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By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By J. Fred Johnson

MORE ORE is mined in the Bingham District than in any other mining district in Utah. In addition to the open-pit operations of the Utah Copper Co., there have been, many large underground mines. Until recent years the principal production was from the Jordan and Commercial limestones, but in the last eight years valuable ore deposits have been developed in the so-called alphabetical or "A," "B," "C," and "D" limestones, mainly by the U. S. Smelting, Refining & Mining Co. The value of these developments has led the company just mentioned to acquire large holdings in the district and within the last year to install at the Niagara shaft a hoist capable of going to a vertical depth of 4000 ft., or 1800 ft. deeper than the present lowest level. Ore from Bingham has been the chief factor in enabling the

Jan 1, 1934

By C. G. Dunn, M. Sharp

IN twinned crystals of the face-centered cubic metals the lattice of one twin is a mirror image of the other in a common twin boundary. When several twins appear within large grain in a sheet specimen, the twin one boundaries form a set of lines at the surface of the specimen which coincide with (111) planes of the large grain. Furthermore, for twins of the same orientation, these lines are parallel. Generally, the presence of identically oriented regions with straight parallel boundaries coinciding with a (111) plane of the surrounding crystal is strong evidence for identifying the island regions as twins of the parent crystal. However, Fig. 1, which shows the macrostructure of a large grain of copper with island regions that satisfy these conditions. is not an illustration of (111) twins. Since the reverse side of the specimen has much the same appearance, it was thought at first that these regions, which appear dark in the macrograph, actually were twins. According to X-ray data, however, these regions are second-order twins of the large crystal. With regard to their formation, these second-order twins formed by secondary recrystallization in a cube texture matrix. Growth occurred in the direction of the arrow (see Fig. 1) as the specimen moved slowly into a gradient temperature furnace as described previously.' Nucleation of the second-order twins occurred, therefore, on the ends facing opposite the arrow. If the origin of the second-order twins were due to repeated twinning, some first-order twin structure should be visible on these ends. This proved to be the case, as very small twins were readily found with the aid of a microscope, and probably could have been seen, in some instances, under ideal lighting conditions without aid of a microscope. Fig. 2 shows a cross-section view taken perpendicular to both the surface and the (111) trace of the parent crystal (visible as a straight boundary in Fig. 1) at the beginning point of growth of a second-order twin and where one first-order twin was relatively thick. In the micrograph, A is the large parent grain; B is the first-order twin of A; and C, which is a first-order twin of B; is a second-order twin of A. Between A and B and between B and C the major straight portions are traces of common (111) twin boundaries. The straight portion of boundary between A and C, however, is not a common crystallographic plane to the two lattices; it is a (111) plane of A and a (115) plane of C. Without considering the mechanism of twinning itself, the origin of the second-order twins may be accounted for in terms of repeated twinning and special growth characteristics. After each nucleation, a selective growth process can be thought of as favoring growth of the first-order twin in local spots only and favoring growth of the second-order twin to an extent comparable with that of the parent grain over relatively large areas in a way similar to that described for twinning in aluminum.' It has already been pointed out that the boundary between the large grain (A) and the second-order twin (C), which is responsible for the straight boundary portions in Fig. 1, involves a (111) plane of A and a (115) plane of C. The same combination of planes is not only possible in first-order twins, but actually appears quite frequently.3 Their prevalence in first-order twins and their presence here in second-order twins, together with the necessary occurrence of a large number of common lattice sites at the boundary, is an indication that this combination produces an "energy cusp"' boundary. (Energy cusp boundaries have been described by Shockley and Read.") The configuration of atoms near a {Ill), (115) boundary in first-order twins is of course different from the configuration near the same type of boundary in second-order twins. References 1 M. Sharp and C. G. Dunn: Secondary Recrystallization Texture in Copper. Journal of Metals (January 1952) Trans. AIME, p. 42. 2W. G. Burgers and W. May: Stimulated Crystals and Twinning in Recrystallized Aluminum. Recueil des travaux chimiques des Pays-Bas (1945) 64, p. 5. aD. Whitwham, M. Mouflard, and P. Lacombe: Discussion of W. C. Ellis and R. G. Treuting, "Atomic Relationships in the Cubic Twinned State." Trans. AIME (1951) 191, p. 1070; Journal of Metals (October 1951). 4 W. Shockley and W. T. Read: Dislocation Models of Crystal Grain Boundaries. Physical Review (1950) 78, p. 275.

Jan 1, 1953

By Reynold Q. Shotts

Data are presented which show that fractions of varying densities-from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals.

