Search Documents

By J. B. Morrow

WITH numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sam-pling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1935

By H. Conrad, E. Stofel

The fracture behavior of 60-deg-oriented sapphire crystals was investigated for both tension and compression. Plastic flow on the basal plane was found to be a factor in reducing the tensile stress required to produce fracture in the temperature RECENT experiments1-' have shown that single crystals of a alumina (sapphire) can deform plastically, particularly at temperatures greater than 1000°C. The effect of this plastic flow on the fracture behavior of sapphire was not established, but range 1100º to 1500ºC. Mechanical twins, both (0001) and (0111) types, were produced by compression in the temperature range 1100" to 1300°C. Cracks propagated more readily along the twin boundaries than in the nontwinned crystal. experiments with other ceramic crystals4'5 have shown that plastic flow can initiate cracks that lead to catastrophic failure. This suggests by analogy that plastic flow might also be an important factor in the fracture of sapphire crystals. A recent experimental investigationS undertaken to determine the mechanism of plastic flow in sapphire provided an opportunity to study the type of fracture produced after various amounts of plastic shear strain. The results of this study of fracture are reported in the present paper. During the course of

Jan 1, 1963

By W. D. Felix, R. D. Smith, J. A. Campbell

The mechanism most consistent with available information on atmospheric trace element emissions involves the volatilization of a significant fraction of many trace elements during coal combustion, with subsequent condensation on fly ash as the combustion gases cool. The larger surface-td-volume ratio of the smaller particles leads to an enrichment of the volatile trace elements. From an environmental viewpoint, the submicron size particles are of greatest concern. These particles show the highest concentrations of trace elements, are least efficiently collected by pollution control devices, have high atmospheric mobilities, and are deposited preferentially in the pulmonary and bronchial regions of the respiratory system. The mechanisms for trace element enrichment and formation of submicron particles will be described.

Jan 1, 1981

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By R. M. Brick, R. G. Treuting

DESPITE the basic importance of slip in the plastic deformation of metals, and the considerable experimental investigation, thought, and speculation that have been devoted to the fundamental nature of these processes, surprisingly few data have been reported regarding the microscopic appear- [ ] ance and distribution of slip lines,[$] the external manifestation of the slip process. Photographs hitherto reproduced in the literature are in general at low or unspecified magnifications with no correlation to the prior shear. A single-crystal cylindrical tensile specimen of alpha brass about ½ in. in diameter, one of many previously prepared by H. L. Burghoff,1 was available for study. A plane about 3/16 in. wide, parallel to the specimen axis and normal to the plane containing the slip direction and the specimen axis, was ground and metallographically polished along the entire 5-in. gauge length. Heavy etching produced a surface free of both scratches and flow. The specimen was strained in tension until slip markings first became visible on the polished surface (Figs. I and 2). Restressing the crystal caused additional markings to appear at an initially lower [ ] stress than previously was required. Stretching the specimen to produce a dense concentration of slip lines caused such variations in level in the polished surface (normal to the slip direction) that microscopic study at higher magnifications became impossible. After annealing 15 hr. at 850°C., the specimen recrystallized to form two grains with a boundary approximately normal to the specimen axis and about midway along its length. Each was X-rayed, and two planes were again polished along the length of the specimen, in this case each parallel to the slip direction in one of the two crystals. A light longitudinal scratch parallel to the specimen axis was drawn down the center of each plane. A Huggenberger extensometer was attached to the crystal A, whose slip plane would have the higher resolved shear stress of the two, and the specimen was again strained in tension.

