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By H. D. Outmans

The paper presents a theoretical approach to the drilling problem based on rock mechanics and drilling fluid hydraulics at the bottom of the hole. The volume of the fractured rock around the vevtically penetrating bit tooth is expressed as a function of the tooth pressure, included tooth angle, drilling fluid pressure and formation characteristics on the assumption that fracturing is preceded by plastic flow. This assumption is verified by comparing the stress-strain state in the rock around the tooth to that in equivalent tri-axial compression tests described in the literature. An expression similar to the above is derived for the tooth penetration in the cuttings which have been retrained at the bottom. Combination of these two expressions leads to a relation between depth of tooth penetration in the virgin rock, the amount of cuttings retained and the other variables. By relating the cutting volume to the drilling rate, the hydraulic bit horsepower and the drilling fluid pressure, it is possible to arrive at formulas which express the drilling rate for viscous or turbulent flow at the cutting surface, for instant clearance, for retained cuttings, or for false tooth foundering as functions of such variables as the drilling fluid pressure, hydraulic horsepower at the bit, rotary speed and bit weight. Plotting the results as drilling curves and comparing them to published field and laboratory data justify the conclusion that the drilling model presented in this paper approximates the actual mechanism. The drilling curves serve to explain some characteristic features of the rotary drilling operation, and the equations may be used for numerical evaluation of the effect of changes in the magnitude of some of the variables on the drilling rate. INTRODUCTION Published laboratory data have established that consistent and relatively simple relations exist between the drilling rate and any one of the important variables. For instance, the drilling rate usually increases at an increasing rate with the bit weight. It increases at a decreasing rate with the rotary speed, decreases at a decreasing rate with increased drilling fluid pressure and plots as an S-shaped curve against the hydraulic horsepower at the bit. This relative simplicity seems difficult to understand considering that the drilling mechanism is a continuous process of generation and removal of innumerable individual cuttings, under different conditions for each. On the other hand, the drilling rate (although determined by this complicated process) only expresses the average rate at which cuttings are produced and cleared away. Ignorance of the drilling mechanism as far as individual cuttings are concerned, therefore, does not exclude the possibility of arriving at a concept of the drilling rate provided the mechanism is properly evaluated for the average cutting. It then may be concluded from the first sentence that this concept also should be rather simple in its final form, although not necessarily in its derivation. Two aspects of the drilling mechanism are difficult to evaluate — (1) the effect a penetrating drilling fluid has on the stresses around a bit tooth entering the formation and (2) the volume of rock fractured by a penetrating tooth which moves both vertically and horizontally. Thus, the scope of this paper has been limited to an evaluation of the drilling mechanism in formations which have a low permeability and are drilled with hard-formation bits. In the following sections, the drilling mechanism is analyzed in three steps. First, the effect of tooth pressure on the volume of fractured rock around the tooth is evaluated, assuming initially that the bottom of the hole is free of cuttings and, then, determining the effect of a layer of these cuttings. In the second section, the thickness of this layer is related to the drilling rate and the chip clearance time, and the latter to the hydraulic horsepower at the bit under conditions of laminar and viscous flow at the cutting surface. In the third section. the previous results are combined with the rotary speed into drilling equations which are then plotted and compared to experimental drilling curves. This section also contains some numerical examples of drilling rate computations. Some mathematical details are given in the appendixes. Finally, it should be mentioned that, although some drilling equations are already available, these equations (with the exception of one' which attempts to relate drilling rate to drilling fluid pressure) are all mathematical expressions for observed laboratory data; none considers the effect of delayed drill-cutting removal, an essential feature of the drilling mechanism.