Jan 1, 1950

By Robert J. Linney

IN the latter part of the year 1943, it was decided to experiment with diamond-drill blast holes in the Old Bed magnetite mine at the Mineville mines of the Republic Steel Corporation, in sections of the ore body where vertical dimensions were large and where development for sublevel bench stopes had already been done. Other possibilities of application for this drilling method were in the reclamation of old floors and pillars in the pitching folds of the Lower Old Bed ore body and in the reclamation of large vertical pillars in the " 21 " Bonanza-Joker ore body. The cross sections and views of the two ore bodies will show the conditions to which the diamond-drill method has been applied. The Lower Old Bed magnetite ore body is lenticular and dips approximately 30° toward the southwest and strikes generally southeast and northwest. An intensely folded structure, which pitches generally on an axis approximately at right angles to the strike, is continuous from the uppermost old workings down to the present bottom of the mine, and probably continues with depth. On successively lower levels this folded structure becomes greater in vertical dimensions and the two folds are closer together in a horizontal dimension. As shown in Fig. 1, this folded structure gives to parts of the ore body considerable vertical dimensions, which provide areas that were developed for sublevel bench stoping above a slushing drift, as shown in Fig. 2. It was in one of these previously developed sublevel bench stopes, No. 26 on the 1185-ft. level, that the diamond-drill blast-hole method was applied for mining the upper sublevel. The lower sublevel was underhand-bench-drilled to the finger raises of the scram drift below. The roof of this stoping area began to break and spall on the lower sublevel, causing the roof to become inclined. Along the hanging wall of the stope this reached an elevation about half way between the two sublevels. A smooth schistose seam in the hanging wall causes the ore to break away freely. Therefore, if bench mining had been carried on in the upper sublevel, a dangerous condition of poorly supported benches would have resulted. When the drillers were slashing across the sublevel to footwall and hanging wall to make a bench, spalling roof of the opening below would probably have carried away part of the bench, and would have left a dangerous place in which to continue underhand benching. A 6 by 8-ft. raise had been driven between the lower stope and the upper sublevel about 200 ft. from a manway. It was decided to use this raise for a starting cut and to arrange holes as shown in Fig. 3, so that a slot would be opened across the ore body between the footwall and hanging wall. This slot would then be used for the purpose of breaking into the ore; by blasting vertical rings of holes drilled at right angles to the axis of the pitching folds as nearly as possible. Layouts of this slot drilling and the rings adjacent are

Jan 1, 1945

By Robert J. Linney

In the latter part of the year 1943, it was decided to experiment with diamond-drill blast holes in the Old Bed magnetite mine at the Mineville mines of the Republic Steel Corporation, in sections of the ore body where vertical dimensions were large and where development for sublevel bench stopes had already been done. Other possibilities of application for this drilling method were in the reclamation of old floors and pillars in the pitching folds of the Lower Old Bed ore body and in the reclamation of large vertical pillars in the "21" Bonanza-Joker ore body. The cross sections and views of the two ore bodies will show the conditions to which the diamond-drill method has been applied. The Lower Old Bed magnetite ore body is lenticular and dips approximately 30° toward the southwest and strikes generally southeast and northwest. An intensely folded structure, which pitches generally on an axis approximately at right angles to the strike, is continuous from the uppermost old workings down to the present bottom of the mine, and probably continues with depth. On successively lower levels this folded structure becomes greater in vertical dimensions and the two folds are closer together in a horizontal dimension. As shown in Fig. I, this folded structure gives to parts of the ore body considerable vertical dimensions, which provide areas that were developed for sublevel bench stoping above a slushing drift, as shown in Fig. 2. It was in one of these previously devel-oped sublevel bench stopes, No. 26 on the 1185-ft. level, that the diamond-drill blast-hole method was applied for mining the upper sublevel. The lower sublevel was underhand-bench-drilled to the finger raises of the scram drift below. The roof of this stoping area began to break and spall on the lower sublevel, causing the roof to become inclined. Along the hanging wall of the stope this reached an elevation about half way between the two sublevels. A smooth schistose seam in the hanging wall causes the ore to break away freely. Therefore, if bench mining had been carried on in the upper sublevel, a dangerous condition of poorly supported benches would have resulted. When the drillers were slashing across the sublevel te footwall and hanging wall to make a bench, spdlling roof of the opening below would probably have carried away part of the bench, and would have left a dangerous place in which to continue underhand benching. A 6 by 8-ft. raise had been driven between the lower stope and the upper sublevel about 200 ft. from a manway. It was decided to use this raise for a starting cut and to arrange holes as shown in Fig 3, so that a slot would be opened across the ore body between the footwall and hanging wall. This slot would then be used for the purpose of breaking into the ore, by blasting vertical rings of holes drilled at right angles to the axis of the pitching folds as nearly as possible. Layouts of this slot drilling and the rings adjacent are

