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By John Tabor, R. B. Spivey

INTRODUCTION Shafts have been sunk in a number of ways. By and large, however, most have been sunk by drill, blast, muck, and slip form methods. Most methods have provided satisfactory means of completion. The major drawbacks to the conventional methods have been: (1) un- reliable cost estimates for completion; (2) unreliable rates of progress; and (3) unreliable integrity of the shaft lining. Recently , engineering design studies have been done that strongly indicate, that, by the use of existing proven technology, shafts can be completed faster, more cheaply, safer, and with a better lining that has been possible using conventional methods. THE METHOD The alternate method utilizes the techniques of big hole drilling, shield excavator tunnelling, and pre-cast concrete lining. Big Hole Drilling - Drilled shafts have been completed for several years and I don't intend to address the technology, only to point out the use of drilled shafts is an alternate method of shaft sinking. Ideally, in a multi-shaft mine, the first shaft would be blind bored and cased to a size, whereby it can handle the muck from the excavation of subsequent shafts. It should be an 8' to 10' completed diameter. The cost of such a shaft in sedimentary formations compares favorably with a conventional shaft. However, it is much faster. For additional shafts, the role of the drill is to complete small holes (3' to 4') to the desired horizon. This is merely a hole to allow slashing to a larger size with easier muck removal from an underground drift connected to the previously drilled shaft. The smaller holes, just as the larger one, should be cased and grouted into place so as to assure a smooth open hole. SHIELD EXCAVATOR Theory and History - Tunnelling Shields have been in common use for several decades, and steam powered shields were used in England over 100 years ago. The purpose of the shield is to provide temporary ground support, protect personnel during operation, and to house the excavating equipment. The excavating equipment approach has varied from attempts at a continuous or semi-continuous boring machine, the tunnel mole, to a mechanical or hydraulic digging arm. The shield may or may not be an active digging element. If not active, the boring tool or cutter is advanced ahead of the shield to full diameter and then the shield is moved up to the cutter, or the shield advances along with the cutter. If active, the cutter opens a conical free face, and the shield is either jacked forward so that the leading edge spalls rock to the free face or poling plates are thrust forward to spall to the free face. In either approach, various methods of muck removal are incorporated into the shield. These may be gathering arms, conveyors, or with moles, hydraulic transport, where the cuttings are sufficiently fine. The efficiency of the muck removal system is critical as excavation is rapid and the system could easily become muck-bound. Application to Shaft Sinking- Technically, the use of a shield to sink vertical shafts is no different than a tunnelling operation. It is, in fact, less complex in most respects. Muck and water removal are difficult in a blind-driven shaft. However, where an underground opening is available for handling muck and water, rapid shield sinking is possible, using a pilot hole for muck and water to fall through and be removed from below. The Tabor Mining Shield is basically a caisson approach, whereby, the ground is only seen at the face or bottom. It does have hydraulic jacks to force it downward and has segmented cutting edges which allows forepoling ahead of the shield. The hydraulic excavator allows mining in the center of the face around the previously drilled hole with the forepoling segments slabbing to this free face. First, the drilled hole is cased and grouted. The machine is a tube with an excavator. The work cycle is as follows: (1) The casing and grout are cut at predetermined intervals by shaped charges. (2) The casing is crushed by the excavator, removed from the hole and hoisted to the surface. (3) The excavator then rips out a face around the hole by digging the formation in tension and breaking the pieces

