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By Richard P. Hight

Abrasives include the substances, natural or artificial, that are used to grind, polish, abrade, scour, clean, or otherwise remove solid material, usually by rubbing action but also by impact (pressure blasting for example). They do not include abrasive tools, for instance, lathe tools and files--or polishing agents such as waxes, which act by filling pores. Detergents and cleaners whose action is chemical rather than physical are omitted al- though some chemical-action polishes and cleaners may also contain solid abrasives, for example, many automobile and metal polishes. General Considerations The most important physical properties of materials that qualify them for use as abrasives are hardness, toughness (or brittleness), grain shape and size, character of fracture or cleavage, purity or uniformity. For making bonded abrasive products such as grinding wheels, additional important factors are stability under high heat and bonding characteristics of grain surfaces. The economic factors of cost and availability are always important. No one single property is paramount for any use. For some uses extreme hardness and toughness are needed, as in diamonds for drill bits; for others, the factors of greatest importance are hardness and ability to break down slowly under use, to develop fresh cut- ting edges when grains become worn-for example: in garnet for sandpaper neither highly cleavable or friable grains nor extremely tough grains are wanted. For still other uses, great hardness is objectionable; for example, abrasives for dentifrices and for glass-cleaning soaps. For the most efficient use in the more critical applications, the different types of abrasives are rarely completely interchangeable; thus, while crushed quartz and garnet are both used in sandpaper, the papers are not at all interchangeable in their use applications. In the last analysis, the choice of a high grade abrasive depends upon the quality and quantity of work done by the abrasive per unit of cost. Initial cost of an artificial abrasive may be much greater than that of a natural abrasive but the artificial abrasive may do so much better work than the natural one, and do it so much faster that the ultimate cost will be less. It is for this reason that artificial abrasives have largely replaced natural abrasives. Abrasive Value Mineralogical hardness or "scratch" hardness as expressed in Mohs' scale is an important property in evaluating abrasive materials, but, as noted before, it is only one of several essential properties. The mineral hardness of pure crystal almandite garnet is about 7.5, but if the crystal is crossed by incipient fracture planes, or if it contains inclusions of other minerals, the apparent or useful hardness may be much lower. While the quartz grains in a sandstone have a hardness of 7, the bond holding the grains together may be so weak that the stone is valueless as a commercial abrasive. In artificially bonded wheels and stones, the hardness, strength, and character of the bond are fully as important as the hardness of the abrasive grains. Thus, in an overall consideration of abrasive hardness of loose abrasive grains, both "scratch" hardness and toughness must be considered. In naturally or artificially bonded abrasive stones, bond characteristics are a third factor, which is most important. The problem of abrasive hardness is further complicated by the inadequacies of methods of testing hardness and of expressing relative values. The Mohs' scale is inadequate both because the methods of testing are very crude and

Jan 1, 1975

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder's joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger's vectors in order to produce a lattice match. The .'dangling bonds'' resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965

By B. S. Crocker

Pebble grinding was used at Lake Shore Mines in 1949. A full description of experimental evidence and test plant results was published in 1952 1 and further operating details in 1954 2.' In more recent years the term autogenous grinding has been coined and is now frequently seen in the technical literature. Autogenous crushing and/or grinding covers any grinding mill in which the larger pieces of ore are made to grind the fine pieces; the crushing and grinding may be either dry or wet. This discussion deals only with wet autogenous grinding, and only in the fine grinding part of the circuit, i.e., from 6 mesh to 92 pct —325 mesh. The term pebble milling could apply to fine autogenous grinding in which the pebbles are made from the ore itself, or it could also refer to grinding with pebbles, such as flint pebbles, from a source outside the mine. The first mill to use screened ore to grind the ore (1949) was Lake Shore Mines, Kirkland Lake, Ont. Pebbles were screened from the jaw crusher discharge and used in 5x16-ft tube mills which had been converted to 6 ft 8 in. by 16-ft grate discharge pebble mills. The same general practice was adopted the following year by the Wright-Har-greaves Mine in Kirkland Lake. Shortly after that the Neptune Mines in Nicaragua started correspondence with the writer concerning the possibility of using screened ore for grinding in their plant. They first ran some plant-scale tests which confirmed the Lake Shore findings, with the ultimate result that their plant was successfully converted in 1956 to an autogenous grinding plant. In 1957-1958 the writer was successful in converting the grinding plant of Renabie Mines in northern Ontario to autogenous grinding. In all these plants the existing grinding equipment was converted, usually by expanding the diameter of the shell to make the change from steel grinding to ore pebble grinding mills. In all the above plants primary grinding was done in either small rod mills or ball mills. These mills first reduced the pebble mill feed to about 6 mesh. The final grinding in the pebble mills varied from 75 pct —200 mesh to 92 pct —325 mesh. At Lake Shore three stages of pebble milling were used, with a different size pebble in each stage. In other parts of the world interest was being shown in this form of grinding, and in March 1952 the writer had some correspondence with the mill staff at Outokumpu in Finland, with regard to the pebble system used at Lake Shore. At Stockholm in 1957 the account of the crushing and grinding system at Outokumpu was presented in a paper by H. Tanner and T. Heikkinen.V his is the only ore grinding plant that does not use grate discharges on its pebble mills; trunnion discharges equipped with heavy reverse spirals retain the pebble load. The first new mill designed to use screened ore as a grinding medium was the Bicroft mill at Bancroft, Ont., which began operation in the fall of 1956. In 1957 this plant was followed by similar installations at Faraday Mines, also in the Bancroft area, and the North Rankin Nickel Mines in the North West Territories. In 1958 the Dyno Mill at Bancroft was converted, using the same type of grinding. Since all these plants, designed by Kilborn Engineering (1954) Ltd., were originally planned as pebble grinding mills, they were able to take full advantage of the latest design and technique. They are neat in appearance and very efficient and easy to operate. Effect of Ore Hardness: It is often commented that this type of autogenous grinding applies only to hard siliceous ores. Experience has shown that this is not so. In the past ten years the author has had an opportunity to test more than a dozen ores, several of which were quite soft. One of these was shale. The softer ores actually make better looking pebbles than the hard ores. These soft ores produced no particles in the intermediate size range which could not be ground by the largest pebbles in the mill charge. Slabby ores, such as shales, make a suitable pebble for the —6 mesh grinding. It is not generally recognized that for fine grinding a spherical medium is not essential or more efficient. Another frequent objection to pebble grinding is the belief held by some operators that there is too much variation in the hardness of their particular ore to make it acceptable as a source of pebble media. Experience has also shown that this is not a serious problem at all. The variation in pebble load due to changes in the ore hardness is nothing like as great as most people would expect, and the method used for feeding the ore and controlling the the load in the mills is more than sufficient to take care of daily variations in ore hardness. This point