By N. H. van Lingen

A laboratory stud], has been made to determine what factors affect the penetration rate of roller bits, diamond bits and drag bits in rock drilling with clay /water muds. The rather simple relations that exist when pressures in and around the borehole are equal become more conzplicated when under down-hole conditions the penetration rate is hampered by the existence of a pressure differential between the mud at the hole bottom and the pore liquid at cutting depth. Expressions that have been derived for both the penetration rate and the magnitude of the pressure differential in permeable rock together fully account for operating, rock, mud and bit variables. In impermeable rock a similar pressure differential is caused by the bit action itself. In all cases, the pressure difierential and the reduction in penetration rate increase with the effectiveness of the plastering at the bottom of the hole by mud particles. Where bits are employed whose action is largely that of crushing, however, the plastering may become even more effective owing to the addition of rock particles rubbed into the pores of the rock. With roller bits, a plastically hehaving layer may be formed, which causes a further reduction in penetration. In the case of bits whose action is chiefly scraping, moreover, penetration may be arrested by the bit's becoming balled-up. The various adverse effects are reduced by thorough scavenging of the hole bottom. This paper shows how with jet bits the efficiency of such scavenging may he improved by suitable choice of the position of the nozzles. INTRODUCTION The reduction in a bit's penetration rate with increasing depth of hole has been the subject of many investigations. Various investigators ',' have independently reached the conclusion that this reduction occurs not so much because the rock-breaking process becomes more difficult as it does because the lifting of the rock fragments is impaired by a fluid pressure differential holding the fragments down. When such a pressure differential can be avoided, as in air drilling and to a smaller extent in water drilling, penetration rates remain high. Although the range of applicability of these techniques is being extended, most oil wells still have to be drilled with mud. In this paper we present the results of laboratory experiments carried out to determine what factors govern the hold down effect encountered in mud drilling. In the course of this investigation, the well known importance of bottom scavenging came more and more into prominence. Not only may it reduce the magnitude of the hold-down forces, but also it appeared to be a means of preventing the accumulation of a plastic mass of cuttings and mud on the hole bottom and bit which may cause penetration to cease almost completely. So that the effects of fluid pressures may be more readily understood, the factors that govern penetration rate in the absence of these pressures will first be discussed. The effect of down-hole pressures will then be assessed for the case of permeable rock where fluid pressures are well defined, and it will be demonstrated how rock strengthening due to confining can be accounted for. Subsequently, fluid pressures in less-permeable rock will be examined; we will show that in impermeable rock it is the bit action that governs fluid-pressure distribution and hold-down. In the case of poor scavenging and/or high bit load. cutting cake manifests itself. The effect, like various others. appears to depend on the type of bit used. From the very beginning, therefore, we shall base our discussion on the three main types of bits used in rotary oil-well drilling— roller bits, diamond bits and drag bits. Since space is limited, it will be impossible to make more than a passing reference to many aspects of the problem. Moreover. certain relations that are not of primary irnportance to our argument will unavoidably have to be stated in a somewhat dogmatic fashion, and the experimental data on which these are based necessarily must be omitted. EQUIPMENT The drilling experiments were performed on three machines, of which one has been designed for the realistic simulation of down-hole pressure conditions. HIGH-PRESSURES MACHINE In this machine (diagramed in Fig. 1) the mud, pore and confining pressures can all be adjusted independently. The foil-covered rock sample contained in the inner pressure vessel is confined by oil that is pressurized by means of a hand pump. The pore space of the watersaturated sample is connected to an arrangement which keeps the pressure in the pore space constant regardless of the rate of filtrate flow through the sample.