Jan 1, 1982

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By W. J. Jordaan

The ability of soils to retain and hold cations is called the cation exchange capacity (CEC). Adsorbed cations, however, can be replaced by other cations through the process of cation exchange. Heavy mineral deposits contain a significant portion of slimes including the very fine clay minerals. In most circuits the slimes fraction hampers efficiency and has to be removed during early stages of the process. Being a nonvaluable process stream, the processing of the slimes is a costly exercise. In thickening applications it might be possible to manipulate the ability of clay minerals to retain and hold positively charged cations in order to optimize flocculation and therefore reduce flocculation costs. The CEC value of the slimes could be a measure of this possibility. To investigate this hypothesis, different slimes samples were characterized for size, chemical composition and clay minerals present. The CEC value of each sample was determined and explained in terms of the mineral phases present. Settling tests were conducted and an attempt was made to explain the CEC characteristics of the clay minerals in terms of settling rate. The scope of this investigation was to test the hypothesis and should not be seen as an in-depth study of the subject matter. A greater number of samples and detailed analyses to identify and quantify minerals and phases present would be required to investigate further the relationships between clay minerals in the deposit, CEC and settling rates. Location and geological setting Exxaro KZN Sands is mining a heavy minerals deposit at Hillendale mine located at Richards Bay, South Africa. The orebody consist of a dune some 8 km inland from the coast to the north of eSikhawini. A geological synopsis undertaken by Botha1 concluded that the Hillendale mining area represents a coastal dune sequence that accumulated north of the Tugela River. The northward movement of sediment by long shore drift currents result in a high sand budget on the beaches north of the river youth and is the dominant contributing factor to the accretion of the coastline and development of parallel dune systems along the coastal zone in this area. Beach swash zone processes and enrichment of the fine sand fraction occurs during wind transport off the beach by ascending parabolic dunes that form the coastal barrier dunes. This process results in heavy mineral concentration on the windward dune face and localized enrichment parallel to the dune forms. The aeolian sedimentary facies processes result in the primary concentration of higher grades in the upper silt-enriched reddish brown horizons of the profile. The synopsis by Botha1 further showed that an additional component of heavy mineral concentration can be ascribed to the post-depositional relative enrichment of heavy minerals due to weathering. Therefore, it is likely that the Hillendale orebody protolith was pedogenically weathered to form the homogeneous, silt-enriched, clayey reddish brown to dark red, palaeosol profile that grades downwards into yellowish brown, less clay-enriched sand. Slimes characterization Samples The Hillendale orebody was divided into geochemically discretized zones based on the concentration of ilmenite and other specific minerals and/or phases. Six composite samples were made up from exploration samples taken from Zone 9, Zone 11 and Zone 12. The red and orange horizons within these composite samples were separated and test samples were prepared to conduct test work and analyses. The test samples were submitted for preparation and analysis to characterize the slimes properties. Each test sample was deslimed at 45 µm representing the slimes fraction (-45 µm) and dried at 40°C. The -45 µm slimes samples were then split to conduct size analysis, chemical analysis, XRD and to determine the CEC. Size analysis The size distribution of the composite samples is shown in Table I. The size analysis shows that there is a difference in size distribution between the orange and red horizons of each zone. The orange horizons contain less 850 µ material as well as less slimes (-45 µm). The red horizons contain yore slimes (-45 µm). The size distribution of the slimes fraction (-45 µm) was determined using Malvern size analysis. The cumulative particle size distribution of the slimes is shown in Figure 1. The red horizons of the different zones show similar size distributions. The orange horizons show some differences. However, there is a difference in size distributions between the red and orange horizons.

Jan 1, 2007

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965

By Leendert de Witte

Conventional resistivity logs consisting of a short normal, a long normal, and one or more long lateral curves do not give data that allow a complete quantitative interpretation in beds thinner than 20 ft. Reservoir rocks usually exhibit zones of continuous homogeneity of quite limited thickness where the long lateral curves become useless because of adjacent bed effects and boundary phenomena. If the beds are 12 ft or thicker, the short and long normals may be used for qualitative interpretation, which can be streamlined by the application of simplified departure curves. For beds of a thickness less than twice the long normal spacing, this procedure breaks down. The combination of the limestone curve, the later-olog or guard electrode log, and the microlaterolog permit quantitative interpretation for beds that are at least 10 ft thick, provided the mud resistivity and the hole diameter are known with sufficient accuracy. For beds thinner than 10 ft, combinations of the microlaterolog with short spaced laterologs and pseudo laterologs appear to be promising. Interpretation of these curves again requires the application of simplified departure curves. Resolution of various possible combinations was analyzed using departure curve data calculated on the Whirlwind I computer at the Massachusetts Institute of Technology. A field example is shown using the microlaterolog-microlog combination, and the combination of a 6-in. modified laterolog plus a 6-in. pseudo laterolog. INTRODUCTION For the purpose of quantitative interpretation of resistivity logs in porous formations, we want to obtain two essential quantities from the logs, namely, the true resistivity of the undisturbed formation, Rt, and the resistivity of the part of the formation invaded by mud filtrate, Rt. The apparent resistivities of all conventional logging devices are functions of these two parameters and are also influenced by a third unknown parameter, the diameter of the invaded zone, d. It has been shown' that from the normal curves alone it is impossible to arrive at a unique solution for the three unknowns, Rt, R1, and d1. In very thick homogeneous beds, if invasion is not too deep, we can obtain a fair approximation to Rt from the long lateral curves and then use the two normal curves to find Rt and d1 Even under the most favorable conditions, the resolution of this system is not very good. The short normal does not give a reasonable approximation to R1 unless invasion is very deep (dl>16 hole diameters). For very deep invasion, however, the long laterals no longer approximate Rt. For bed thickness between 20 and 40 ft, the long laterals are affected appreciably by the adjacent beds; and the curves are distorted by boundary anomalies to the extent that they lose their quantitative usefulness in most cases. For the same bed thicknesses, the normal curves still function reasonably well. Although it is impossible to find unique solutions Lor R1 and Rt using the normal curves alone, we can obtain a reasonable approximation for the ratio R1/Rt through the use of simplified departure curves. This fact was brought to our attention by A. J. de Witte, geologist with Continental Oil Co. As the magnitude of Rl/Rt is a major clue to the presence of oil in formations, this method can be used to good advantage for qualitative analysis and will be discussed in somewhat greater detail. With the aid of suitable bed thickness corrections, the analysis of the normal curves may be used for bed thicknesses larger than 12 ft. For thinner beds, the method rapidly loses its resolution; and we have to resort to different types of resistivity logs if we want to attempt to analyze the curves quantitatively. The inadequacy of conventional resistivity curves in thin beds is far more serious than generally realized. Fig. 1 shows a conventional E. S. with a 16-in. and 64-in. normal and a 16-ft lateral through a section of Lansing-Kansas City lime, in comparison to a guard electrode survey through the same section in a neighboring well. The porous zones, which show up as low resistivity breaks on the guard electrode log, are completely masked by adjacent bed effects and boundary anomalies on the conventional curves. Even the short normal shows most of the porous Zones only as Vague deflections and in many cases fails to register Their