Jan 1, 1960

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O'Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By H. H. Klepfer, K. J. Gill, P. Chiotti

SOME observations relative to the U-Zn system have been made by other investigators. Chipman1 and Carter2 have reported the preparation of several U-Zn alloys and point out that these alloys are generally difficult to prepare. Chipman1 reported evidence for a high melting compound at about 90 atomic pct Zn and the possible existence of a eutec-tic between the compound and uranium. Raynor," in a theoretical discussion of the alloying properties of uranium, included zinc among the elements predicted to have little or no solubility in a, p, or y uranium. In the present investigation, thermal analyses, X-ray, metallographic, and vapor-pressure data were obtained to determine the phase boundaries. The relatively high zinc pressure over most of the alloys at temperatures of 900 °C and above proved troublesome and special techniques had to be employed in preparing suitable alloys. Materials and Preparation of Alloys The metals employed in this investigation were Ames Laboratory biscuit uranium containing less than 500 ppm total impurities and Bunker Hill slab zinc or Baker Analyzed reagent granulated zinc, both with a purity of 99.99+ pct. Due to the high vapor pressure of zinc and the high reactivity of both uranium and zinc with oxygen at only moderately high temperatures, alloys were prepared in closed containers which had either been evacuated or evacuated and filled with helium. High purity magnesia, magnesia containing 10 pct calcium fluoride, and tantalum proved to be suitable crucible materials. Tw-o different procedures, described below, were used to prepare alloys, the latter being the most satisfactory. The metals, uranium turnings and granulated zinc, were cleaned with dilute nitric acid, rinsed, dried, and placed immediately in a helium-fill'ed dry box. The two metals were placed' in a 10 mil Ta crucible. The charge was enclosed in the tantalum crucible by welding on a preformed tantalum cap. This assembly was enclosed inside a stainless steel (AISI 309) bomb. The bomb was made by welding a piece of stainless steel plate on each end of a stainless steel pipe. All these operations were carried out in a helium atmosphere. These assemblies were heated in a muffle furnace at temperatures between 1100" and 1200°C for 10 to 15 min or held as long as 15 to 20 hr in the 950" to 1000°C temperature range before quenching. Spectrographic and chemical analyses showed no tantalum pickup by the alloys, indicating no reaction between the alloys and the crucibles. However, some of these crucibles failed, probably due to imperfections in the welds of the stainless steel or tantalum crucibles. The second and most satisfactory method was to prepare the alloys by powder metallurgy techniques. The procedure was to press degreased and acid-etched uranium turnings with granulated zinc into 20 g compacts under 20,000-psi pressure. The compacts were placed in MgO crucibles, and sealed in evacuated Vycor or fused silica tubes. The alloys were then heated as long as two weeks at about 550°C in a muffle furnace. The pressed compacts were observed to expand by several volume percent during heating and it was necessary to make allowances for this expansion in order to avoid breaking the crucible and Vycor tube. This method was found very satisfactory for preparing alloys which were suitable for thermal analysis or vapor pressure studies. Experimental Methods and Results The phase diagram for the U-Zn system at 1 atrn pressure, shown in Fig. 1, is based primarily on vapor pressure measurements and on thermal analysis taken at temperatures below 950°C. Fig. 2 shows the U-Zn diagram at 5 atrn pressure, constructed on the basis of thermal analysis of alloys in sealed containers up to 1150°C and on the basis of metallographic, X-ray, and analytical data. The alloys sealed under vacuum were actually under their own vapor pressure and those sealed in an atmosphere of helium were under an additional pressure due to the helium. At temperatures up to 1100°C the zinc pressure is 5 atrn or less for these alloys; consequently the maximum pressure over the alloys sealed under a helium atmosphere was 10 atrn or less at temperatures up to 1100°C. Changes in pressure of this order of magnitude do not appreciably alter the position of most solid-solid or liquid-solid phase boundaries. In constructing the phase diagram for a pressure of 5 atm, the effect of pressure on all phase boundaries except those for liquid-vapor or solid-vapor regions was considered negligible.