By M. A. Goudie

The deposits occur in a large salt basin of Middle Devonian age. The potash, the final deposit in the salt basin, results from several interrupted cycles of evaporation and dessication. The deposits are extensive, and, at first glance, relatively undisturbed. With more and more wells being drilled, it has now become evident that salt solution has played a large part in changing the original deposits, resulting in some cases in partial to complete removal of the potash and the underlying halite. The most dominant factor in the removal of salt by solution appears to have been tectonic movement and consequent faulting, probably of relatively minor dimensions but of major importance. Evidence which indicates the tilting of the evaporite basin to the north and northwest is shown by the changing pattern of the basin during succeeding eras of potash deposition. The potash minerals of most importance economically are sylvite and carnallite. Reserve calculations indicate that 6.4 billion tons of recoverable high grade potash in K2O equivalent exist in the basin. The Devonian salt basin, which contains the Saskatchewan potash deposits, extends from just east of the foothills in Alberta, north as far as the Peace River area, across Saskatchewan and into Manitoba as far east as Range 10 west of the First Meridian and south into Montana and North Dakota (Fig. 1). The basin is closed everywhere except to the northwest. The known potash deposits are confined almost entirely to the Province of Saskatchewan, with the exception of a small area in western Manitoba bordering the Saskatchewan boundary. The following discussion will concern only the Saskatchewan part of the basin. The evaporite series in the basin is defined as the Prairie Evaporite Formation of the Elk Point Group, of Middle Devonian age. Recent work done by potassium-argon dating methods has indicated an Upper Middle Devonian (Givetian) age of from 285 to 347 million years for the potash. The Elk Point Group consists in ascending order of the Ashern, Winnipegosis, and Prairie Evaporite Formations. The Ashern formation, with an average thickness of 30 ft, sometimes called the Third Red Bed, consists of dolomitic shales and shaly dolomites. The Winnipegosis, is a reef-type dolomite, usually with good porosity, and in many cases oil-staining, although to date no production has been obtained. The thickness varies from 50 to 250 ft. The Prairie Evaporite formation, varying from 0 to 600 ft in thickness, consists of halite with interbedded anhydrite and shale, with considerable amounts of potassium salts in the upper part of the formation. The potassium salts are chiefly chlorides, although very minor occurrences of sulfates have been re- ported. The anhydrite beds do not appear to be continuous, although generally one or two bands of anhydrite underlie the lowest potash zone and are used as marker horizons. The shale occurs as seams interbedded with the salts, as large irregular inclusions in the salts and as very fine particles in intimate mixture with the salts. The Prairie Evaporite Formation is overlain by the Second Red Bed member, the Dawson Bay Formation and the First Red Bed Member of the Manitoba Group, listed in ascending order. The Red Beds are shales which vary in color from red to green, maroon, grey, grey-black, and reddish purples. They serve as marker horizons for coring the potash. The Second Red Bed averages 14 ft in thickness, the First Red Bed 35 ft. The Dawson Bay Formation, which everywhere overlies the First Red Bed and the Prairie Evaporite Formation in the area under discussion, is a reef type of carbonate, in some places limestone, in others limestone and dolomite, with vugular to pinpoint porosity averaging 130 ft in thickness. In some parts of the area, it has a salt section near the top of the formation, usually with interbedded shales and limestones. In other parts of the area, it is waterbearing and the salt is absent. Detailed mapping has indicated that the areas in which the Dawson Bay is water-bearing are areas which have been disturbed by faulting. Where the Dawson Bay is salt-bearing, the porosity has been plugged by salt. The total thickness of the salt varies from between 600 to 700 ft in the center of the basin to zero at the northern edge of the basin (Fig. 2).* The salt-free area in the center of the Province is believed to have resulted from removal of salt by solution. Evidence from several wells suggests that salt removal has been a continuing process from the time of deposition to the present day. One well drilled between the Quill Lakes for potash information encountered

Jan 1, 1961

By Lewis E. Dr. Young

MINING engineers in the United States understand that mining conditions in the British coalfields are much more difficult than in most of the mines now being operated in the United States. We realize also that in the near future we must face some of these same difficult problems. Early Mechanization The progress made in mechanical loading in the United States is the result of a long struggle in many coalfields to mine with power tools safely and to increase output per man-shift. Attempts to use power to loosen coal and to transport broken coal in the U. S. may be said to date from the Stanly Header, or Entry-Driver brought from England in 1888. The principle of this boring machine was used in the McKinlay Entry-Driver, almost continuously used in the U. S. since 1920. Since 1888 experimental loaders, scrapers, and conveyors were installed with more or less success. Beginning in 1918, considerable progress was made with mobile loaders, and in 1920 the first wage agreement for the operation of mechanical loaders was made in Indiana. In 1923 the Pocahontas Fuel Co. loaded nearly 1 million tons of coal using 23 Coloders. Labor Policy The United Mine Workers of America have never officially opposed the Mechanization movement. On December 10, 1945, in a statement before the House of Representatives Labor Committee, John L. Lewis said, regarding the policy of the United Mine Workers of America: "We have welcomed progress; we have welcomed machines. We have told our people that they had to accept that condition; that it was the process of progress, and that they would have to take their chances." Recent Development In 1951 about 71 pct of the tonnage mined underground was mechanically loaded. Over 4000 shuttle cars are in service and it is estimated that much more than half of the tonnage loaded underground is produced by trackless mining. In 1947 roof-bolting was introduced extensively and it is estimated that more than 2 ½ million bolts are now being used per month in about 600 mines. The use of roof bolts has permitted the more effective and safer use of loaders and shuttle-cars. Continuous Mining The McKinlay Entry-Driver could have been used for continuous mining, but for many years it was used only .for entry driving. In 1946 the Silver machine was developed in Colorado, and in 1947 this was acquired by the Joy Mfg. Co. and called the Joy Continuous Miner. Other types of combination mining-loading machines which eliminate drilling and blasting operations are the Marietta Miner, the Colmol, the Lee-Norse Miner, the Junior Miner, the Goodman and the Konnerth machines. There are several other types in the process of development. Probably by January 1953 there will be about 250 continuous miners in operation in the U. S. Payment of Mine Labor One of the most important problems in mechanizing was the establishing of rates of pay that would be attractive to the best men. Prior to the installation of mobile loaders the hand loaders and cutters have been paid by the ton. It was felt that a system of a day's pay should be established and that piece and tonnage rates should be abolished completely. Without exception, all coal loaded in mines equipped with mobile loaders is prepared and loaded by men paid an hourly rate. Trends in Mining Research There are two diverse approaches in coal production research; to try to design a mining machine to fit current methods, or to adapt mining practice to take advantage of proven machines. A great deal of credit must go to the mine operators who have been enterprising and dynamic enough to use available equipment intensively and to discard it as soon as an improved or new machine is available. Effect of Changing Markets Formerly there was an important demand for lump and prepared coal in the larger sizes for domestic use. The use of bituminous coal for house heating has decreased so that not more than 19 pct of the annual tonnage goes to retail trade, only 12 pct is used by the railroads, and much of the retail and most of the railroad coal is in stoker size. As a result of this decline in the market for coarse coal most of the large mining operations have crushers installed in the tipples or preparation plants. Mass production at the face requires increased preparation facilities. Another important trend is in connection with complete seam mining with mechanical loading. In many mines where the immediate roof is apt to fall with the coal no effort is made to separate roof material from coal prior to

