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By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

Executive SCOTT TURNER, Chairman FREDERICK M. BECKET JOHN A. MATHEWS H. A. GUESS WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL D. MERICA ROBERT E. TALLY Admissions JOHN M. LovEJOY, Chairman GEORGE D. BARRON ERLE V. DAVELER WILLIAM H. BASSETT W. D. B. MOTTER, JR. Alternates HENRY B. FERNALD F. JULIUS Polls AMOR F. KEENE

Jan 1, 1932

Jan 1, 1968

By Richards J. W.

J.W. RICHARDS, South Bethlehem, Pa. (communication to the Secretary?).-Mr. Howland's paper, data and conclusions have interested me intensely, and have led me to study carefully the record-of his 26 furnaces therein given. Mr. Howland is undoubtedly right in his conclusion that when expressing the amount of carbon burned at the tuyères in percentage of the total

Jan 1, 1917

By R. Salter, C. K. Chase

Although Asarco's Silver Bell Unit, 40 miles west of Tucson, Ariz., is known primarily for copper production, molybdenite is also produced as a byproduct in the 8000 tpd flotation mill. The Silver Bell ore comes from two pits approximately two miles apart. Copper mineralization is essentially chalcocite resulting from two to three-fold secondary enrichment in a highly altered zone. A typical porphyry copper deposit, Silver Bell ore is of medium hardness. The ore consists of about one part molybdenum to 65 parts of copper. In the copper concentrate which is the starting point for separate molybdenum recovery, the ratio is also one part molybdenum to 65 of copper. Molybdenum mineralization is primary. Enrichment is not evident but it is notable that the molybdenite is more common in the more siliceous, harder rocks. The actual molybdenite occurs as diversely oriented flakes of fairly constant grain size, mostly in fractures associated with quartz veins. Most of the mineral appears unoxidized; secondary coatings on the molybdenite flakes are fortunately rare. In May 1962 a modified, improved version of the molybdenite circuit was put into operation.

Jan 7, 1964

By K. S. Seljesater

SINCE the development of dispersion-hardenable lead-antimony alloys1 in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. EXPERIMENTAL In order to-study the effect ,of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per FIG. 1..-CHANGE OF MICRO-BRINELL HARDNESS WITH TIME OF 1 PER CENT. LEAD-ANTIMONY ALLOY. cent. lead). The alloys were cast into bars 1 ½ in. wide by ¾ in. thick and cold-rolled to about 1/8 in. thickness. Three samples of each composition were annealed 1 hr. at 225° C. and quenched in water. One set was aged at room temperature, one at 50° C., and the third at 100° C., the

Jan 1, 1929

Jan 1, 1967

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

Jan 1, 1967

By Khosrow Bakhtar

A series of nineteen shear tests were performed on fractures 1 m2 in area, generated in blocks of sandstone, granite, tuff, hydro- stone and concrete. The tests were conducted under quasi-static and dynamic loading conditions. A vertical stress assisted fracturing technique was developed to create the fractures through the large test blocks. Prior to testing, the fractured surface of each block was characterized using the Barton JRC-JCS concept. The results of characterization were used to generate the peak strength envelope for each fractured surface. Attempts were made to model the stress path based on the classical transformation equations which assumes a theoretical plane, elastic isotropic properties, and therefore no slip. However, this approach gave rise to a stress path passing above the strength envelope which is clearly unacceptable. The results of the experimental investigations indicated that actual stress path is affected by the dilatancy due to fracture roughness, as well as by the side friction imposed by the boundary conditions. By introducing the corrections due to the dilation and boundary conditions into the stress transformation equation, the fully corrected stress paths for predicting the strength of fractured blocks were obtained.

Jan 1, 1984

By R. G. Burdick, W. R. Peters

Shallow underground voids resulting from early coal mining and other resource recovery activities over the past several decades are now being recognized as a significant cause of ground subsidence problems. Uncertain knowledge of abondoned coal mines also imposes potential hazards in current underground mining operations, since water inundation or the release of methane gas is a serious hazard when mine excavation operations break into an abandoned mine. Requirements for detecting and mapping subversive manmade tunnels in previous work has led to the development of a surface-operated automatic earth resistivity survey system and associated computer data reduction process for military applications. Field demonstration tests of this system have resulted in successful detection of tunnels at depth-to-diameter ratios greater than 10 to one. Under the sponsorship of the Bureau of Mines, a similar high-resolution earth resistivity system was designed and constructed for use as a potential means of detecting abandoned coal mine workings. The hardware and software aspects of third new system are described together with applications of the method for surveying and mapping abandoned coal mine workings. Field tests are presented to illustrate the detection of both air-filled and water-filled mine workings.

Jan 1, 1984

By Charles Berkey

CONTENTS PAGE C. P. Berkey-Responsibilites of the Geologist in Engineering Projects (with discussion) 4 Kirk Bryan-Problems Involved in the Geologic Examination of Sites for Dams 10 0. E. Meinzer-Relation of Ground-water Conditions to Leakage of Reservoirs (with discussion) 19 Charles Terzaghi-Effect of Miner Geologic Details on the Safety of Dams (with discussion) 31 G. H. Matthes-More and Better Geologic Data for Use in Hydraulic Projects (with discussion) 47 L. W. Fisher and R. D. Ohrenschall-Geologic Examination of Dam Sites in the Tennessee and Cumberland River Basins 60 C. K. Wentworth-The Geology of Dam Sites (with discussion) 78 L. C. Glenn-The Geology of Dams and Reservoirs 97 H. T. Stearns-Success and Failure of Reservoirs in Basalt (abstract) 111