Jan 1, 1955

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.' Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.' Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By W. W. Eckles

This paper is presented as a suniniary report of the use of well gas composition correlations obtained from mass spectrometer recordings as a means of identification and determination of reservoir continuity. Conventional methods for detecting composition differences are en-pensive, elaborate, and difficult to obtain. This excludes the use of extensive composition data for most applications. During recent years the mass spec-trometer has come into general use as an analytical tool in petroleum refineries. The use of mass spectrometer composition patterns ir~ characterizing or "finger-printing" the produced gas from a reservoir, presents a novel method for correlatitlg gas samples from well to well. The mass spectrometer provides a trace similar to an electric log. having peaks which represent the abuntlnnce of certaitz hydrocarbons in the well gas sample. Without going further into the detailed analysis the idea has been advanced that these traces or patterns could be used as a means of identifying a particular natural gas. This theory has proven to be essentially correct. The mass spectrometer pattern method is simple and cheap as COi?7pared to other standard methods. It greatly facilitates the solution of reservoir and geological problems in which correlation of well gas Com-positions is a factor. Specific field applications have been made. This paper concerns the results obtained in 465 individual gas analyses from 35 fields and 77 res- ervoirs. In a number of cases it has been found that such data have been extremely valuable in the determination of reservoir continuity. In at least one case, the method was a valuable contribution in tracing a reservoir from sand to sand in a coinplex fnulted field involving n11rnerous gas reservoirs. Field applications are presented to illustrate the possibilities of the method at the present stage of developnient and to stimulate the ernployrnent of this new approach by geologists and petroleum engineers in the industry. INTRODUCTION Identification of producing horizons and the determination of reservoir continuity are often a problem in those areas where dome structures and highly faulted sands are encountered. To complicate the picture further, there may be numerous sands, one on top of the other which dip and diverge in different directions. Even though it may be possible to develop some solutions to the preceding problems on the basis of the geological and reservoir data on hand. it is readily recognized that substantiating data based on independent methods would he extremely valuable. It has been found through field studies that correiation of well gas composition can be used to advantage in the geological and engineering study of a complex reservoir identification problem. METHOD FOR COMPARISON AND CORRELATION OF WELL GAS SAMPLES Since a large number of well gas samples are required in a gas identification or reservoir con- tinuity problem, it is necessary that a method of analysis be employed which can detect differences in composition readily and inexpensively. Although detection would be possible by means of low temperature fractional distillation (POD) analpsis, the method requires a relatively large sample and is comparatively slow and expensive to run. The mass spectrometer affords an inexpensive and precise analysis of small well gas samples taken at the surface which are about 1/300 as large as a POD sample. These samples can be obtained by regular field personnei and shipped to the spectrometer for analysis. It is, therefore, a practical approach to the problem. A typical record from the mass spectrometer is illustrated in Fig. I. The peaks on the record represent the abundance of ions produced from the different hydrocarbon molecules making up the gas sam-ple. In well gas comparisons only five peaks are employed, since the other peaks are formed from the same gas molecules and furnish no additional information. The five peaks used represent the abundance of methane, propane, ethane, butane and heavier, and oxygen. They are referred to respectively as the 16, 29, 30, 43, and 32 peaks. The oxygen peak is used to correct for air content in

