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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 C. Richard Tinsley

INTRODUCTION Documentary complications arise from the risk apportionment in project financing which generally means that once the project is up and running and has satisfied the lender's completion test, the loan agreement specifically limits the lender's recourse to the project and its assets. It is the purpose of this paper to describe the special considerations which apply to industrial minerals projects and explore the reasons why so few project financings are negotiated in this industry. SIZE Small projects do not warrant the relatively high costs of negotiating and documenting project financing. The extent of the documentation is directly proportionate to either (a) the degree of risk apportionment, or (b) the amount of control given to lawyers to negotiate the documents. Although one would like to believe that project-finance documentation could be off-the-shelf, it is almost always necessary to tailor the documents to the mine development itself and the individual desires of the borrower. Accordingly, the documentation costs and initial expenses are seldom less than $40,000, and for complex projects can reach $400,000. In addition, banks often charge an up-front fee to partly compensate them for their staff time and partly to increase their yield on what is deemed to be a "riskier" loan asset. Another factor is the generally lower debt:equity ratio when bankers are uncertain of the accuracy of the cash flow projections. The ratio of the amount of cash flow left over after debt service to debt service itself is a key tool for project finance (debt service coverage). Bankers will require a higher coverage ratio for industrial minerals projects because of the relatively higher uncertainties in the following categories: Prices Markets Geology/Quality Transportation Environmental This, in turn, means that lower debt:equity ratios are the norm for new industrial minerals projects. INDUSTRY STRUCTURE It is hardly worthwhile to generalise about a field as diverse as industrial minerals, but there are four other structural reasons why project financing has not been widely applied. 1. The most obvious example is the predominance of small-sized operations, largely a function of transportation economics. Geological conditions also contribute to their dispersion. 2. Often, the product is only a small part of a company's business in contrast to many petroleum, metals, or coal companies whose sole business is the production of the raw material. The construction industry is a good example here for cement, gypsum, crushed stone, sand and gravel, and the drilling-mud services business for barite and bentonite. A company is unlikely to jeopardise its main business through the failure of a project financing on one of its key inputs. The corrollary is that the mined input is often regarded as a cost centre and not run on the sort of economic basis suitable for project financing. 3. There may be a reluctance to reveal key aspects of an industrial minerals venture to an outsider for purely competitive reasons. Unlike the other minerals industries which readily share technical information at plant visits and

Jan 1, 1985

By Stuart E. Buckley, C. R. Hocott

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By C. R. Hocott, Stuart E. Buckley

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence' gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By George R. Cowan

A number of studies hare been reported of the effects produced in metals subjected to deformation by shock waves with maximum pressures ranging from tens to hundreds of kilobars. On the basis of the equations for the flow of mass, momentum, and energy through a stationary shock front, the macroscopic stress-strain curve for the resulting shock deformation can be calculated within narrow limits from the experimentally determined Hugoniol curve. In relatively weak shocks which are preceded by an elastic wave, the stress rises above the clastic limit only as plastic deformation proceeds cold thus the shock has a long toe. In strong shocks that override the elastic wave a high stress is applied without prior plastic deformation. A more important effect of increasing the shock pressure is the generation of shear stresses, called supercrilical shear stresses, that exceed the strength of the perfect lattice. A change in the mechanism of deformation is expected to result from the onset of supercritical shear. The shock disordering of ordered Cu3Au in strong shocks appears to be an example of such a change. It is suggested that the formation of fine twins in copper and nickel and the formation of structures which enable visible twins to be formed in the rarefaction ware, observed in copper and presumably in disordered Cu3 Au, are related to the occurrence of supercritical shear in shock dcformation. In recent years several studies1,2 have been made of the changes in structural and mechanical properties of metals produced by the passage through the metals of strong shock-compression waves ranging from about 50 to 800 kbar pressure. Recent work involving dynamic measurements of the shock compression "Hugoniot" curves 3-8 of many metals has developed techniques and provided data required to obtain the shock pressure and the (transient! plastic deformation produced in the shock-conlpression experirnents.9 Shock deformation has been found to be much more effective than slow deformation in changing the mechanical properties of metals, when the two are compared on the basis of equal plasti strain, Holtzman and Cowan9 made quantitative estimates of the shearing stress occurring in a shock front in a metal by assuming that the shearing stress is similar to that occurring in a shock front in a viscous, heat-conducting fluid, with the addition of a yield stress. Taylor's solution9 for a weak shock was used to estimate pairs of values of shearing stress and thickness of the shock front obtained by assumed choices of the ratio of effective kinetic viscosity to thermal diffusivity. It was noted from these values that. unless the shock front is extremely thin. heat conduction has slight effect, and the shearing stress is nearly independent of the mechanism of deformation. This mechanism does, however, determine the thickness of the shock front and the rate of strain. Furthermore, since the maximum possible shearing stress occurring in shocks of moderate strength does not greatly exceed the shear stress occurring in conventional slow deformation, the mechanism of deformation is not expected to be qualitatively different. The greater effectiveness of shock deformation in changing the mechanical properties of metals can be attributed partly to the fact that dislocations, when driven by near-conventional stresses, cannot keep up with the shock front, thus necessitating a higher dislocation density than required for an equivalent slow strain. The fast uni-axial strain occurring in the thin shock front would also be expected to cause a larger number of dislocation intersections to occur. In the upper range of shock pressures that have been studied the estimated values of the shearing stress exceeded the estimated shear strength of a perfect crystal. Under these circumstances it is reasonable to expect that the mechanism of deformation might be considerably different from that involved in slow deformation. Except for the observation by smith1 of twins in shocked copper, the effects of shock waves on metals did not show any obvious or large changes in properties that would indicate the onset of a change in the mechanism of deformation. The recent investigation of the effect of shock waves on ordered and disordered specimens of Cu3Au by Beardmore, Holtzman, and ever" showed a spectacular decrease in the amount of long-range order retained by initially ordered Cu3Au when the shock pressure was raised from 290 to 370 kbar. Since Dr. Holtzman and I suspected that this behavior probably was due to the onset of a shearing stress in the shock front in Cu3Au which exceeded the limiting shear strength of the perfect crystal. it was considered appropriate to examine directly the shock-front equations for a solid. and to obtain a sound estimate of the shearing stress occurring in the front using equation of state data obtained from shock studies. In this paper an estimate is made of the