Jan 1, 1952

By C. S. Smith, L. Guttman

It is shown, from a study of geometric probabilities, that the average number of intercepts per unit length of a random line drawn through a three-dimensional structure is exactly half the true ratio of surface to volume. Since the surfaces can be internal or external, the area of grain boundary or of the interface between any two constituents in a micro-structure can be measured. Other metric relations are tabulated that may be of use in studies of the microstructure of polycrystalline, cellular, or particulate matter generally. IN many fields of scientific investigation the structure of cellular aggregates or random arrays of discrete particles imbedded in some matrix is observed on a two-dimensional section and inferences are drawn therefrom as to the real structure in three dimensions. The biologist's microtome slice, the petrologist's thin section, and the metallurgist's plane polished and etched sections are common examples, although the problem is a general one. Scientists have commonly limited their thinking to the same dimensionality as their structures, and the few attempts that have been strictly three-dimensional in character have been laborious and noteworthy. From a metallurgical standpoint it is often of considerable importance to know, in addition to the volume fraction of two or more components in an alloy, the amount of two-dimensional interface between crystals. Such grain boundaries (which may separate either two identical crystals differing only in orientation or two crystals differing in structure, and possibly also in orientation) have a determining factor upon the mechanical behavior. It is at these boundaries that melting commences, that stress-induced corrosion occurs, and that various precipitates (harmful or otherwise) first appear. The boundary is doubtless of equal importance in nonmetallic crystalline aggregates such as rocks, ceramics, and concrete, and the biologist is deeply concerned with the area of cellular membranes. Many synthetic cellular foams involve similar structural problems. The very term structure usually implies the presence of interfaces and a complete understanding of structure involves nothing but an analysis of the geometrical, metrical, and topological relations between the various interfaces (zero, one and two-dimensional) that exist in a three-dimensional structure. Even systems lacking sharp physical interfaces often have interrelated gradients of composition or velocity (as cored crystals or turbulence cells) in which a neutral surface can be treated as a two-dimensional interface. In an earlier paper by one of the authors' the question of cell shape was considered in terms of simple topological principles without regard to physical dimensions. The determination of the actual size of grains in two dimensions is carried out in a routine fashion in innumerable metallurgical laboratories (see, for example, the ASTM standard methods of grain size determination2), though this is done merely to check the uniformity of a product and has no relation to the actual three-dimensional shape or size of the grains. Some authors have discussed the three-dimensional problem but only on the basis of assumptions as to idealized grain shapes.:'-' Quantitative measurements of microstruc-tures to obtain the volumetric relations of various phases have been carried out by petrographers for many years and are of increasing popularity among metallurgists." The present paper will show how, on the basis of no assumptions other than randomness of sectioning (usually realizable in experiment), it is possible to learn a great deal about the three-dimensional structure. The relations to be derived will generally be used on random arrays of cells or other particles, although they are equally applicable to ordered arrays and even to isolated objects of complex shape provided that suitable random sections can be made. Total Area of Interfaces in a Sample Consider a typical microstructure of a single-phase polyerystalline metal, such as that shown pres- in Fig. 1. The plane cross section shown contains a network of lines which subdivides the area into two-dimensional cells. The lines, of course, represent merely the intersection of the two-dimensional plane of sectioning with the two-dimensional interfaces between adjacent three-dimensional cells. The structure also contains points at which two or more lines intersect: in three dimensions the points are, of course, lines. In the more general case there may be in three dimensions isolated particles surrounded by a single interface without contact with others, and both two and one-dimensional features which do not necessarily connect with others. On the two-dimensional section these will appear as areas delineated by a closed line (as at a and b, Fig. 2), as isolated lines