Jan 1, 1946

By E. J. Whittenberger

OVER the past two decades, the Cr-Ni stainless steels, popularly termed 18-8 steels, have been used in ever increasing amounts in the aircraft, automotive, chemical, transportation, and building industries.' The contribution of nickel to these steels is associated with its strong austenite forming tendencies which assure good hot and cold forming characteristics, and with its beneficial influence upon corrosion resistance, especially in oxidizing acids. The adjustment of the chromium and nickel contents has been used advantageously in controlling the rollability and the response of the mechanical properties of these steels to cold reduction. With the advent of the jet age and the government stockpiling of nickel, considerable emphasis has been placed upon the development of satisfactory low nickel or nickel-free substitute austenitic stainless steels, especially for nonmilitary applications.2 Fer-ritic 17 pct Cr (AISI Type 430) stainless steel has been effectively substituted for the austenitic grades in applications with mildly corrosive exposure. However, the limited formability and ferromagnetic behavior of this grade do not permit its satisfactory use for many applications. To achieve better formability in a nenmagnetic steel and conserve nickel, a number of low nickel substitute austenitic grades of stainless steel have been developed in recent years. In most of these steels, manganese and nitrogen have been substituted for a portion of the nickel content, for example, 17 pct Cr-4 pct Ni-6 pct Mn (AISI Type 201), 18 pct Cr-5 pct Ni-8 pct Mn (AISI Type 202), and 16 pct Cr-1 pct Ni-17 pct Mn, all of which contain approximately 0.15 pct N.1 The precipitation of ferrite when large ingots of these Cr-Ni-Mn-N steels are heated to temperatures high enough for conversion to slabs on conventional universal slabbing mills has seriously affected the hot workability of these steels. This has been especially true in the case of the 16 pct Cr-1 pct Ni-17 pct Mn (sometimes referred to as 15 pct Cr-1 pct Ni-15 pct Mn) composition." Because it is possible that little, if any, nickel will be available for nonmilitary stainless steel applications in the event of a national emergency, a need has existed for a nickel-free austenitic stainless steel containing hot and cold forming characteristics similar to 18-8 steels and corrosion resistance at least comparable to the 17 pct Cr ferritic steel. The aforementioned deleterious effect of ferrite upon the hot working characteristics of the 16 pct Cr-1 pct Ni-17 pct Mn, steel indicates the importance of establishing the austenite-austenite plus ferrite phase boundaries as the first step in the development of nickel-free or low nickel substitute steels. This paper presents the data collected in an elevated temperature constitutional study of the Cr-Ni-Mn-N system at the South Works of the United States Steel Corp. Experimental Procedure The 300 compositions used in the investigation were melted in a 26 Ib induction furnace and cast in 3 14 in. diam by 18 in tall hot-tcpped ingot mo1ds.