Jan 1, 1958

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.' Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.' Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.' Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.' In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.' It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By G. W. Ostroot, S. Shryock

Cementing deep, high-temperature oil wells where static temperatures range from 350 to 400F has become routine in the part decade. In the United States there were 271 wells drilled deeper than 15,000 ft during 1963. Many of these wells had static temperatures higher than 400F. Bottom-hole static temperatures near 700F are now realities in the geother-mal (steam producing) wells of California's Salton Sea area. The detailed planning initiated prior to drilling the wells is discussed together with the methods, materials and equipment used in solving the cementing problems which are encountered. Data are also presented that lead to development of cementing compositions that provide adequate thickening time, do not retrogress in strength, and maintain low permeability under these extreme temperature conditions. Field data include the cementing programs used on eight relatively trouble-free geothermal steam wells in the Salton Sea area. INTRODUCTION Not too many years ago cementing oil wells with temperatures in the range of 300F caused considerable anxiety. In some areas of the United States it is now fairly common to cement wells having bottom-hole static temperatures in excess of 400F. We are now confronted with the problem of cementing wells with temperatures ranging from 500 to 700F. Temperatures in this order of magnitude are often found in geothermal steam wells. From where does this extreme heat emanate? There are many theories as to the source of this steam flow. The most widely held views are: (1) heat- ing of ground water fairly close to the surface by an intrusive mass of hot rock; (2) steam generation from a reservoir of metamorphic rock, normally found below 25,000 ft and not at the shallower depths of the Salton Sea reservoir; and (3) high-temperature gases (water vapor) escaping and migrating from molten or semi-molten rock (magma) at a considerable depth. Of these. No. 3 seems to be the most generally acceptable explanation. Heat from springs and fumaroles has been used for years as a means of heating and cooking; however, significant progress in harnessing the vast power of underground steam reservoirs has been relatively slow. The first large-scale attempt to use the heat generated by steam from wells was made in Italy around the beginning of the 20th century. In excess of 250,000 kw of electrical power is now being produced from holes around Larde-rello, Italy. Another very active drilling program was initiated in the volcanic area of New Zealand in 1949.' Natural steam for power projects in the United States began in the early 1920's. An early commercial steam field is located at the Geysers, approximately 75 miles north of San Francisco, an area discovered in 1847 and used for many years as a health resort. Steam originates from 15 wells that have been drilled since 1957. The present output from this project is 25,000 kw. Success of the Geysers operation has been responsible for several companies taking a careful look at the feasibility of producing steam for power generation in the Salton Sea area of Southern California's Imperial Valley. Geothermal steam activity in this latter area began in 1961 when O'Neill, Ashmun and Hilliard completed Sportsman No. 1, at that time the hottest wellbore in the world.' Since its References given at end of paver. completion seven additional wells have been successfully completed in this area. Many problems encountered in drilling steam wells had to be overcome to make the ventures successful. Formation temperatures encountered in the Salton Sea seemed to be a straight-line function (a gradient of 13F per 100 ft of depth).' This imposed severe conditions on all aspects of drilling and completion. This varied, to some extent, from gradients in the older geothermal areas. Not to be overlooked is the effect of these temperatures on casing creep or elongation by thermal expansion (Table I), because standard API flanged wellhead equipment makes no provision for this kind of performance. Floating equipment was redesigned, and changes in types of downhole equipment were made in an effort to eliminate anticipated problems. In the later completed wells, standard oil-well cementing equipment has been used. During the early development of geothermal steam wells there were some problems resulting from blowouts. However, these were eliminated in the deeper Salton Sea wells and no problems were encountered with the drilling mud. A sodium surfactant mud was used on the Sportsman No. 1 to drill from 2,690 to total depth. Nevertheless, it was necessary that a cooling system be added and the mud cooled before circulating it back into the well. The difficulty in evaluating the size of the steam area and its potential in terms of pounds of steam and years of productivity still has not been resolved. Economic complexities have also entered into the steam play in the Salton Sea. The wells at the Geysers were drilled at a cost of $15,000 to $20,-000, whereas the Salton Sea wells will cost more than $150,000. This cost differential has to some extent been accounted for because of the heavily