Jan 1, 1958

By G. Kraemer, J. A. Le Gac, P. R. ZETTWOOG

I. INTRODUCTION During the course of our activities in assisting mining companies, we have had access to the monitoring results for personnel from a large number of uranium mines. The results differ greatly from one mine to another. One of our objectives has been to discover the origin of these differences. It is evident that they are largely due to variations in the geological context, to mining methods, and to the organization of the work ; but we also found that the rigor with which measures are implemented to prevent the personnel from being exposed to radiations is also a cause. In order to advise mining operators effectively, we have asked ourselves the following question Given the dosimetric results of a mining site, how can it be known - if occupational exposure has been reduced to the lowest possible level (dose optimization principle recommended by the ICRP) ; - if the exposures were justified, which would not necessarily be the case following a questionable choice of the mining method, for instance, or a lack of efficiency in the maintenance and repairs of ventilation apparatus or even an excess of radiation protection. It is necessary to establish some criteria, while taking into consideration the specific conditions for each mine, in order to determine whether a mining company is adequately implementing radiation protection procedures. This need led us to attempt a modelization of the occupational exposures of uranium miners ; the preliminary phase is presented here. Although voluntarily still very basic, this model makes it possible to demonstrate the role of certain dynamic or passive variables. Moreover, the model presents the concept of specific irradiation of a mining site equal to the collective dose received per ton of uranium metal supplied to the uranium mill. The specific irradiation can therefore be used to indicate the effectiveness of radiation protection procedures at a given mining site. This model can be used for - previsional exposure studies based on the use of data gathered at each site, making it possible to compare various work methods and to determine prevention means ; - qualification of "radiation protection" procedures at a mining site ; - detection of unjustified exposures ; - research of ways to reduce inevitable exposures. 2. DETRIMENT TO BE ASSOCIATED WITH A GIVEN EXPOSURE DISTRIBUTION Respecting exposure limits ensures that delayed stochastic effects are the only health risks to workers. If the hypothesis of linearity in the dose-effect relationship is applied, the detriment to a group of workers is proportional to the sum of exposure for all the workers, or the collective exposure usually expressed as man x rem. On this point the linearity of effects hypothesis makes it possible to consider that two different standard deviation distributions having the same mean value are equivalent. It would be possible, then, to reduce the standard deviation by changing the distribution of workers at the various working places without changing the mean exposure value. In other words, without taking into consideration the practical implications, individual limits can be respected by rotating the personnel or by reducing the individual working period which would be compensated by increasing the number of workers. The collective dose would remain the same, which would justify the use of the concept of collective exposure. 3. "RADIATION PROTECTION" QUALITY INDEX AT VARIOUS MINING SITES Each mining site is responsible for its own collective dose, but it is also responsible for producing a certain amount of uranium metal in the ore sent to the uranium mill. These two quantities must be brought together in order to establish the "radiation protection" quality index of a mining site. This quality index, called-specific irradiation (Ir) is expressed in rem.ton -1 for external irradiation, in mJoule.ton-1 for inhaled [a]-energy, and in Ci.ton -1 for inhaled radon *. The specific irradiation represents the health hazard which must be associated to the extraction of one ton of uranium metal. Figures la and lb present a system of coordinates for which the axis of the abscisses is graduated in tons of U metal and the axis of the ordinates is graduated in units of collective exposures. In the EEC, the regulation is based on the measurement of the amounts of radon 222 inhaled.