Jan 1, 1958

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By J. A. Botin, K. H. Singh

INTRODUCTION The Alfredo underground mine is one of the three mining operations of Rio Tinto Minera, S.A., all near the community of Rio Tinto in Huelva province of southwest Spain. The other two operations are Corta Atalaya open pit (Pyrite ore) and Cerro Colorado open pit (Copper ore 1. Underground mining of Alfredo Mine for pyrites started in the nineteenth century and continued without interruption until 1979 when it was discontinued due to economical reasons. In 1972, a new project was started for the mining of copper bearing ores on the footwall of the pyrite deposit. This copper ore is locally named “Cloritas” and it forms a nearly vertical and tabular shaped orebody which forms an envelope at the footwall of the San Dionisio pyrite orebody. Mining of the Cloritas commenced in 1975 using cut and fill stoping. In 1977, the original project was completely revised which led to the introduction of a bulk mining system to achieve a planned production of 3,000 tonnes of ore per day. This paper covers the economic and planning aspects of the mine and discusses the evolution of the mining method for the Cloritas orebody. A GENERAL DESCRIPTION OF THE CLORITAS OREBODY The “Masa San Dionisio” (figure 1 ) is a massive sulphide orebody located in the town of Rio Tinto, about 90 kilometres west of Sevilla, Spain. Extensive vein-type sulphide mineralization exists in the volcanic host rocks of the Masa San Dionisio. Within this area of stockwork veins, there is a higher concentration of copper in the form of chalcopyrite in a zone adjacent to and paralleling the contact with the massive sulphides. This copper envelope is locally referred to as the "Cloritas Orebody” and the ore within it is called "Cloritas”. The main zone of the Cloritas orebody, (figure 11, is tabular and nearly vertical having a length of 375-400 m east-west, a thickness of 20-50 m north-south, and a vertical extension of 500 m from the surface. In addition to this area, there is a second less important low grade area called zone 2A located to the north of the main zone below 26 Level which, in some sections, is not fully separated from the main zone. MINING METHODS Mining in Rio Tinto area can be traced back to the Phoenecians and the Romans. Modern day mining started with the demand for sulphuric acid during the last half of the nineteenth century. By 1971, more than 33 million tonnes of pyrite had been mined out of Alfredo Mine, (San Dionisio Orebody), using labor intensive drift and fill methods and also by open pit method. During the last decade, underground mining of the pyrite had become uneconomic due to lower prices and a slackening demand for pyrite, and the underground mining operations for pyrite were finally stopped in 1979. In 1971, a major change in the long range mining plans for Masa San Dionisio was established. Between 1971 and 1975, underground mining of pyrites was progressively reduced while open pit extraction was increased in

Jan 1, 1981

By Paul Billingsley

THE development of the North Lily ground, which lies in the East Tintic district, Utah,. about half a mile northwest of the famous Tintic Standard mine, was undertaken by the International Smelting Co. on purely geological reasoning. The geologic theory on which this work was based resulted from several years' intensive study of the East Tintic district by the geological department of the International Smelt-ing Co., who were, during this period, indebted to many for valuable suggestions that were adopted and became part, of the gradually maturing concept. For example, E. J. Raddatz, president of the Tintic Standard Mining Co., first called attention to the significance of rhyolite alteration; J. W. Wade, assistant manager, contributed greatly to our knowledge of the great Tintic Standard orebodies; and so on all along. the line. In short, the ultimate theory embodies the aggregate experience and thought of all those most familiar with the area in question. The problem in brief was this: is the Tintic Standard deposit an isolated occurrence of ore, or are other ore deposits to be found in the vicinity? If the latter is the case, where can these others be looked for? The difficulty of the problem lay in the fact that most of the area is covered by rhyolite; beneath which lies the limestone in which the orebodies occur; so that the available evidence as to the structure of the formations, and, their mineralization; is of the slightest. The sav-ing features of the case, by means of which it proved possible to solve the problem, are three in number first, the rhyolite is pre-mineral and hence has been exposed to alteration by the mineralizing agencies; second, certain persistent dikes and fissures are con-tinuous through the rhyolite into the limestone below; and third, the extensive underground workings of the Tintic Standard gave a good basis for study of the sub-rhyolite structure and the occurrence of ore. The rhyolite overlies the Tintic Standard orebodies, and over them shows a large patch of brownish altera-tion. This patch proves to be due to chloritization and sericitization, which has spread out from certain zones of dikes, pebble-dikes and fissures. The dikes are com-posed of a light fine-grained rock which has been altered to an aggregate of quartz, alunite, and magnetite. They can be traced southwest to a common center in Big Hill, the entire mass of which is composed of the same material. The pebble-dikes, which consist of a mass of rounded pebbles, mainly quartzite, in a matrix ranging from the same quartz-alunite-magnetite rock as above to almost pure vein quartz, are closely asso-ciated with these light dikes, but in general extend farther northeast. They thus represent a specialized phase of the intrusive action of which Big Hill is the center. The brown chloritized rhyolite, then, is an alteration product due, in all. probability, to emana-tions closely associated with this phase. Since it coin-cides geographically with the Tintic Standard area of highly altered limestone, with its many great ore-bodies, it has been concluded, that it is the expression in the rhyolite of activities which have also altered and mineralized' the underlying limestone.