Jan 1, 1965

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.' Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author's method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By W. Weissberger, Frankiewicz, L. Pommier

Introduction In the U.S., about one-quarter of the fuel oil and natural gas consumption is associated with power production in utility and industrial boilers and process heat needs in industrial furnaces. Coal has been an attractive candidate for replacing these premium fuels because of its low cost, but there are penalties associated with the solid fuel form. In many cases pulverized coal in unacceptable as a premium fuel replacement because of the extensive cost of retrofitting an existing boiler designed to burn oil or gas. In the cases of synthetic fuels from coal, research and development still have a long way to go and costs are very high. Another option, which appears very attractive, is the use of solid coal in a liquid fuel form - coal slurry fuels. Occidental Research Corp. has been developing coal slurry fuels in conjunction with Island Creek Coal (ICC), a wholly-owned subsidiary. Both coal-oil mixtures and coalwater mixtures are under development. ICC is a large eastern coal producer, engaged in the production and marketing of bituminous coal, both utility steam and high quality metallurgical coals. There are a number of incentives for potential users of coal slurry fuels and in particular for coal-water mixtures (CWMs). First, CWM represents an assured supply of fuel at a price predictable into future years. Second, CWM is available in the near term; there are no substantial advances in technology needed to provide coal slurry fuels commercially. Third, there is minimal new equipment required to accommodate CWM in the end-user's facility. Fourth, CWM is nearly as convenient to handle, store, and combust as is fuel oil. Several variants of CWM technology could be developed for different end-users in the future. One concept is to formulate slurry at the mine mouth in association with an integrated beneficiation process. This slurry fuel may be delivered to the end-user by any number of known conveyances such as barge, tank truck, and rail. Slurry fuel would then be stored on-site and used on demand in utility boilers, industrial boilers, and potentially for process heat needs or residential and commercial heating. An alternative approach is to formulate a low viscosity pre-slurry at the mine mouth and to pipeline it for a considerable distance, finishing up slurry formulation near the end-user's plant. Finally, at the other extreme of manufacturing alternatives, washed coal would be shipped to a CWM manufacturing plant just outside the end-user's gate. Depending on fuel specifications and locations of the mine and end-user facility, any of these alternatives may make economic sense. They are all achievable in the near term using existing technology or variants thereof. The Coal-Water Mixture CWMs contain a nominal 70 wt. % coal ground somewhat finer than the standard pulverized ("utility grind") coal grind suspended in water; a complex chemical additive system gives the desired CWM properties, making the suspension pumpable and preventing sedimentation and hardening over time. Figure 1 shows the difference between a sample of pulverized coal containing 30 wt. % moisture and a CWM of identical coal/water ratio. The coal sample behaves like sticky coal, while the CWM flows readily. The combustion energy of a CWM is 96-97% of that associated with the coal present, due to the penalty for vaporizing water in the CWM. Potentially any coal can be incorporated in the CWM, depending on the combustion performance required and the allowable cost. CWMs are usually formulated using high quality steam coals containing around 6% ash, 34% volatile matter, 0.8% sulfur, 1500°C (2730°F) initial deformation temperatures, and energy content of 25 GJ/t (21.5 million Btu per st). Additional beneficiation to the 3% ash level can be accomplished in an integrated process. There are a number of minimum requirements which a satisfactory CWM must meet: pumpability, stability, combustibility, and affordability. In addition, a CWM should be: resistant to extended shear, generally applicable to a wide variety of coals, forgiving/flexible, and compatible with the least expensive processing. It was found that a complex chemical additive package and control of particle size distribution are necessary to achieve these attributes simultaneously, while maximizing coal content in the slurry fuel. Formulation of Coal-Water Mixtures A major consideration in the manufacture, transportation, and utilization of a slurry fuel is its pumpability, or effective viscosity. Most CWM formulations are nonNewtonian, i.e., viscosity depends on the rate and/or duration of shear applied. Viscosities reported in this paper were obtained using a Brookfield viscometer fitted with a T-spindel and rotated at 30 rev/min, thus they are apparent viscosities measured at a shear rate of approximately 10 sec-1. The instrument does reproducibly generate a shear field if spindle size and rotation rate are held fixed. By observing the apparent viscosities of several slurries at fixed conditions it is possible to obtain a relative measure of their viscosities for comparison purposes. A true shear stress-shear rate relationship at the shear rates at which the CWM will be subjected in industry may be obtained using the Haake type and a capillary viscometer. These viscometers are used for specific applications. However, for comparison purposes, apparent viscosities are reported.