Jan 1, 1954

By J. E. Hove

The high temperature physical properties of graphite are reviewed and interpreted in the light of present day knowledge of the mechanisms affecting these properties. The thermal and mechanical behaviors only are discussed and, whenever possible, comparisons are made with other refractory materials. Possible further studies are indicated, including some carbide work. AS long as the term high temperature implied only temperatures up to about 1000°C, the materials problems which arose could usually be handled by fairly conventional metal alloy types, such as the Co-Cr-Ni superalloys, for which there exists a great deal of technology. Perhaps this temperature can still be considered an upper limit for normal applications, but it is certainly true that the number of abnormal applications is increasing rapidly. The advent, in recent years, of ram-jet and rocket missiles and of high power nuclear reactor heat sources has raised a host of questions concerning the basic problem of what material to use in the temperature range up to 2000°C and higher. While there are, of course, many metals, in the second and third transition series, which melt at considerably higher temperatures than this, these metals are, at present, pretty well excluded from practical use by other considerations, such as re-crystallization, chemical activity, or excessive plastic deformation. The behavior of metals, from the standpoint of dislocation theory, is just beginning to be understood and thus there is some hope for the future development of very high temperature metals, but the immediate problems would most logically appear to have solutions involving the nonmetals, such as the refractory ceramics and graphite. For this reason, there is presently a great deal of engineering and experimental research being performed on the latter materials, much of this research being exploratory in the sense of gathering new property data. The situation, so far as graphite is concerned, is somewhat more fortunate than with the other refractory solids in the sense that a great deal is already known about its basic properties. This stems both from the fact that the carbon-carbon bond has been of interest to chemists for a long time (and graphite can be considered as a very large aromatic molecule, if desired) and the fact that its properties, both as a function of temperature and of radiation damage, are of critical importance to nuclear reactor designers. It is still true, of course, that such fundamental questions as why graphite remains solid to such a high temperature and why it has such a high thermal conductivity cannot entirely be answered at the present time. It is, nonetheless, meaningful and instructive to consider such problems in the light of existing knowledge. This is what the present paper will attempt to do. Before going on, it may be appropriate to classify graphite and justify its discussion before readers primarily interested in metals. Graphite is comparatively unique among materials in that there is always a property or group of properties which precludes calling it either a metal, a semiconductor, or a ceramic. It has the high electrical and thermal conductivities of a metal, but the artificial, poly-crystalline types show a negative thermal coefficient of electrical resistivity, generally characteristic of semiconductors. On the other hand, semiconductors, by definition, show an ever increasing resistivity as the temperature is lowered, whereas graphite approaches a finite, and, indeed, a rather low resistivity in the region of 10°K and, furthermore, a good single crystal of graphite has a positive temperature coefficient, as for a metal.' On still another hand, its porosity and brittleness at lower temperatures would put graphite in the ceramic class although, unlike most ceramics, it is readily machinable and has a high resistance to thermal shock. All things considered, it is probably more nearly appropriate to call graphite a metal than anything else. Although certainly outstanding in some ways, graphite has its peculiarities and, especially if the reader is unfamiliar with the data, it is probably valuable to review some representative property variations at high temperature. This review is meant to be mainly illustrative and no attempt has been made to be exhaustive. Review of High Temperature Properties At ordinary pressures, graphite does not melt, but sublimes directly into the gaseous phase at about 3700°C. Although the phase equilibrium diagram is still in some doubt, graphite will melt, at a slightly higher temperature, at pressures in excess of about 100 atm. The chief difficulty of using graphite in an oxidizing atmosphere is that the reaction rate becomes quite high at fairly low temperatures. If a threshold oxidation temperature2 is defined as the temperature at which graphite loses 1 pet of its weight in 24 hr, the value in air is 450°, the value in steam is 700°, and the value in carbon dioxide is 900°C. Efforts are presently being made to raise this threshold temperature either by impregnation with a retardant of some type (sodium tung-state and phosphoric acid, for example) or by a suitable metal or oxide coating. It is probably fair to say that, to date, these attempts have not shown any outstanding success in all respects. Most commercial graphites are fabricated by impregnating a carbon flour (say of coke or lampblack particles) with some type of hydrocarbon