Jan 1, 1965

By E. A. Lucero, H. E. Robbins, T. H. Dudley

EL Salvador mine of Andes Copper Mining Co., E subsidiary of Anaconda Co., is in northern Chile about 18 miles north of Potrerillos, 7825 ft above sea level. Initial production is planned for the first half of 1959. Plant capacity will be 30,000 tpd, and there are 308,835,000 tons of proven ore reserves, averaging 1.49 pct Cu. The Inca adit is being driven as part of the mine-to-mill haulageway. Because of the overburden it is planned to mine the deposit by block caving. Ore will be dropped from upper gathering levels through ore passes to the Inca adit, through which it will be transported out of the mine to the primary crushing plant located a half mile from the portal.

Jan 3, 1958

By Frank C. Schrader

Page Introduction.............................. 196 Geology of the District......................... 196 Ore Deposits of the District....................... 198 Gcncral Description........................ 198 The Cerbat Mountains Group................... 199 General Description...................... 199 Tennessee Mine....................... 203 Midnight Mine........................ 203 Mineral Park........................ 204- Golconda Mine........................ 204 Other Ore-bearing Districts.................. 205 Lost Basin District ...................... 205 The Black Mountains Group.................... 206 Tom Reed-Gold Road District...................... 208 General Dcscription........................ 208 Development........................... 209 Topograplly............................ 210 Geology.............................. 210 Ore Deposits........................... 213 General Dwcription...................... 213 Zones.......................:....215 Structure of Ore Shoots.................... 217 Gold Road Mine ......................... 218 General Description...................... 218 Geology........................... 218 Ore Deposits......................... 219 Tom Reed Minc......................... 222 General Description..................... 222 • Ore Deposits.......................... 222 Development......................... 223 Character of Ore....................... 224 Other Mines........................... 224 Fields Similar to the Ton1 Reed-Gold Road District......... 227

Jan 1, 1917

By AIME AIME

LEWIS EMANUEL YOUNG was elected a Director of the A.I.M.E. at the last Annual Meeting as a representative of District '4, including. Ohio, West Virginia, and western. Pennsylvania and New York. He also represents the Coal Division, in which industry lie has actively participated- for nearly twenty years. Dr. Young was horn in Topeka, Kan., Oct. 1, 1873, received mining degrees from Penn State and ,-Iowa. State, and a Ph.D., from Illinois. The first part of his professional life was spent in teaching first as instructor in mining at Iowa State, second .as professor of mining at the Colorado School' of Mines, third as director of the School of Mines and Metallurgy at Rolla, Mo., and finally he taught business

Jan 1, 1937

Conquista, the uranium mining and milling complex owned jointly by Continental Oil Co. and Pioneer Nuclear, Inc., has begun operations in Falls City, Texas. The mill has been designed to produce 1.5 million lb of U3O, from 600,000 tpy of ore mined. Currently, the plant processes a maximum 2000 tpd of ore. Mine Planning Texas ore deposits are small and scattered in comparison to other uranium mining districts. Those to be mined at Conquista range from a few acres to more than 100 acres in size. Ore thickness ranges from a few inches to over 15 ft, and depth from less than 20 ft to more than 170 ft below ground surface. Distance from the mill ranges up to 35 mi.