Jan 1, 1941

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By Robert Henderson

SEVERAL very interesting articles have been written on the caving system of mining, but most of these papers have dealt separately with the slusher system or the chute and grizzly system. In this paper, a comparison will be made of the two methods, both of which are being used at the Climax mine. The mine is on the Continental Divide, in central Colorado, at an altitude of approximately 11,500 ft. above sea level. The long, cold winters, characteristic of the high Rockies, create a number of operating problems not usually found in other mining areas. THE ORE BODY The Climax ore body is just east of the Mosquito fault. This structural deformation has brought the granite on the east against the sedimentary rocks on the west. The ore occurs in an intensely altered granite and schist around a silicified granite core. The ore is in a highly fractured zone of moderate silicification. The principal mineral, molybdenite, is found in these fractures. Barren dikes of granite porphyry cut through the ore body and core with no apparent regularity. The grade of the ore is fairly uniform and gradually decreases toward the footwall core and also into the hanging-wall granite. The footwall and hanging wall are determined entirely by assays. The ore body is roughly dome-shaped, with the apex truncated at the surface. It is covered to varying depths with talus. A horizontal section of the ore body on the Phillipson level appears as an annular ellipse surrounding the footwall core. The ring of ore varies in width from 300 ft. to as much as 800 ft. The north-south axis of the core is about 1200 ft. and the east-west axis is about 1800 ft. In the ore zone, the rock is sufficiently strong to maintain reasonably large openings, and openings larger than haulage drifts usually have to be supported. The ore is cut by a great many fractures and shears and breaks into rather large blocks when caved, necessitating considerable secondary blasting. The waste that overlies the ore body breaks relatively fine in comparison with the size of the blocks of the caved ore and tends to run through the broken ore in the cave, causing dilution unless the draw is carefully controlled. MINING SYSTEMS For several years the ore was mined by the chute and grizzly system, a system that differs from that used in other caving mines only in the size of openings and equipment. In the chute and grizzly system, main haulage laterals were driven along the footwall core and also along the

Jan 1, 1944

By Arthur Smith

THE Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district-the United Verde and the United Verde Extension-lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., . a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to? the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Wood chute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the . smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. This strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the vicinity of Allen Springs, at the south end of Mingus mountain and all within the boundaries of the Prescott national forest reserve.

Jan 3, 1924

By Albert Ledoux

SEVERAL years ago my firm was representing the Mt. Lyell Co. of Australia, which was shipping its blister copper to a refining works in the United States. After the contract had been running for many months, the superintendent of these works discovered that if water was poured upon the surface of the bars much of it would disappear into the interior through blow holes. -Some experiments made by him showed that this could be a considerable amount, so that copper which had been rained on before it was weighed, although the surface appeared dry, nevertheless would contain water. It had frequently occurred in our experience-as samp-lers that the drillings from a lot taken by boring would come out quite wet, and in some cases, indeed, water would drip into the sample pan placed below the bars, due to the fact that the drill had penetrated a cavity or cavities containing water, which presumably got into the cavities at the time the copper was water-cooled after casting, there being, perhaps, no outlet to the surface. So far as I know, until this discovery at the refining works, no. one had thought that rain could penetrate into the interior of blister copper; at least in any quantity sufficient to be considered.

Jan 10, 1922

By Millard K. Shaler, Sydney H. Ball

During the past 50 years the attention of mining-men has been turned to Africa, and within the past decade prospecting-expeditions sent into Central Africa have resulted in the open-ing-up of several mines. Having recently spent two years in the Belgian Congo for the Societe Internationale Forestiere et Miniere du Congo, it is our purpose to outline briefly the mining-conditions in that part of Central Africa. Before it became, in 1908, a Belgian colony, this region was known as the Congo Free State. 11. Location and Area. The Belgian Congo lies in southwestern Central Africa, west of the continental divide, as illustrated in Fig. 1. It has a coastline of but 20 miles on the Atlantic, but widens rapidly eastward to points 5 north and 14 south of the equator. Its area is 908,000 sq. miles, which is almost one-quarter that of the United States and Alaska, or more than one and one-half times that of Alaska. Stated in other terms, its area is nearly one-third that of the United States, exclusive of Alaska and the insular possessions, or more than that of all the United States east of the Mississippi river. III. Topography and Drainage. From north to south, Africa is made up of three topographic elements: 1, the Atlas mountains, a highly-accentuated region