Jan 1, 1981

By G. W. P. Rengstorff, H. B. Goodwin

A method is described for purifying iron in batches of 150 Ib or more. Oxygen, carbon, nitrogen, and sulphur are removed from flakes of electrolytic iron by treatment in wet and then dry hydrogen. A special consumable-electrode arc furnace is used to remove hydrogen and to melt the flakes into ingots. A LTHOUGH iron and steel have been made and used for hundreds of years, there are still wide gaps in the knowledge of these metals. One reason for this is that the true properties of the base metal, iron, are not well known, simply because really pure iron has never been readily available for research purposes. Commercial iron, and even the "pure" irons which are readily available, are really complex alloys of iron with oxygen, nitrogen, hydrogen, carbon, sulphur, silicon, and other elements. With such materials, it has not been possible to prepare steels and other iron-base alloys in which all elements are present in exactly controlled amounts. It is an almost impossible task to determine the separate effects of each element or the intereffects of several elements unless alloys can be prepared containing only the desired elements. The ability to make controlled alloys of low impurity content is of far more than academic interest. It will assist in the study of such practical problems as the brittle failure of ship hulls or high pressure gas pipelines, determination of the factors which affect the deep-drawing properties of steels, the improvement of magnetic and electrical properties, the phenomenon of aging, and many others. In 1949, the American Iron and Steel Institute asked Battelle Memorial Institute to prepare high purity iron on a larger scale than had been attempted up to that time. The work was directed toward the preparation of iron as low as possible in carbon, oxygen, nitrogen, hydrogen, and sulphur because these are the contaminating elements of major interest in many research investigations on iron-base alloys. The initial goal was to prepare iron with not more than a few thousandths of one percent of each of these impurities. The purpose was to set up a "bank" of high purity iron on which researchers could draw when a supply was needed and which could be replenished from time to time as the stock became depleted. Of several possible purification methods, heating in hydrogen was selected as the most promising for the removal of both carbon and oxygen from solid iron. Metallic impurities are not removed by hydrogen. Electrolytic iron was chosen as a starting material because it is the most readily available form of iron low in metallic impurities. Decarburization and desulphurization were obtained by annealing in wet hydrogen at relatively low temperatures. The optimum temperature, as found by previous investigators,' is about 1400°F. This treatment also removes nitrogen. Deoxidation is favored by dry hydrogen and higher temperature. There is evidence from previous work that an anneal at 2200°F in dry hydrogen will deoxidize the iron, reduce the nitrogen content, and reduce the sulphur content. These facts suggested the use of a two-stage process: treatment in wet hydrogen followed by treatment in dry hydrogen. To carry out the purification process in a reasonable time, it was necessary that the iron be in thin pieces. Flakes of electrolytic iron were used. Because most research requires that the iron be in massive form, it was nccessary to melt the purified iron to consolidate it into large pieces. For this work, it was decided to prepare ingots weighing at least 15 lb by using a cold hearth arc-melting process in which the iron was melted in an inert atmosphere of argon or helium. This method of melting was selected because the water-cooled copper crucible is not wet by the iron and does not contaminate it as a refractory crucible would. Because the crucible is also the ingot mold, contamination from mold materials was also eliminated. Contamination from electrodes was avoided by making them from purified electrolytic iron. The melting procedure finally developed was an adaptation of the Kellogg electric ingot process.' Two batches of purified iron weighing about 100 Ib each in ingot form were prepared with analyses as shown in Table I. The remainder of this paper describes the procedures in more detail. In general, the process con-

Jan 1, 1956

MEMBERSHIP In terms of By-laws7.7.1 members are hereby notified that the membership of the following has been cancelled and their names removed from the Membership Register: H. Digby Roberts, R. J. P. van Tonder, S. D. Williams (Members), A. I. de Klerk, M. F. Ford, A. W. Hine, H. A. Johnston, R. T. Joyner, H. D. Small, P. White (Associate Members), J. de F. Agrella, A. Leibowitz (Affiliates), J. P. M. Maidment, C. P. J. M. Steyn (Graduates), H. C. M. Fourie, B. C. P. Job, J. P. Kruger, E. C. Nicolas, A. P. Prinsloo, B. Schuitema (Students). INSTITUTE PUBLICATION Transactions of the Seventh Commonwealth Mining and Metallurgical Congress Requests are still being received by the Institute for sets of the above transactions. Members who wish to dispose of sets in good condition are requested to contact the Secretary, P.O. Box 1183, Johannesburg or 304 Kelvin House, Johannesburg. As these are for resale a price of not more than R10.00 can be offered per set of three volumes. INTERNATIONAL SOLVENT EXTRACTION CONFERENCE, 1971 The Society of Chemical Industry has agreed to sponsor an International Conference devoted to the science and technology of solvent extraction. This will be held in The Hague in the Netherlands during the week commencing 19th April, 1971. The organisation of the Conference will be in the hands of a Conference Committee under the chairmanship of Mr B. F. Warner. The emphasis of the Conference will be on technical solvent extraction of both inorganic and organic substances, including basic principles and practical applications. Sessions are envisaged covering the chemistry of solvent extraction, industrial processes and economics, the performance of contacting equipment and the underlying phenomena involved, and the response characteristics and control of such units. The Conference Committee will welcome offers of papers for presentation at the Conference. In the firts instance, intending authors should submit a preliminary title and an indication of the scope of their contribution to the Conference Secretary: Dr. C. Hanson, University of Bradford 7, U.K. It is hoped to have available in September a first circular giving further details of the Conference. Copies may be obtained from: International Solvent Extraction Conference, 1971, 14, Belgrave Square, London, S.W.1. SOUTH AFRICAN TUNNELLING CONFERENCE TO BE HELD IN 1970 A South African Tunnelling Conference, to be known as TUNCON 70, is to be held in Johannesburg during the latter half of July, 1970. South Africa, in common with other countries, has a vital and growing interest in tunnelling. Apart from the 800 kilometres of tunnel excavated annually in the gold mines, the 82 kilometre-long Orange-Fish Tunnel is being driven to carry water from the Orange River to the drier areas of the Eastern Cape Province. This and the realization that services such as water and transport are increasingly being carried underground in various parts of the world have emphasized the need for a forum at which the technology and potential of tunnelling can be discussed. TUNCON 70 is being supported by three professional engineering societies representing some 6,000 engineers, namely, the South African Institute of Mining and Metallurgy, the South African Institute of Civil Engineers and the South African Institution of Mechanical Engineers, as well as by the Geological Society of South Africa. The conference has three main purposes. Firstly, to pool and exchange expertise by authorities on tunnelling; secondly, to discuss future developments in tunnelling technology with the aim of making those concerned with long-term planning aware of the potentialities of tunnelling; thirdly, to propose standards for tunnel shapes and sizes. Adoption of standards for tunnelling equipment and accessories would be a major step forward in improving tunnelling efficiency. The five themes of the conference will be: tunnel utilisation, exploration, design, construction and standards. The conference will be held at the University of the Witwatersrand, Johannesburg, from 21st to 24th July, 1970. Arrangements will be made for visits to be paid to mines and tunnelling projects before the start of the conference. Further information is obtainable from the Organising Committee, TUNCON 70, P.O. Box 1183, Johannesburg, South Africa.