Jan 1, 1985

By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

By L. A. Rapoport, W. J. Leas

The original Burkley-Leverett theory has been extended and a more detailed formulation of the waterflood behavior in linear horizontal systems is presented. Particular consideration has been given to the evaluation of capillary pressure effects and differential equations permitting an explicit evaluation of these effects have been derived. On the basis of the developed theory it is recognized that the flooding behavior is dependent upon the length of the system and the rate of injection. At the same time it has been determined that systems of different lengths yield the same flooding behavior if the injection rates and or the fluid viscosities are properly adjrrsted or "scaled." It has also been found that the sensitivity of the flooding behavior with respect to rate and length decreases as any one of these {actors increases in value and that for sufficiently long systems and high rate.; of water injection the flooding behavior becomes independent of rate and length. or "stabilized." To such stabilized conditions the theory formulated by Buckley and Leverett is applicable. A number of laboratory flooding tests have been made and good agreement Iraq been found between theory and experimental observations. The experimental results are discussed and it is shown that under field conditions the flooding behavior is usually stabilized. As a result of these finding; a procedure is indicated for evaluating field performances either on the basis of tests performed with commonly available core samples or by means of calculations using relative permeability data INTRODUCTION In recent years the development of methods for evaluating oil recovery by waterflooding has been the object of considerable research. A theoretical analysis of the mechanisms involved in the displacement of immiscible fluids was originally established by Buckle!- and Leverettl and experimental investipatio~~s have been made by numerons workers." Many of the experimental results are in mutual agreement and bear out several significant features of the flooding mechanism as predicted by theory. Thus it lias been generally recognized that a flood corresponds to the movement of a steep saturation hank or "front" (primary phase), followed by additional gradual oil displacement (subordinate phase). It has also been found that for any porous medium the flooding behavior is largely dependent upon the oil-water viscosity ratio and that for increasing values of this ratio the relative importance of the primary displacement phase decreases while that of the subordinate phase becomes more pronounced. Although the studies to date have clarified certain aspects of the flooding process. they have given rise to observations of a somewhat contradictory nature that cannot he explained in terms of the original theory. These observations pertain mainly to the effect of injection rate or pressure gradient upon recovery. Some investigators report laboratory tests that indicate incresing oil recoverieq with increasing rates of water injectill, others find the flooding behavior to be independent of and other. mention lower oil recoveries with increased injection rates.3 The conflicting evidence indicated above creates considerable uncertainty with respect to laboratory testing procedures and the utilization of the resulting data for field evaluations. The principal purpose of this paper, then, is to resolve these Uncertainties by means of a comprehensive theoretical and experimental investigation of the flooding meanism. THEORETICAL DEVELOPMENT Derivation of Flooding Equations The mathematical description of transient flow phenomena is based upon the consideration of the various processes occurring during an infinitesimal time interval in an infinitesimal volume element and upon the correlation of these processes with those occurring in the adjacent elements. The volume elements are defined as being infinitesimal in comparison to the overall dimensions of the porous system, yet each sufficiently large so aS to encompass the full range of pore openings encountered throughout the system. If a porous system can arbitrarily be subdivided into an infinite number of volume elements all possessing the same distribution of pore openings and if this distribution is unformly continuous. the system may be said to be homogeneous. Such a homogeneous porous medium is considered in the present studivs. It is furthermore postulatecl that only oil and water are present in the pornu wediu. that they act a- totally incompressible and immiscible fluids. and that gravity effects are negligible. In n linear flow system of unit cross sertional area. as treated here. the infinitesimal volume element.; to he considered are cylindrical ".slices" of thickness dx. oriented perpendicularly to the direction of flow. The equations applicable to any such volume element. at my time. describe the movement. of oil and water across the element:

Jan 1, 1953

By C. F. Allen, G. B. Walker

K. F. TROMP*—In dealing with the question of the most suitable kind of solid media for heavy density suspension processes Walker and Allen point out that the particle size of the solid media should not be taken too fine, as the viscosity increases with the area of the solid media and a low viscosity is essential lor high tonnage and accurate separation. A coarser particle size of the solid media will, in their opinion, of necessity give rise to a differential density in the bath (higher gravity at the bottom of the bath than at the top) but they advocate acceptance of the differential density rather than a higher viscosity. Though I fully agree with the choice the authors have made, I cannot subscribe to their view that only by accepting a differential density in the bath a coarse particle size of the solid media can be used. There certainly is another alternative: stronger agitation. Applying sufficiently strong vertical currents, a uniform gravity can be obtained quite well in a suspension of a coarse solid media. Of course, this is not a very attractive solution, for it means a degradation of the true gravity separation and a step backwards to hydraulic classification, which makes the washing dependent on size and shape of the particles. However, to a greater or lesser extent, this is what actually takes place in all the heavy density suspension processes relying on a uniform gravity in the bath. The so-called "stable" suspension processes make no exception. They all "stabilize" their suspensions by introducing or creating vertical currents, be it upwards or downwards or both, be it by hydraulic or by mechanical means. In fact, there is no such thing as a "stable" suspension in gravity separation, as the very reason for the use of suspensions in this field is the property that the solid media is able to settle and so facilitate the recovery. I have been enlarging on this point because the characteristics of the various processes can only be well understood and viewed from the same angle (from Bar-voys up to Chance) when the fact is recognized that mechanical or hydraulic agitation is a condition sine qua non for obtaining a uniform density from top to bottom in a suspension. Is a Cone-slraped Vessel Essenlial? Of the two alternatives for getting a low viscosity Walker and Allen have preferred correctly the sacrifice of uniform gravity in the bath instead of increasing further their vertical current arid agitation. The resulting differential density of the bath brings the problem of bow to prevent accumulation of intermediate gravity products in the bath, an accumulation which, if not prevented, would ultimately plug their cone. According to the authors an open-top cone combined with a downdraft current of the bath liquid would he the only suitable way to cope with such suspensions and they assume as a fact that "in any vessel other than a cone, such a differential density could not be tolerated." My experience is quilt: different. In my process, which has been in successful operation for more than a decade, differ-ential density of the suspension is applied ranging from values below 0.1 up to differentials above 0.5, according to the prevailing requirements of the individual plant. In this process, which is charac-terized by the use of horizontal currents in a suspension of differential density, the form of the vessel is of secondary importance and different types are in operation. It so happens that none of these are in the, form of a cone. The fact that 24 washboxes on my process have been installed and 12 others are under construction may constitute sufficient proof against the opinion that only a cone-shaped separator would be suited for differential density separation. Horizontal Currents in Differentia1 Den-sity Sepparation I myself have some doubts as to the suitability of a cone with downdraft for dealing with differential density (or, for that matter, any other washbox relying on vertical currents for removing the intermediate gravity products). It ap-pears to me that it is restricted to feed of small size only and even then with watch-fulness. If we take, for example, a piece of 2 in., the draft necessary to pull such a piece down to a zone wherein the den-sity of the suspension is, say, 0.03 higher, is quite considerable. For a suspension of, say, 1.6 sp gr the downdraft will have to be in the region of 3 in. per second. Unfortunately. most of the differential in density is in the part immediately below the reach of the top current which transports the floats. Consequently, we need the downdraft where we like it least: in the upper part of the cone. This entails the risk that light float particles are carried away with the downward current. This current of, say again, 3 in. per second would carry particles up to 1.3 sp gr and 3/8 in. size into the 1.6 gravity zone. This is prohibitive. It is also prohibitive because a downdraft of 3 in. per second in the upper part of the cone would require a tremendous circulation of medium. IIalf way up a 20 ft diam cone, a downdraft of 3 in. per second would correspond with 8500 gpm. With the downward current following the way of least resistance, the strength of the downdraft will not be exactly the same at different places of a cross area. If, as I anticipate, the center of the cone is favored, the strength of the downdraft will fall below the critical value near the

Jan 1, 1950

By C. S. Finney, John Mitchell

The decline of the beehive coking industry was inevitable, but it had filled the needs and economy of its day. A beehive plant required neither large capital investment to construct nor an elaborate and expensive organization to run. The ovens were built near mines from which large quantities of easily-won coking coal of excellent quality could be taken, and handling and preparation costs were thus at a minimum. The beehive process undoubtedly produced fine metallurgical coke, and low yields were considered to be the price that had to be paid for a superior product. Few could have foreseen that the time would come when lack of satisfactory coking coal would force most of the beehive plants in the Connellsville district, for example, to stay idle; and if there were those like Belden who cried out against the enormous waste which was leading to exhaustion of the country's best coking coals, there were many more to whom conservation was almost the negation of what has since become popularly known as the spirit of free enterprise. As for the recovery of such by-products as tar, light oil, and ammonia compounds, throughout much of the beehive era there was little economic incentive to move away from a tried and trusted carbonization method simply to produce materials for which no great market existed anyway. With the twentieth century came changes that were to bring an end to the predominance of beehive coking. Large new steel-producing corporations were formed whose operations were integrated to include not only the making and marketing of iron or steel but also the mining of coal and ore from their own properties, the quarrying of their own limestone and dolomite, and the production of coke at or near their blast furnaces. As the steel industry expanded so did the geographic center of production move westward. By 1893 it had moved from east-central to western Pennsylvania, and by 1923 was located to the north and center of Ohio. This western movement led, of course, to the utilization of the poorer quality coking coals of Illinois, Indiana and Ohio. These coals could not be carbonized to produce an acceptable metallurgical coke in the beehive oven, but could be so treated in the by-product oven. By World War I the technological and economic limitations of the beehive oven as a coke producer were being widely recognized. After the war the number of beehive ovens in existence dropped steadily to a low of 10,816 in 1938, in which year the industry produced only some 800,000 tons of coke out of a total US production of 32.5 million tons. The demands of the second World War led to the rehabilitation of many ovens which had not been used for years, and in 1941, for the first time since 1929, beehive ovens produced more than 10 pet of the country's total coke output. Production fell off again after 1945, but the war in Korea made it necessary once more to utilize all available carbonizing capacity so that by 1951 there were 20,458 ovens with an annual coke capacity of 13.9 million tons in existence. Since that time the iron and steel industry has expanded and modernized its by-product coking facilities, and by the end of 1958 only 64 pet of the 8682 beehive ovens still left were capable of being operated. Because beehive ovens are cheap and easy to build and can be closed down and started up with no great damage to brickwork or refractory, it is likely that they will always have a place, albeit a minor one, in the coking industry. The future role of the beehive oven would seem to be precisely that predicted forty years ago by R. S. McBride of the US Geological Survey. Writing with considerable prescience, McBride declared: "A by-product coke-oven plant requires an elaborate organization and a large investment per unit of coke produced per day. Operators of such plants cannot afford to close them down and start them up with every minor change in market conditions. It is not altogether a question whether beehive coke or by-product coke can be produced at a lower price at any particular time. Often by-product coke will be produced and sold at less than cost simply in order to maintain an organization and give some measure of financial return upon the large investment, which would otherwise