Jan 8, 1972

By J. M. Duke, A. J. Naldrett

Significant resources grading less than about 1% nickel occur in magmatic sulfide deposits of two types. In the Mt. Keith type, extensive zones of disseminated nickel sulfides occur in the central portions of certain synvolcanic dunite-peridotite sills of komatiitic affinity in Archean greenstone terranes. In the Duluth type, disseminated copper-nickel sulfides occur near the basal margins of intrusions of flood basaltic affinity associated with intracontinental rifring. In both types, the parent magmas became saturated with sulfide following the onset of fractional crystallization and the separation of the immiscible sulfide melt was accompanied by the precipitation of a relatively large proportion of silicates. The abundant silicate crystals impeded the coalescense and accumulation of the sulfide droplets with the resulting formation of large but low grade deposits.

Jan 1, 1983

By D. W. Duncan, A. Bruynesteyn

An ore containing chalcopyrite was microbiologically leached in 6 ft columns at particle sizes ranging from -2 +1 ½ inches, to -3/8 + 3/16 inches. The rate of leaching increased exponentially as the particle size decreased. The controlling factor was the active leaching volume made up of the particle surface area and the depth of penetration of the bacteria and leach liquor into the particle. This volume became an increasingly larger part of the total volume as the particle size decreased. The sample under test leached poorly at larger particle sizes and it was calculated that under commercial conditions, it would produce at best a pregnant solution containing 100 mg/l (0.2 lb/ ton) of copper per 100 ft of dump height.

Jan 1, 1974

By Zhu Weishen, Xu Dongjun

In the 1st part of this paper a comparassion of the different methods for determining the modules of elasticity and deformation of hard rock is made. It is found that the plate bearing method has a serious shortcoming. The slit flat-jack method seems to be a mare reasonable technique, which is recommended as a desirable method for in situ testing. In the 2nd part, a new test method to determine the properties of deformation and strength of weak plane in rock mass is recommended. Then the relation of weak plane character to the character of stress-strain curve, the relation of normal stress to the character of shear displacement curve and the yielding criterion of weak plane are discussed.

Jan 1, 1982

By H. Conrad, K. Janowski, E. Stofel

In a previous paper,1 the occurrence of (0001) and (0111) twins was reported for compression tests of 60-deg-oriented sapphire rods in the temperature range from 1100° to 1300° C. Subsequent to this initial work, additional tests have been conducted, and twinning has been found to occur at temperatures as high as 1500° C. Also, the temperature and strain-rate conditions for the two types of twins and for slip have been established in more detail. The present note covers this more recent work. The compression-test data are summarized in Table I. The techniques for identifying the twins are optical examination up to X1000 and X-ray analysis.' It is evident that (0711) twins are pre-