By George S. Rice, W. L. EGY, H. P. Greenwald, L. M. JONES

CHAPTER I. INTRODUCTION AND SUMMARY. BY GEORGE S. RICE. PREFATORY STATEMENT. This bulletin describes the second series of coal-dust explosion tests conducted by the Bureau of Mines in the experimental mine near Bruceton, Pa. It covers a period from 1913 to 1918, inclusive, of more or less consecutive testing, during which many important conclusions were drawn regarding the way a coal-dust explosion may originate, the mechanism of an explosion, and the methods of pre- venting explosions and of limiting incipient explosions. The manuscript was prepared in 1918, but its publication had to be put aside during the World War for more pressing publications and it was not until this fiscal year 1922 that funds could be allotted for its printing. Meantime the general facts concerning methods of preventing explosions have been made known to the mining industry, with great advantage, it is believed, as explosions of coal dust in mines in the United States have become infrequent. This fact, however, must not lull the consciousness of mining men to the terrible potential danger that lurks in untreated coal dust. The experiments described in this volume should be of aid to them in planning to keep the ever present coal dust in an innocuous condition. The first series-reported in Bulletin 56, "First Series of Coal-Dust Explosion Tests in the Experimental Mine"-included only pre- liminary tests of the ability to start explosions of coal dust under the conditions in the experimental mine. After this fact had been determined and several violent dust explosions had been demon- strated before large audiences of mining men, the work had to be suspended in order that necessary repairs and extensions might be made in the fall and winter of 1911-12. Although the question of the possibility of coal dust causing explo- sions had been considered for more than a century, and much testing in laboratory apparatus and in small surface galleries had been done, coal-mining men generally did not believe that coal dust was explo- sive and considered that fire damp or gases of unknown composition were responsible for the mine explosions that had cost thousands of lives in the various coal-mining countries during the last century. As coal mines increased in number, size, and depth, explosions became alarming in their frequency. Finally came the Courriéres disaster in northern France, 1906, by which 1,100 lives were lost, and the following year in this country, the Monongah mine explosion, in West Virginia, which killed 361 men, and the Darr explosion, in Pennsylvania, which killed 239 men. These two disasters, both in December, 1907, led Congress to make an appropriation for an in- vestigation of the causes of mine explosions. The funds became available July 1, 1908, and the work was placed under the United States Geological Survey's technologic branch, with the late Dr. Joseph A. Holmes in charge. Before undertaking the investigations Dr. Holmes visited Europe, accompanied by the senior author of this bulletin, to study the methods foreign countries used to prevent mine explosions, to obtain details regarding tests being made in several countries, to procure safer explosives and better safety lamps for use in gaseous and dusty mines, and to study the methods used in coal-dust explo- sion tests in the recently completed galleries at Altofts, England, and Liévin, France, and in the older galleries at Gelsenkirchen, Germany, and Frameries, Belgium. At all of these stations the explosions tests were made in surface galleries. The Austrian gallery at Segengottes, near Brünn, Moravia, visited by the writer in 1911, is an underground gallery, but the testing done in it was limited, dealing with ignition of coal dust rather than with propagation. Although the results obtained in the foreign galleries had indicated that coal dust was explosive, mining men in the respective countries were of the opinion that the dust would not explode under mine con- ditions. This situation led Dr. Holmes to the conclusion that testing must be done in a real mine, to make certain that the conclusion would be reliable and would be accepted by the mining public as decisive.