Jan 1, 1959

By Axel Hultgren

IN ingots of silicon-killed carbon steel made without addition of - aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially. In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents arid, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,10,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis17 and their amount to increase from the top downward in the axial region .2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form," by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.15 Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19,20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping' or of refractory material from various sources1,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistance to hydrofluoric acid, imparted by the alumina content. Silicate inclusions, are often referred to as. the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1948

By Norman Weiss

MOST papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in.small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sulphidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthatc by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridann and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1918 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1947

By K. Prins

ONE of the more pressing problems faced by the coal industry today is the development of adequate means for meeting conservation laws, particularly those involving stream pollution, in various parts of the country. Discharge of dirty coal washery water into streams and rivers is almost universally frowned upon. Many states have enacted laws carrying heavy fines to curb the practice. The Prins stream-cleaner is one of the latest machines to enter the market. It is closely related to the cyclone thickener in principle. Eleven stream-cleaners are currently operating, ranging in size from 4 to 16 in. diam. In more recent installations the water enters directly in line and on a tangent with the impeller. The impeller consists of a vertical shaft up through a packing gland and bearings, and a V-belt pulley. The lower part is a tubing fastened to the shaft above, extending through the water intake compartment and provided with six vertical flat bars welded to the tubing. Portholes are situated in the upper end of the tubing, immediately below the point where shaft and tubing join together. The portholes are placed so that they are in open communication with the upper compartment of the stream-cleaner from which the processed water is discharged. The impeller is motor driven with a wide range vari-pitch drive employed between motor and impeller. The motor is mounted vertically, and the mounting provided with a vertical hinge allowing for needed adjustment of the wide range vari-pitch drive. The dirty coal washery water entering the machine under 20 lb psi pressure, flows from the compartment above the impeller, between the impeller blades, and is whirled around in the vertical section of the impeller enclosure. The speed of the impeller supplies centrifugal force and velocity required for separating suspended solids from water. The lower part of the machine consists of a cone, whose action is similar to other machines of the same type. The underflow discharge orifice is a cold rolled steel block machined to correspond with the cone angle and allows insertion of steel tubes of different diam. On 16 in. machines a 1 ¾ in. ID vertical discharge pipe is used. Provision is made for attaching a curved section of the same diam to the vertical pipe, to which, in turn, different lengths of horizontal pipe can be connected. Curved Pipe Advantageous It has been found that a curved pipe offers resistance to discharged material flow. In addition, the rotary motion of the underflow can be easily arrested in a curved pipe. Impeller speed of the 16 in. diam machine is provided from 400 to 800 rpm. A speed of about 474 rpm is suitable for maintenance of a constant underflow in coal slurry. In one installation 5x ¼ in. coal is cleaned in a Jeffrey Baum type washer at a 225 tons per hr rate. Washer installation is of the conventional type and a drag type sludge tank is used for water clarification purposes. Capacity of the water system, including the Baum washer, is about 40,000 gal. Before placing the stream-cleaner in operation, it was necessary to flush out the entire system every five days of two shift operations. The only time the system is drained now is for repair work on the sludge conveyor or the rig. The suction line of the stream-cleaner pump terminates in a number of small branch lines located at a depth of about 4 ft above the sludge conveyor. Each branch line extends the full width of the tank and is provided with four intake ports, each one with a funnel shaped inlet projecting downward. The arrangement provides an extensive pick-up area, for dirty water, and the inlets are arranged for a low rim velocity, preventing the taking in of coarse particles. The funnels are also arranged to extend up or down in the tank. They are set to pick up -60 mesh material exclusively.' The material is a high ash and high sulphur product and thus has to be disposed in the refuse conveyor. The underflow of the stream-cleaner is discharged on top of the washery refuse which is carried in a drag type horizontal conveyor, discharging into another refuse conveyor inclined at 30º with a short horizontal loading section. Some Disadvantages The impeller inherits certain disadvantages because of the nature of its construction. Additional moving parts make it subject to wear and maintenance costs. The advantage of being able to maintain a constant speed, however, to produce desired water velocity in the machine outweighs the drawbacks. Better separation between water and solids can be obtained by regulating time of residence of water through adjustment of valves in the intake and discharge lines. The amount of fines encountered during plant operation will vary because of higher or lower moisture in coal passing over fine coal vibrating screens. Even the amount of fines picked up by underground loading machines will be inconstant. Consequently, the percentage of solids will vary in water to be processed. The velocity in the feedlines to the slurry thickeners will fluctuate, with the required water velocity lacking. Another advantage advanced for the machine is its ability to operate on 15 to 25 lb line pressures at the water intake, reducing pump power required and pump maintenance.