Jan 1, 1965

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Vito J. Colangelo

The primary object of this study was to determine the effect of ferrite and its orientation upon the mechanical properties of a precipitation -hardening stainless steel with particular attention to the short-transverse properties. The investigation consisted of Jour major parts : the preliminary investigation of billet properties, the effect of forging reduction and ferrite content upon mechanical properties, the effect of notch orientation upon impact strength, and the relationship of heat composition to ferrite content. Low ductility and impact strength in the short transverse direction were found to he associated with the orientation and shape of- the ferrite plates. It was also determined that impact strength varied with notch orientation. The test values obtained with the notch perpendicular to the plane of the ferrite plate were lower than those obtained in the notch-parallel condition. The over-all investigation showed that high ferrite contents in general had a deleterious effect upon mechanical properties and that the ferrite content could he minimized by exercising rigorous control of the heat composition. A careful balance of elements, nitrogen in particular, must he maintained in order to reduce the formation of ferrite. THE precipitation-hardening stainless steels were developed to fulfill a need for high-strength corrosion-resistant alloys. In the annealed condition they are soft and ductile and possess many of the desirable characteristics of the austenitic stainless steels. In the hardened condition, the alloys exhibit the high strength and hardness of the martensitic stainless steels. The alloy under consideration in this investigation has a nominal composition as follows: C Mn Si Cr Ni Mo N 0.13 0.95 0.25 15.50 4.30 2.75 0.10 The hardening mechanism is identical to that of other hardenable steels in that it depends upon the transformation of austenite to martensite. This alloy because of its annealed structure and its ability to be hardened combines the desirable forming and corrosion properties of the austenitic grades with the high hardness and strength levels attainable with the hardenable grades. The reason for this apparent duplicity of proper- ties can be explained by considering a basic metallurgical difference between the hardenable stainless steels and those of the austenitic group. Both types are austenitic at 1800°F but, while the martensitic grades transform to martensite upon rapid cooling to room temperature, the austenitic grades remain austenitic even when cooled to temperatures below room temperature. The major difference then is in the degree of austenite stability. This stability can quantitatively be described by the Ms temperature. The Ms is defined as that temperature at which austenite begins to transform to martensite. The austenitic grades for example may be cooled to -300°F without producing significant quantities of martensite. The hardenable stainless steels on the other hand have an Ms temperature in the vicinity of 400" to 700°F. In cooling to room temperature, these alloys traverse the entire Ms-Mf range and show almost complete transformation to martensite. The semiaustenitic stainless steel, however, occupies an intermediate position with respect to its austenite stability. The analysis is so balanced that the Ills temperature lies at or slightly above room temperature. The resulting alloy retains much of its austenite at room temperature and yet responds to hardening heat treatments. Achieving this delicate balance of elements is therefore of great importance. Slight imbalances of the equivalent Cr-Ni ratios frequently result in the presence of 6 ferrite. It is the effects of this ferrit with which we are concerned, more specifically the effect of the quantity and ferrite orientation upon mechanical properties, particularly ductility. PROCEDURE A) Preliminary Investigation of Billet and Forging Properties. In order to determine the effect of ferrite on billet properties, billet stock from three heats with various ferrite contents was utilized. Tensile specimens were obtained in the transverse and longitudinal directions from this material and heat-treated as shown in Tables I and 11. Forgings were made from these same heats, the purpose being to determine what effect, if any, the ferrite might have upon the mechanical properties. These forgings were made in such a manner as to elongate the ferrite in the longitudinal and transverse directions. The method of forging was as follows. A section was cut from a 6-in.-sq billet of Heat A and flat-forged to 1-1/2 in. thick. Working was done from one direction only with no edging passes as shown

Jan 1, 1965

By G. R. Leverant, C. P. Sullivan

To evaluate the effect of a dispersion of nondeform-able, incoherent, second-phase particles on high-strain cyclic deformation and fracture, recrystallized TD-nickel (Ni-2ThO2) and a commercially pure nickel, Ni-200, were fatigued under strain control at total strain ranges varying from 0.009 to 0.036. Relative to the Ni-200, the slip at the surface of the TD-nickel was more wavy and discontinuous due to the presence of the thoria particles. This made crevice formation (incipient cracking) within slip bands more difficult in TD-nickel than in Ni-200. Both materials cyclically hardened to a constant (saturation) flow stress which increased with increasing plastic strain amplitude. Cellular substructures were developed in both materials during cycling. The cell size in TD-nickel was controlled by the thoria particle distribution and was independent of plastic strain amplitude over the range investigated. The cell size in Ni-ZOO was larger than that in TD-nickel at similar plastic strain amplitudes and was a function of plastic strain amplitude. These results, together with the cyclic stress-strain curves for both materials, are discussed in terms of a model for fatigue strain accommodation at saturation recently proposed by Feltner and Laird. NUMEROUS fatigue investigations have considered the interrelation of slip character, dislocation substructure, and cracking in pure metals and solid-solution alloys. However, except for the studies of the low-strain fatigue of internally oxidized copper alloys1 and cast, dispersion-strengthened lead,&apos; little is known about the effects which small, incoherent, nondeform-able, second-phase particles have on cyclic deformation and cracking processes. Effects due to the particles alone are often obscured by a dislocation substructure introduced during thermomechanical processing of dispersion-strengthened metals. In the present study, recrystallized TD-nickel and a commercially pure nickel, Ni-200, were employed to evaluate the effect of a thoria dispersion on high-strai fatigue deformation and cracking at room temperature. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in.-thick stress-relieved plate which had been subjected to a proprietary schedule of thermomechanical treatments, and the Ni-200 as 3/4-in. bar which was subsequently annealed for 2 hr at 850°C in argon resulting in an average grain diameter of 0.05 mm. The compositions of these materials are given in Table I. The microstructure of the TD-nickel consisted of elongated grains parallel to the primary working direction with an average width of 0.16 mm, Fig. l(a). Many fine annealing twins were present indicating that the starting material was in a recrystallized condition; this supposition was confirmed by the absence of of any extensive dislocation substructure, Fig. l(b). Sheetlike stringers parallel to the rolling direction were occasionally seen both within grains and at grain boundaries. Some approximately spherical particles about 2 in diam, which may correspond to exceptionally large thoria particle aggregates, were also present. The average Young&apos;s modulus of the plate material in the rolling direction was 21.8 X 106 psi which is consistent with a {100}<001>recrystalliza-tion texture3&apos;* being prominent. In transmission microscopy, the 2.3 vol pct of thoria particles generally appeared to be uniformly distributed although some clusters, 0.1 to 0.3 in diam, of larger particles were observed as previously reported for TD-nickel sheet,5 and stringering of particles was present in some areas as welt. The average diameter of the thoria particles was 450A with a calculated mean planar center-to-center spacing of 2100A, as determined by quantitative metallographic analysis.= The 0.2 pct offset yield stress was 36,000 psi which agrees with the value predicted by the modified Orowan relation7 for edge dislocations bowing between thoria particles of the size and spacing observed in the present investigation. Fig. 2 illustrates the specimen design employed for the axial high-strain fatigue testing. Adapters were screwed onto the threaded portions of each specimen so that testing could be performed in the same manner as that reported for buttonhead specimens.8 Stressing was coincident with the working direction for both materials. The gage section of each specimen was electropolished and lightly etched prior to testing. The total strain was controlled, being varied between zero and a maximum tensile strain ranging from 0.009 to 0.036. In addition to these tests, a circum-ferentially notched TD-nickel specimen was cycled over a total strain range of 0.0075. The same strain