Jan 1, 1929

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy's obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:'l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By John Dilworth

THE word "development," as used in connection with .mining, is a rather general term and in most instances must be qualified or explained before the exact thought in the mind of the user is made clear. For instance, by the development of a mining district is often meant its entire facilities of mineral production, such as railroads, towns, mine plants, etc. In speaking of the development of a property its prospecting by test pits or diamond drill borings may be referred to; or it may be the mines, strip pits or quarries from which the coal, ore or rock is won. But, as a rule, when the development of an individual mine is spoken of the idea in mind is the system of underground workings by means of which the mineral is recovered and transported to the surface. It is this character f development that is considered in this paper. The discussion will be confined to the ordinary room-and-pillar, system of mining. practically horizontal coal seams that is used in most bituminous coal mines in this country, and to only two phases of this subject; viz., what is properly included under the head of "Development"' as it appears on the books of a coal company or the inventories of an examining engineer, and how its "value" should be determined -by the accountant or engineer. No absolute rule or definite agreement covers these points, yet these questions are far more than academic. Development is often an important part of a mining company's assets, affecting the amount of its invested capital (and hence its rate of taxation under present Federal income tax laws) as well as the value of its total assets and the amounts chargeable to cost of coal and to depreciation.

Jan 7, 1921

By E. S. Moore

ALTHOUGH nickel was in use in alloys long before the Christian era, the metal was not discovered until 1751, when Cronstedt recognized it in niccolite from Sweden. The Chinese apparently used a nickel alloy, known as "pahfong" thousands of years ago and Persian coins dating farther back than 200 B.C. consist of a copper-nickel alloy similar to some of those now in use in coins. The pure metal was first prepared about 1775 and the metal was refined for commercial purposes some years later. The nickel industry did not attain much prominence until the ores in New Caledonia were discovered. Exports of ore from that country began in 1875 and since that date there has been an ever-increasing world output of nickel and a great expansion in the uses of the metal except during short periods of commercial and industrial depression. Previous to 1875, for a number of years, Norway was the chief producer, although the metal was mined also in Sweden, Finland, Italy, Germany, Austria, France, China, the United States and other countries. With the dis-covery of nickel deposits in the Sudbury district, Ontario, a new factor was introduced into the nickel industry and Sudbury has since become the overwhelmingly dominant feature in the world's nickel markets. Although nickel was first discovered in Canada as early as 1848 near the north shore of Lake Huron and nickel-copper sulfides were found in 1856 by surveyors working close to the present location of the important mine at Creighton, in the Sudbury field, it was not until 188.3 that any importance was attached to this field. In that year copper sulfide attracted attention where the main line of the Canadian Pacific railroad was being projected across Canada to the Pacific coast. Mining began near this discovery in 1889 but in the meantime operations had begun in 1886 in other parts of the field and by 1890 about 100,000 tons of ore had been raised. In the Sudbury field, as in Norway and at the old Lancaster Gap mine in Pennsylvania, the ore was first mined for its copper content and difficulty in the refining of the copper led to the discovery of the important proportions of nickel in the ore. No. 3 property of the Inter-national Nickel Co., now known as the Frood, the greatest deposit in the

Jan 1, 1932

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By C. W. Spencer, J. T. Smith

GRAIN-BOUNDARY surfaces are penetrated by a liquid phase when the liquid-solid interfacial tension is less than one-half the tension of the grain-boundary surfaces. Grain growth may occur in the presence of this liquid phase. burke1 reports that grain growth of this nature has been observed in two-phase ceramic systems. He suggests that the presence of a grain-boundary liquid may accelerate or decelerate the

Jan 1, 1963

By N. A. Gokeen, M. Ohtani

EFFECT of elements on the solubility of carbon in liquid iron is useful in calculating and correlating a number of thermodynamic properties as shown elsewhere in detail.' Kitchener, Bockris, and spratt2, and later Turkdogan and Hancock3 have investigated the effect of sulfur on the solubility of carbon at various temperatures and concentrations. For any chosen sulfur concentration, the solubility of carbon reported by Kitchener et al. is considerably lower than that by Turkdogan and Hancock. It was therefore felt that a reinvestigation of this problem was necessary. EXPERIMENTAL METHOD An alloy of Fe-C-S .was prepared with electrolytic iron and ferrous sulfide melted by induction in a graphite crucible, 4 in. high 1 1/2 in. ID under a CO-atmosphere. The temperature, held at 1500" ± 5°C in all experiments, was measured with a Pt-Pt + 10 pct Rh thermocouple immersed into the melt. In order to assure saturation with carbon, the melt was stirred with a graphite rod. After approximately 1 hr at 1500 °C, a sample was obtained by sucking the melt into a silica tube, 4 mm ID. The sample was then analyzed for carbon and sulfur by usual methods. RESULTS The results are presented in Table I and plotted in Fig. 1 with the individual values of Turkdogan and Hancock.3 Scattering in the data is equivalent to 3 pct or less in carbon analysis. The broken line represents the empirical equation obtained by Kitchener et al. from their data. It is evident that the present data are in good agreement with those of the former investigators but in disagreement with the latter. The cause for this discrepancy cannot be readily offered since the experimental methods in the three investigations were nearly identical. Additional evidence corroborating the author's results may be presented in the following manner. The difference between the solubilities of carbon in the ternary Fe-C-X melt with a small concentration of any element X, and in the binary Fe-C melt is %?C = %CIII-%CII [1] where %?C is the change in solubility, and %CIII and %CII are the solubilities in the ternary and the binary systems respectively. The value of %Cii

Jan 1, 1961