Jan 1, 1952

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By V. C. Allison

Large-scale testing of the explosibility of coal dust as conducted by the Bureau of Mines in its Experimental Mine involves a large initial investment, and a high charge for maintenance and conduct of the test; in addition the work is necessarily slow because of the time required for the preparntion of the tests and the cleaning and repairing of the mine after each test. These tests have been made along practical mining lines that admit of a range of mixtures of dust varying from 5 to 10 per cent. and with gas as low as 0.5 per cent. increments. Because of the time and expense involved, efforts have been made to devise a type of gallery for laboratory use in which the results obtained in the Experimental Mine may be correlated as an aid in a study of dusts, the explosibility of which might be approximately determined quickly and at a minimum of expense. The explosibility of coal dust has been studied by a number of European investors, using small laboratory devices; among these may be mentioned the experiments conducted by Galloway, Vital, Hall and Clark, Abel, Mallard and Chatelier, Thorpe, Bedson and Widdas, Engler, Holwartz and Meyer, and Taffanel, results of whose experiments have becn reviewed by the Bureau of Mines.' The Bureau has conducted many tests with the Frazer-Cle1ncnt5 apparattus, which gives the pressures set up when the dust cloud within is ignited with a platinum coil or tube, heated to different temperatures, but for these tests the sample must be especially prepared as to size (200 mesh) and must be dry. Need for a Dust-testing Apparatus An attempt has been made to design an apparatus that may be used for checking and correlating the expcrimental tests. The first design was a wooden gallery, 8 by 10 in., inside cross section, and 12 ft. long, and having a number of strips along each side for creation of turbulence. The wooden gallery did not get beyond its period of calibration; it mas difficult to make the gallery sufficiently tight, for it was necessary that the top be removable in order that the gallery could be cleaned. In the use of the wooden gallery, however, sufficient operating data were obtained to be a guide in the design of a steel gallery having a circular cross-section. One of the features was a flap valve, at the closed end of the gallery, that would open inwardly thus preventing a reduced pressure within, caused by the cooling of the gases of combustion, and the explosions propagated much better than when the valve was not used; another feature was the determining of the best method for getting a cloud of dust simultaneously in all parts of the gallery, which was accomplished by the use of the concussion wave of a small quantity of powder or by the use of compressed air.

Jan 1, 1927

By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB's does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman's work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

By Herbert H. Kellogg

DEPOSITS of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (-325-mesh) sand assaying 95.5 per cent Si02, and a very fine (-3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. EXPERIMENTAL PROCEDURE The Sample.-The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.-By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fraction was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper.