Jan 1, 1922

By John A. Davis, Karl L. Kithil

The principal deposits of carnotite, so far as now known, are con- fined to a well-defined area lying in the southwestern part of Colo- rado and the southeastern part of Utah (see Pl. I). Approxi- mately, this area is bounded as follows: On the east by a line ex- tending from a few miles east of the southwest corner of the State of Colorado, to a point about 6 miles west of Naturita, thence di- rectly north to the San Miguel River, thence along the course of this river and the Dolores River to Mesa Creek, thence toward the head- waters of Mesa, Blue, and Calamity Creeks on the south side of the Uncompahgre Mountains; on the north by a line extending from the last-named point westerly to the San Rafael Swell near Green River, Utah; on the west by a line extending from San Rafael Swell to the Henry Mountains, and on the south by a line extending from the Henry Mountains toward the southeast corner of the State of Utah. This area includes the main districts wherein carnotite has been found, claims have been located, and the ore produced. There are of course, extensive tracts within this area which do not contain carnotite in paying quantities. In places the carnotite beds have been entirely eroded or are not present, or lie so deep that mining is not practicable. The main deposits of carnotite within the area lie in different districts which in Colorado are as follows: Summit and Bush Canyons in Dolores and San Miguel Counties; McIntyre, Gypsum Valley, and Bull Canyon districts; the Paradox Valley, La Sal Creek, Roc Creek, Long Park, Hieroglyphic, Saucer Basin, and Hydraulic districts in Montrose County; Mesa, Blue, and Calamity Canyon districts and the Gateway area in Mesa County. The included dis- tricts in Utah are as follows: The Green River and San Rafael Swell district in Garfield County; the Thompson deposits in Grand County; the Dry Valley, Yellow Wash, and Lisbon Valley districts in San Juan County; the district around the Henry Mountains in Garfield County; and the deposits recently reported in Montezuma Canyon (south of Monticello) in San Juan County. Outside of the area described there are scattered deposits north of the Denver & Rio Grande Railroad at Coal Creek, near Meeker, Rio Blanco County; along Skull Creek and Red Wash, near Rangely, Routt County; on Horse Mountain, near Eagle, Eagle County, and in South Park, near Garos, in Park County, Colo. The claims leased from the Crucible Steel Mining & Milling Co. by the National Radium Institute are situated on the north side of East Paradox Valley, in the Long Park and Hydraulic districts. The National Radium Institute has mined no ore except from its leased claims in the Long Park district. For information regarding the general geology of the region, the probable origin of the ores, and descriptions of other carnotite deposits, the reader is referred to the literature on these subjects. The carnotite of the area described is deposited in a light-colored, cross-bedded sandstone that lies almost horizontal between the La Plata formation below and the Dakota sandstone (conglomerate) above, and is included in the McElmo formation, which is of Jurassic age. Underlying the white sandstone of the La Plata is the Dolores formation, or "Red Beds," which is plainly visible along and just below the rim rocks of the steep canyon walls in many of the carnotite districts. Along such canyons the ore crops out at different places, so that prospecting is comparatively easy. For ore on the benches and on the mesa prospecting is more difficult, especially where the ore lies at some depth and no surface indications are visible. The carnotite deposits are flat, lenticular, and irregular, varying greatly in extent and thickness. The carnotite itself forms incrustations on exposures of the white sandstone, in joints and fractures of the rock, and is deposited around and between individual sand grains, replacing the original cement. The Utah and Colorado carnotite is amorphous, and to the naked eye appears as a very fine yellow pow- der. It is often granular, and as a rule can be readily separated from the individual sand grains.