Jan 1, 1911

By Arthur Philips

THE purpose of this paper is to present certain data and observations resulting from a series of experiments dealing with the heat treatment and microstructure of commercial white cast iron and its derivative, malleable iron. In planning the experimental work, particular pains were taken to secure for the tests white cast iron of "normal" composition; i.e., within the composition limits commonly prescribed by manufacturers of malleable castings. A review of the literature leads us to believe that much data of a fragmentary character treating of the graphitization of white cast iron have been of little value, mainly because of the diversity in chemical composition of the materials employed in the tests. Moreover, when feasible, annealing periods at least comparable to those of current practice have been adopted. We wish to acknowledge our indebtedness to the members of the research department of the Eastern Malleable Iron Co. for the white cast iron used in the tests and, particularly, for their active cooperation during the experimental stage of the work. In this paper the following subjects will be discussed in the order indicated: Data on the thermal critical points of white cast iron and malleable iron. Changes produced in tensile properties and microstructure of white cast iron by annealing at different temperatures within the range, 760 to 1100° C. Relation of thickness of wall section of hard iron to microstructure and tensile properties of malleable iron obtained under normal annealing conditions. Notes on mechanics of graphitization of normal white cast iron as observed in specimens quenched after various periods of anneal at approximately 800° C.

Jan 1, 1922

By C. O. Brawner

FACTORS THAT INFLUENCE STABILITY AND STABILIZATION METHOD The most effective stabilization method and design can only be developed if the cause(s) and mechanics of the slide are known. Therefore, it is important that the stability be evaluated by an engineer who has had extensive rock stability experience. The most important factors that influence stability are structural geology, ground water, blasting and the mining method or methods. Structural Geology - The majority of failures in rock slopes occur along discontinuities in the rock (joints, bedding planes, shear or fault zones, etc.). Therefore, on all surface mining projects, the development and maintenance of a comprehensive structural geologic mapping program should be a first priority program that is considered a part of the operations function. This program should include mapping all major features - faults, shear zones and through going joints. All structural features which could influence stability should be mapped and presented in a structural domain format for the entire mine (Canmet, 1977). Where planes, wedges or blocks will be undercut by the mining excavation, shear strength and strain to failure tests should be performed on the joints, fault gouge and gouge-rock contact surfaces. These tests must be performed on the samples in the direction of potential slide movement and must determine the range of peak and residual shear strength values. A preliminary assessment of friction angle can be obtained from measurements of failed surfaces in the field (Figure 1) or from core sliding tests (Barton, 1981). An assessment must be made of the past geologic history of

Jan 1, 1983

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

THE binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean' and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-Antimony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Tin These three systems are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

Jan 1, 1928

By P. G. Beckett

THE problem of handling the large quantities of water encountered in the Old Dominion mine presents many features of interest. In the present paper are discussed the probable sources of water, the pumping equipment, the increased flow into the mine in the early part of 1915, culminating in the flooding of the 18th and 16th levels in March of that year, and the difficulties that were met with during the high-water period. I. PRELIMINARY The Old Dominion mine, situated 1 mile north of the town of Globe, Ariz., has long been one of the prominent copper producers of the State, and until the opening up of the copper schist deposits in the neighboring mines of Miami, was responsible for the greater part of the copper output from the Globe district. As the gradual exhaustion of its orebodies near the surface led to the downward development of the mine, more water was encountered in the western portions directly underlying the dacite formation until the drainage problem became a serious factor in the operation of the mine and in the economical extraction of the ore. A heavy inrush of water on the 10th level of the mine in 1906, preceded by still earlier water difficulties, rendered imperative the immediate installation of a pumping equipment capable of handling large flows of water. While the Old Dominion has been recognized as a wet mine since its early clays and one in which the complete control of the water situation was of paramount importance in the development of the lower levels, it is chiefly in the last nine years, since the installation of the increased pumping equipment, that the mine has developed and handled large quantities of water.