Jan 1, 1945

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By Norman Weiss

Most papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sul-phidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthate by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridan and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1919 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1949

The production of bituminous coal in Pennsylvania started a few years after that in Virginia. For forty-five years all the production came from the Pittsburgh bed, and since that time its total output in value has exceeded that of any other single mineral deposit in the world. It has been impossible to separate the outputs of the four counties producing it at that time, as none of it came from Greene County until many years later, and the figures in the first column of Table 49 represent all the coal coming from Allegheny, Fayette, Washington and Westmoreland Counties. The years prior to 1790 are grouped on account of space limitations, they were made in the same manner as the later ones. All outputs have been rounded into hundreds, or thousands of tons because their accuracy does not warrant further subdivision. All figures are net tons, and all represent production and not shipments; this distinction in the early days when transportation facilities were scarce meant a great deal. In the period 1820-1835, more coal was used in salt-making in western Pennsylvania than for any other single purpose, but not a ton of such coal was handled by any transport agency. Later the iron industry used large quantities of local coal without shipment, and other instances can be cited. Prior to 1832, the only means of shipment of coal, excepting by wagons, was by the rivers, and this tonnage was larger than is generally believed. In Table 23, all of the available data about production from the Pittsburgh bed have been shown. After 1844 the river shipments above Pittsburgh are accurately reported by the Monongahela Navigation Company, but its figures do not include tonnage loaded on the river below Dam No. 1, nor that brought down Saw Mill Run. Prior to 1844 no tonnage records were kept although the amount moved was considerable. The information about local production, not shipped, whether used domestically or for manufacturing is necessarily incomplete. Column 7, shipments by railroad, river and canal, includes the figures in column 4, and until at least 1857 are quite evidently too low. The figures in column 9 are largely estimates based on the data shown and prior to 1870, and perhaps later, are much more likely to be lower, rather than higher, than the actual ones. This table was prepared over a period of years, and as additional data were found the revisions necessary were almost always upward. Clearfield County was the next producer in the state, shipments-in small amounts going down the Susquehanna River; some were made later via the West Branch Canal. Railroad facilities became available in 1862, and the growth in production increased rapidly and steadily. All available data and the estimated totals are in Table 24. Butler County began mining a few years after Clearfield, the early output

Jan 1, 1942

By H. R. Ogden, A. G. Imgram, D. N. Williams

The effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. Increasing the chromium, vandium, or aluminum content increased the strength of quenched structures with chromium being the most effective strengthener. Appreciable aging response was obtained with low chromium alloys, but high chromium alloys age softened rather than. hardened. High vanadium contents had a similar effect. Aluminum additions shifted the aging behavior toward that observed in lower chromium alloys, enabling high chromium alloys to be age hardened. DURING the course of titanium alloy development many a and a-ß alloys have been evolved to commercial status. However, only one all-ß alloy has achieved this same stature. This is the Ti-13V-11Cr-3Al alloy. It is characterized by a very sluggish ß-phase decomposition reaction such that very slow cooling rates can retain the 0 phase at room temperature. In addition, very high strength levels can be obtained by long-time aging treatments. Combinations of cold or warm working followed by aging produce even further improvements in strength. This paper describes the results of a research program in which the effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. EXPERIMENTAL PROCEDURES Electrolytically refined, high-purity titanium was used as the alloy base for these studies. Iodide chromium, electrolytically refined vanadium granules, and high-purity aluminum sheet were used as alloying additions. The compositions of interest were melted as 250-g ingots in a direct current arc melting furnace under a flowing atmosphere of argon. The ingots were hot forged to 3/4-in.-diam bars, vacuum annealed for 6 hr at 1800°F to reduce residual hydrogen content, and then hot swaged to 1/4-in.-diam rods. Fabrication history, and interstitial analyses after fabrication are given in Table I. All specimens to be heat treated were sealed in Vycor capsules under a partial pressure of argon. Samples used to define the ß transus were quenched from temperatures ranging from 1350° to 1100°F after holding at temperature for 15 min. Samples for aging studies were quenched from above the ß transus temperature and then aged for up to 64 hr at 750°F and for 100 hr at 850°, 900°, and 950°F. The effects of straining prior to aging were also investigated. The results of these studies were used to select the heat treatments for the tensile specimen blanks. Heat treatments of the tensile specimens are described in Table 11. Alloys were aged after solution heat treatment or after solution heat treatment and cold swaging to 50 pct reduction in area. Standard 0.125-in.-diam tensile specimens were machined from the heat-treated blanks. All tensile tests were performed in a Baldwin-Southwark uni-

Jan 1, 1963

By Cyril Stanley Smith

ON the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1958, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Cavallo3,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold-working restored it. He encountered some samples of brass that could not be rendered magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condition, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitters in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant,9 Honda and Shimizu, 10,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1941