Jan 1, 1961

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By A. N. Holden

A DISLOCATION mechanism has been described by Cottrell' by which metals can yield locally, I. form Liiders bands, giving rise to a characteristic stress-strain curve with a sharp yield point and appreciable strain at constant or decreasing stress. It is undoubtedly the best mechanism that has been suggested to date." In its present development, however, the dislocation mechanism provides a more satisfying explanation for the sharp yield point than for the extensive localized flow occurring at the lower yield stress. The primary objective in this paper is to extend the dislocation mechanism to account for localized cataclysmic flow by a dislocation collision process and to give experimental evidence to support such a process. Only the yielding of iron containing carbon -will be discussed, although other metal-solute systems are known to behave similarly. Cottrell Mechanism In brief, Cottrell explains the yield point in the following way: The dislocations in iron which must propagate to produce slip usually lie at the center of local concentrations of carbon atoms, since segregation about these dislocatlons relieves some of the local stress resulting from them. A dislocation surrounded by a "cloud" of carbon atoms is thus anchored, and a higher stress is required to set it in motion than to move a free dislocation. Considering all available dislocatlons to be anchored in this fashion, the iron exhibits a yield point when the first dialocations break free and move through the lattice causing slip. This first breaking away of a dislocation enables other dislocations to break loose by "interaction" and the process becomes a cataclysm producing local deformation or Luders bands. The yield point in the stress-strain diagram for iron is absent in freshly deformed material, but returns gradually with time; the phenomenon is one aspect of what is called strain aging. The rate at which the yield point returns following straining depends on the temperature of aging. According to Cottrell the rate of return of the yield point in strained iron is limited by the rate of diffusion of carbon at the aging temperature, the mechanism is onr: of reforming the solute atmospheres around carbon-free dislocations that had stopped moving coincident with the removal of stress. If the specimen is retested immediately after straining and unloading, carbon will not have had time to diffuse to, and re-anchor, dislocations and the yield point will not occur. The carbon diffusion limitation for the rate of strain aging apparently applies if the criterion for strain aging is either the change in hardness" or the change in electrical resistance" of the strained speci- men with aging time. The possibility exists, however, that the yield point actually returns to strained iron at some rate other than that deduced from hardness or electrical resistance data. Therefore, as a preliminary experiment, the rate of yield point return in a rimmed sheet steel strained 6 pct in tension was measured at 27°, 77°, and 100°C. A plot of yield-point elongation for each of these temperatures against aging time appears in Fig. 1. The aging process is described by curves which rise to a plateau value of elongation that seems independent of temperature, but at a rate that depends on temperature. Very long times lead to a further rise in the yield-point elongation above the plateau value. However, if the later increase in yield-point elongation is ignored and the log of the time to reach half the plateau value of elongation is plotted against 1/T, a straight line results for which an activation energy of about 25 kcal pel- mol may be assigned. Within the accuracy of this sort of experiment this is approximately the activation energy for the diffusion of carbon in iron (20 kcal per mol), and the carbon diffusion limitation suggested for the yield-point return on strain aging is valid. The Cottrell mechanism thus explains in a qualitative manner the occurrence of a yield point in iron and its return with strain aging. It fails, however, to explain some of the other experimental observations that have been made of the yielding behavior of iron. For example, it is known that the yield point in iron becomes less pronounced with increasing grain size. Annealed single crystals of iron have very small yield-point elongations .if indeed they have any,' compared to a polycrystalline steel. If the only requirement for a yield point is that the dislocations in the lattice of the annealed. material be anchored by carbon atoms, the difference in the behavior of single crystals and polycrystals is not explained. That a dislocation mechanism may be entirely consistent with little or no yield point in an annealed single crystal will become apparent later when dislocation interaction is discussed. Strain aging produces a definite yield point even in single crystals. This accentuation of the yield-point phenomenon in single crystals after strain

