 5 weight per cent titanium at 878" C., which is the eutectic temperature. The melting point of copper is lowered gradually by adding

Jan 1, 1932

By R. S. Burns, J. G. Erskine

The performance of the nine 5.5 m diameter x 6.4 m mills (18 x 21 ft) initially installed at Bougainville Copper Ltd. did not meet the laboratory and pilot plant derived design expectations as measured by Bond Work Index. During the post-commissioning period, inefficient grinding of coarse material resulted in a build-up of large circulating loads and led to reduced throughputs because of pump and cyclone overloading. Installation of larger pumps and cyclones and development of an improved circuit control philosophy alleviated materials handling problems and permitted higher tonnages to be attained. Since 1977, plant throughput has been increased by installation of three additional mills. These are 0.9 m (2.9 ft) longer than the other nine and have a higher capacity. Developments in classification and mill speed-up, together with a finer ball mill feed size and substantial improvements to mill availability (99% in 1982) have further increased plant capacity. There is a continuing emphasis on improving grinding circuit efficiency in terms of throughput/grind. Current development work includes trials of graded ball charges, different liner profiles, and assessment of scalping/regrind proposals.

Jan 1, 1985

By Robert C. Freas, William H. Lane, David J. Krohn

Maysville, Kentucky, is the location of Dravo Lime company's new 9 070 mt(10,000 tons) per day limestone mine and 2 727 mt (3000 tons) per day calcination plant. This complex has been designed as a unit, and capitalizes on recent technological advances. Geologically the Dravo facility is.located on the eastern flank of the Cincinnati Arch, with the high calcium limestone being found at a depth of approximately 274 m (900 ft). A systems approach has been employed in designing and equipping the mine. This allows for maximum production while maintaining flexibility and versatility. All hydraulic drilling, large LHD equipment, and an extendable mine conveyor system are utilized in a five-part mining cycle. A modular concept modifies the room and pillar system to optimize ventilation. The limestone is calcined in three 5.18 x 61.87 m (17 x 203 ft) KVS rotary kilns with a design capacity of 909 mt (1000 tons) per day of lime per kiln. The kilns are coal fired and equipped with preheaters. Lime storage is provided by three 57 m (186 ft) high concrete silos with a combined capacity of 40 909 mt.

Jan 1, 1976

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10'3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey' to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N's are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen's computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.' The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By Robert Linton

This paper deals with work that has been carried on for over three years by the management and staff of the North Butte Mining Co. in an effort to standardize mining methods, to eliminate lost motion in the operating organization, and to improve the efficiency of the individual workman. Naturally, much of this work is an adaptation of ideas suggested by other mining operations or by practice in manufacturing and other productive industries. The studies, however, have developed some features that it is believed are new. Both new and adapted features are given in detail. The normal capacity of the North Butte mines is about 2000 tons per day. Hoisting is done principally through the Granite Mountain shaft, which is 3740 ft. (1140 m.) deep and equipped with an electric hoist capable of hoisting 200 tons per hour from a depth of 4000 ft. (1219 m.). The lowest stoping level is the 3400-ft. The Granite Mountain shaft is connected with the Speculator shaft, about 850 ft. (259 m.) south, and with the Gem, about 1150 ft. (350 m.) east, which are 3000 (914.4 m.) and 2000 ft. (609.6 m.) deep, respectively. These two shafts are equipped with reversible fans for ventilation. The Speculator has a steam hoist with a capacity of 150 tons per hour from the 3000-ft. level. The Granite Mountain shaft is concrete lined from the 1600-ft. to below the 3000-ft. level and gunited with cement from the 1600-ft. level to the surface. Sections of the Speculator shaft with a total combined length of 500 ft. (152.4 m.) are also concreted. There are approximately 36 miles (58 km.) of drifts and crosscuts in the mine, in which there are 15.2 miles (24.5 km.) of track. At normal capacity, about 75 stoping faces, 20 raises, and 30 sill development faces are working. Stoping is usually by the standard square-set method. Where the size of the oreshoot and character of the walls permit, the rill (or cut-and-fill) system is employed. Scope and Limitations of Standardization Standardizing mining operations presents problems quite different from the problems of the manufacturer. Methods of a successful

Jan 1, 1922