Jan 4, 1927

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.&apos; Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By EDWARAD A. SIVEDENBORMG

REPORTS have been made at different times on the progress of water encroachment in the Frontier sands in the Salt. Creek oil field, Natrona county, Wyoming. All previous reports have, -however, been largely based on the position of water in the sands as determined by various physical tests. Subsequent information has been secured through a preliminary investigation of the porosity, grain size and degree of saturation of the Frontier sands. Also, a closer differentiation has been made between the waters encountered incident to the production of oil by means of chemical analysis. In view of the more recent developments there has been a need of a water encroachment map of the first Wall Creek based on a field survey and additional information acquired since the water encroachment map of the sand of 1926, by J. S. Ross and E. W. Henderson, petroleum engineers of the U. S. Geological Survey. The present report is confined to a study of the first Wall Creek sand and was written in connection with the preparation of the map, showing water encroachment in this sand. The first Wall Creek sand was the discovery sand in the field, the first well having been drilled in 1908. Its thickness averages 120 ft. and, varies between 90 and 160 ft. The sand is in the Colorado group of the Upper Cretaceous series and is further considered as a part of the Frontier formation found in other parts of Wyoming.

Jan 1, 1930

By Arthur Notman

THE raw material men in all industries, and copper is no exception, are accustomed to think of them- selves as the whole show, and not without justice, for if there were no copper mines the world would have no copper. Nevertheless, many different things costing money and resulting in profits must be done to their product before it is ready for the world&apos;s use. In other words, they are making the frequent mistake of Chinking in terms of partial costs. Nobody really uses electrolytic copper. Possibly that is why nobody seems willing to pay anything for it. The manufacturers, being canny, do not buy any more electrolytic than they feel that they can work up and sell profitably, although they like to make the raw material men Chink that they will take all that can be produced. This is a state of affairs that has aroused my sympathy and curiosity, and has induced me to study the financial history of the copper wire and brass industry of the country or such portion of it as publishes any records readily available to the curious minded. About 60 per cent of the electrolytic copper used in this country is drawn into wire and consumed by the electrical industries. The remaining 40 per cent is

Jan 1, 1926

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision&apos;s prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision&apos;s prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By R. E. Allen

THERE was once a time when a practical oil man would appraise or buy a producing property on the basis of from $200 to $500 per barrel of average daily settled production. Curtailment-has, for the present at least, caused a virtual abandonment of the "barrel -of settled production" as a yardstick of, oil property value and in its place has come the "barrel of allowable production," which, although an artificial thing, is nevertheless now the principal factor governing the rate of ?pay out? or investment return. The potential production of a well, settled or otherwise, is of less importance in determining the present worth of a well than is the rate at which it may be produced. Speaking only of true potential for the moment, it is obvious that of two similar wells having the same potential, the one having the highest rate of allowable production would be worth proportionately more than the one of lesser allowable. The discount factor for deferred return and risk can easily vary the present values of the two wells by as much as 20 per cent when allowable rates are not greatly different.

Jan 1, 1934

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick&apos;s law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert&apos;s law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick&apos;s Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By Samuel S. Wyer

THE installation of the gas-producer power-plant in America has been so unusual that all engineers have viewed it with in¬terest; a large majority, however, regard it with a lack of con-fidence and many with positive distrust. Despite the fact that European engineers have usually been less inclined to take the initiative along experimental lines than are Americans, they have, nevertheless, developed the gas-producer plant to a very high state of efficiency to which they were forced by the neces¬sity of economy in fuel-consumption. The gas-producer power-plant is so common in Europe that engineers as well as the general public regard it with the same degree of confidence that is now universally placed in steam¬plants. Gas-engines, both small and large, are in general use there, and central stations, aggregating several thousand horse¬power, are quite numerous. The fact that gas-producer power-plants have received so little attention in America may be attributed to five conditions:-1&apos;, ignorance and prejudice; 2, newness of work; 3, in-

Mar 1, 1905

By W. A. Forbes

OUR present-day geological surveys show that 36 of our States are underlain with bituminous coal, covering a total area of 496,709 square miles. The North American continent possesses 69 per cent of the world&apos;s coal reserves, with the United States alone having an estimated 55 per cent. The American coal reserves, in tons, are calculated to he about 3,500,000,000,000 tons, of which we have exhausted about 1 to 1 1/2 per cent. If this coal were mined at the rate of the 1918 production-a record output of 579;000,000 tons-it would not be depleted for 4,000 years. The more easily accessible and high-grade coals would obviously be consumed much before this; some estimates are 100 years. The natural progress of the nation&apos;s industries up to 1910 encouraged on every hand the development of new mines, especially where cheap and easy access to coal measures was coupled with short hauls to the consumer. Over-development resulted, which is perhaps today one of the fundamental causes for the many difficulties faced by the coal industry, which is highly competitive; about 70 per cent of the production cost is labor. Salient statistics for 1930, recently issued by the U. S. Bureau of Mines, follow:

Jan 1, 1932