Jan 4, 1916

By James G. Crawford

Correlation Of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the petroleum engineer. The water in each producing zone tends to have diagnostic characteristics by which it can be distinguished from every other water above or below that zone in that immediate vicinity. Representative analyses of oil-field waters from producing oil and gas fields in the Rocky Mountain region are included, and the diagnostic characteristics are discussed briefly. It is concluded that the generally dilute nature of Rocky Mountain oilfield waters is a result of dilution by meteoric waters, and that there is no relationship between presence or absence of commercial oil and the character of water in a structure. Introduction The study of waters associated With oil and gas began more than 50 years ago and has been well recognized by operators, engineers, and geologists for about 30 years. It appears unnecessary at this time to recite the history of oil-field water analysis; suffice to say that it has proved its worth many times to the production engineer suddenly confronted with water problems in producing oil and gas wells. Chemists and geologists have studied the possible origin of these waters and as Yet the subject is unsolved in many important phases. There are both local and regional problems connected with the explanation of concentrations and character- istics peculiar to each field, each subsurface zone and each province. Criteria useful in postulating the Occurrence of oil Or gas in One province completely fail when applied to another, and data carefully prepared and analyzed from one field may be actually misleading when applied to another. Correlation of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the engineer. The concentrations and characteristics of the waters are essential to the engineers and geologists making interpretations of electric logs in this region. The behavior of water under conditions of reservoir temperature and pressure is dependent to a great degree upon its concentration and characteristics, and thus important to the reservoir engineer. With the advent of secondary recovery methods in the Rocky Mountain region the characteristics and treatment of water will become increasingly important. Premises upon which Correlation Is Based A brief review of the geochemical history of oil-field waters will suffice to present the premises upon which correlations of the waters are based. Sedimentary rocks which are now stratified were first sediments in seas, lakes and streams. These sediments were filled interstitially with connate water. With burial the sediments were compressed arid consolidated, integrated and indurated into bed rock and much of the connate water was dispelled. Following the formation of bed rock the strata were sub-

Jan 1, 1949

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By Roscoe C. Clark

A study of the effect of various corrosive waters on five different types of cements indicated that those cements containing less than 5 per cent tricalcium aluminate were the most resistant to corrosion. INTRODUCTION Oil field experience indicates that some formation waters are excessively corrosive to some cements. A study has been made to determine the most corrosive waters and the relative resistance of various types of cement to these corrosive waters. PROCEDURE This study of the corrosion of cement was limited to an evaluation of the effect of various corrosive waters on five different types of cements. A determination was made of the types of cements which offer the greatest resistance to corrosion and of the chemical contents of waters found to be the most destructive to cements. The laboratory tests were conducted by immersing small cylinders of 20 samples of set cement in various corrosive waters. The initial mixing of most of the cement slurries was done using Tulsa tap water as the mixing water; however, a few of the slurries were mixed using a sulfate water as the mixing water. When the 20 samples had been immersed for a period of nine months, they were removed from their corrosive baths, inspected and photographed. The field tests were conducted by placing ten cement specimens, each contained in a screen wire thimble, in the gas anchors of insert pumps in wells in six different fields. The specimens were observed whenever it was necessary to pull the pumps and were returned to the 1aboratory when deterioration had reached a serious state. EXPERIMENTAL RESULTS In both the field and laboratory tests the resistance of the different cements to corrosion was determined by the condition of the samples and the number of samples of each that were in good condition at the end of the immersion period. Table I lists the various cements tested in the order of their resistance to corrosion with the most resistant at the top and the least resistance at the bottom. An analysis of Table I reveals that the upper half of the table predominates in slow set and sulphate resisting cement.: (low 3CAO.A12O3 content) while in the lower half the port-land and high early strength cements are in the majority. Of the last two the high early strength cements appear to offer less resistance to sulfate water corrosion. An investigation of the composition of the cements listed in Table I indicated that as a general rule the cements containing less than five per cent tricalcium aluminate will exhibit the greatest resistance to corrosion. The destructive action of various corrosive waters was compared by listing the waters in the order of those containing the largest number of samples that failed completely. These ratings are presented in Table II with the most corrosive waters listed first and the least corrosive last. Figs. 1 and 2 show the end views of cement samples which had been immersed in the baths of five per cent MgSO, water and the five per cent Na2SO4 water respectively in the laboratory. These .pictures are representative of the results obtained and present a pictorial evaluation of the corrosive resistance of various types of cements.

Jan 1, 1950

By S. L. Hoyt

The writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + b range, first described in 1913. These notes are offered, not at all as the final explanation 'of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520' C. and the other at about 600" C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600" C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + B range and increased in magnitude with the amount of B up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + B field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 1, 1919