Jan 1, 1953

By R. L. Rickett, S. H. Kalin, J. T. Mackenzie

Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By K. W. Nelson, John N. Abersold

INDUSTRIAL hygiene has been defined by Patty' as "the science and art of recognizing, evaluating, and controlling potentially harmful factors in the industrial environment." This definition implies thorough study of operations, evaluation of potentially harmful factors through air sampling, micro-analyses and other means and finally, appropriate medical and engineering control wherever indicated. The prevention of industrial health injuries is a vital part of operations of American industry today. Progress and interest in this field has increased steadily for many years, the most rapid progress having been attained, perhaps, during the last three decades. It is significant to note that there are now official agencies in 46 states actively concerned with industrial health problems and that a western field station has been established recently in Salt Lake City by the U. S. Public Health Service to augment its industrial hygiene services directed from headquarters of the National Institute of Health, Bethesda, Md. Many of the larger industries have found it advantageous to establish their own industrial hygiene departments. The American Smelting and Refining Co. is a world-wide organization engaged in the mining, smelting, and refining of lead, copper, zinc, silver, gold, by-product metals, including cadmium, arsenic, and others. In the United States there are 13 smelters and refineries, 11 secondary smelters or foundries, and a number of mines. Approximately 9000 workers are normally employed. It has long been the established company policy to seek out occupational hazards and provide safeguards for employee health. Protective equipment has been supplied to individual workers and exhaust ventilation installations have been in use in some operations for more than 40 years. All of the major units have their own medical departments which provide employees with excellent medical and hospital care. In 1937 full scale industrial hygiene studies were undertaken at the Selby Plant and were extended to most of the other smelters during the next three years. In 1945 the Department of Hygiene was organized with Professor Philip Drinker of Harvard University as Director and with Dr. S. S. Pinto as Medical Director. The department is responsible for coordinating and maintaining a program for the good health of all employees from top management down to the lowest paid day worker. It is essentially a service organization serving all of the United States plants regardless of location or size. Full and part-time physicians employed in all of the company's American plants and working in close cooperation with the Medical Director are responsible for de- termining the state of health of all the employees and giving treatment when necessary. In general, medical care is confined to accidents or illnesses occurring while the men are on the job. Among the duties of the doctors is the making of careful physical examinations of new employees and routine check-ups of old employees. In addition to medical care a primary responsibility of the department is the prevention of occupational illnesses. In this the main concern is with the working environment in relation to its effect on the worker. Environmental factors may be dusts, fumes, gases, toxic materials, heat, humidity, radiation, or noise. The objectives are: (1) Immediate control of these factors through the education of the worker, through providing the wearing of respirators or other protective devices, and through careful medical examinations and regular analysis of urine specimens; (2) a long range control program which may be accomplished by local exhaust ventilation, wetting of materials, changes in metallurgy, changes in methods of handling, or by use of special devices and special equipment. To accomplish these objectives a fine industrial hygiene laboratory was built in Salt Lake City and equipped to do routine and experimental work. Trained and experienced industrial hygienists obtain the facts by making frequent hygiene surveys. These surveys include tests of the air, studies of all processes, and careful investigation of ventilation, lighting, and general working conditions. Except in emergencies, the air contaminants and often the substances handled by the worker are sent to the laboratory for analysis by chemists and technicians specially trained in industrial hygiene methods. The findings are evaluated in terms of limits recommended by various State and Federal agencies, and in light of all available medical data. The methods used for studying the working environment involve all of the usual chemical and physical procedures employed in industrial hygiene. The Impinger, electric precipitator, thermal pre-cipitator, and filter paper sampler have been used to collect atmospheric dust and fume samples. Of special interest here is the filter paper sampler, shown in Fig. 1, which was developed by Dr. Silver-man at Harvard University. The instrument has been improved and is used very extensively in field studies. A water manometer connected behind an orifice is used to determine the rate of air flow. Calibration is effected by use of a standard gas meter or rotameter. The dust or fume is collected on a filter paper clamped between two rings, as shown in Fig. 2. The filter paper, such as Whatman No. 52, collects both dust and fume with a very high efficiency. The instrument is very convenient and easily transported. The solids collected on the filter paper are analyzed in the laboratory usually by use of a polar-ographic procedure. By this procedure it is possible to measure quantitatively in a single analysis the

Jan 1, 1952

By AIME

One of the operations of the J. L. Shiely Co. is quarrying in a hard granite gneiss with intrusions of gabbro or trap. During the winter of 1948-1949 the quarry ramp was lowered about 30 ft and during the 1949 season practically all drilling was done from the quarry floor, developing a face from 72 to 83 ft for the entire quarry area. The performance and cost table shows our record for 1948 and 1949.

Jan 1, 1950