Jan 1, 1917

By C. A. Allen

In presenting a summary of the uses of fine and pulverized coal the writer has borne in mind that we are not trying to determine what a combustion engineer should know but we are only trying to find out in what ways the consumption of slack can be stimulated. First discussing the use of powdered coal it can be stated that it has passed the first experimental stage but is still capable of much development and improvement. It has already found successful application in stationary and locomotive boilers, cement kilns, calcining furnaces, reverberatory smelting furnaces and many other types of furnaces, such as open hearth furnaces and annealing furnaces. For stationary boilers it seems to have been thoroughly demonstrated that powdered coal is more efficient than stoker installations. Over-all efficiences of boiler and furnace in stoker installations of the best type run from 70 to 76 per cent; whereas the efficiency of powdered coal installations averages slightly over 80 per cent. However, due to the increased cost of pulverized coal, the increased efficiency of these installations over stokers, from a money stand-point, will not be more than 1 or 2 per cent. The fusing of the ash in pulverized coal installations has given some trouble but apparently is easily overcome, on the other hand the fine ash, which is carried along with the draft, causes trouble both in the boiler and by settling on surrounding buildings or ground. Offsetting the disadvantages the great advantages of pulverized coal for stationary boilers seem to be: First-the ease with which a change in the load on the boiler can be taken care of. Second-when a boiler is cut out for a short period the "stand-by" losses are much less and, Third-a much poorer grade of fuel can be used. In many cases where pulverized coal has been used it has replaced slack coal which is of little advantage to the coal operator. However,, in other places it has replaced gas or oil and this is where the coal man is interested. Pulverized coal has the same advantages as the liquid or gas fuel but the question as to which is preferable depends on their relative cost at the point of use. In small stationary boilers where stokers are not used, very frequently the larger sizes of coal are, and it would be an advantage to the coal industry for them to be converted so as to burn pulverized coal, but so far there are only records of a few of such small installations having been a success and there is apparently room for a large amount of experimentation. In furnaces, such as smelting and assaying furnaces, annealing furnaces, etc., slack coal is not used and where pulverized coal has been installed it nearly always replaces fuel oil or gas. Just how much increased consumtion of coal can be made by pulverizing it for use in furnaces of this type can not be determined but it seems worthy of investigation. For locomotive boilers pulverized coal has found some application up to date but where it was being used in the United States it was stopped when we entered the war. In Brazil, however, the Central Railway has been using pulverized coal for locomotives with excellent results. If it could be possible to apply it to locomotive use where fuel oil is now used, or the larger sizes of coal, it would certainly make a big difference in the slack situation. Now as to the uses of slack coal without pulverizing. The writer's investigations lead him to believe that the greatest opportunities in this direction are in the line of increasing its use by apartment houses and small home owners. In fact in looking into the subject I found that a number of men in Salt Lake City are using run of mine coal in the usual type of house furnaces, some of them by separating the fines and wetting them down before feeding to the furnace claim they get no loss whatever through the grate. However, for best results with fine coal different types of furnaces must be installed and for apartment houses it would seem necessary to have either a small automatic stoker or else spray the fine coal in with an air blast from

Jan 1, 1922

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct'" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct'" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By Árpád B. Palotás, Adel F. Sarofim, John B. Vander Sande, Paolo Ciambelli, Lenore Rainey

"The evolution during oxidation of the internal structure of soot and carbon black particles was studied using high-resolution transmission electron microscopy (HRTEM) and an image analysis system. Increasing ordering to the carbon structure with increasing oxidation is observed. Measures of the increased order are increases in the fractional coverage of a cross section of the particles with a layered structure, a decrease in the mean interlayer spacing, and a decrease in the spread of the interlayer spacing. The changing structure of the carbon black impacts its properties, such as the rate of oxidation.There is considerable interest in the study of the structural changes of carbonaceous materials as a function of oxidation. Davis et al.1 measured the variation of carbon dioxide surface area of various coals as a function of residence time in a flow reactor. HRTEM measurements revealed that crystallite dimensions and interlayer spacings are altered by combustion. Ishiguro et al.2 showed that oxidation alters the structure of diesel soot. The aim of our current research is to develop a better understanding of the microstructural reordering of carbon blacks with implications to their properties. The carbon blacks used in this research have already been studied and their reactivities as a function of oxidation measured.3The methodology used in this work has already been described in detail elsewhere.4 This paper presents an application to quantify the structural changes of carbon black particles as a function of oxidation and graphitization. The technique used is based on the use of HRTEM (high-resolution transmission electron microscopy) and computational image analysis.It is well-known that carbonaceous materials like graphite, soots, coals, chars, etc., possess characteristic structural appearances which can vary from mostly random or amorphous to a perfectly ordered graphitic crystalline structure. The carbon structure has been variously described as turbostratic5 or as crumpled sheets6 to indicate that parallel layering, reminiscent of graphite, is observed over dimensions of nanometers but that these planes or crystallites show disorder over larger scales. The degree of order of such structures is strongly dependent on the thermal treatment of the material as well as the composition of the source of the carbonaceous material. The value of electron micros¬copy in studying the morphology of such materials has been well established,2,7,8 although only a few attempts toward quantification have been made.The sample observed was carbon black CB330 from De¬gussa. One set of carbon black samples were oxidized in a thermo-gravimetric analyzer (TGA) in air at 575 0C, so that the conversion varied from 0 to 96%. Another set of carbon black samples were graphitized (Graphpac-GB by ALLTECH) and then oxidized in the TGA at 680 °C until 92% burnout was reached. The latter samples are called GB 0% and GB 92%, respectively.For the HRTEM observation a small portion of each sample was ultrasonically dispersed in ethanol. The suspension was deposited dropwise on a copper TEM grid coated with a lacey carbon film. The examination of the samples was carried out on areas that extend over the holes in the supporting film in order to avoid interference from the amorphous carbon background film An oriented gold crystal was used as a calibration standard and subjected to the same techniques as the carbon black samples."

Jan 1, 1998

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962