Jan 1, 1969

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,&apos; but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By David B. Brooks

Identified potential resources of lead and zinc are lower, relative to reserves, than the same ratio for other metals, Either there is little material below present grades or, if it exists, there are no data on it. The author examines both these factors in detail, and also introduces a third possibility. In their 1961 monograph, The Future Supply of the Major Metals, Bruce Netschert and Hans Landsberg noted that identified potential resources (that is, known but submarginal resources) of lead and zinc were much lower relative to reserves (that is, known and supermarginal resources) than was the same ratio for other metals.&apos; Put another way, it seemed that for such metals as iron, manganese, copper, and aluminum, slightly more favorable economic conditions or modest advances in technology would greatly increase reserves by permitting the exploitation of vast quantities of leaner or deeper or otherwise less valuable mineral deposits. But for lead and zinc, Netschert and Landsberg concluded that either: "(1) there is relatively little material below present cutoff grades; [or] (2) such material exists, but for some reason there are no data.&apos;12 This situation, which they called "the lead-zinc anomaly&apos;&apos; has been subsequently discussed by other authors. The purpose of this paper is to carry the discussion further by examining the evidence in favor of (1) and (2) and by advancing a third alternative. There are at least two reasons for devoting time to the lead-zinc anomaly. First, while it is unlikely that we shall have to turn to alternative lead or zinc resources in the near or middle-term future, the longer run resource picture for the two metals is not so certain.3 Both within the United States and for the world as a whole, new discoveries will have to come at a fair pace to keep up with growing rates of consumption. Thus, it is important to see whether there exist lower grade or nonconventional potential sources of two such useful metals that we could turn to at some time in the future. The second reason for studying the lead-zinc anomaly is also related to resource adequacy, but is of more general significance. Depending upon whether the anomaly is technologic, geochemical, spatial, or temporal in origin, we shall be able to draw some conclusions about the resource picture for other metals. Can we expect the apparent pattern of lead-zinc resources to be repeated? If so, will technologic advances in either exploration methods or mineral processing be able to alter the pattern? Or is the pattern unalterably set by geochemical distribution? Most important, are metals characterized by what seems to be an anomaly, different in any way from metals for which low-grade or nonconventional sources already have come to be exploited, as the porphyry deposits have for copper. In sum, investigation of the lead-zinc anomaly represents a case study combining both physical and economic aspects that may open up a neglected area in evaluating mineral resource adequacy. WHAT IS THE LEALLZINC ANOMALY? There are two dimensions to evaluations of the potential of any mineral resource? The first involves the degree of certainty that we ascribe to the estimate: how much do we know about the size of the resource as a result of geological mapping, exploration, and mine development? This dimension is expressed by the terms measured, indicated, and inferred reserves (and, if you wish, &apos;undiscovered reserves&apos;), all of which terms carry with them the implication of exploitability under current cost-price conditions. The other dimension to evaluations of a mineral resource involves the economic limits of the estimate: how will the size of the resource vary with different (usually more favorable) cost-price conditions? (This economic dimension should be understood broadly to include all factors bearing on the cost-price relationship. In this sense it subsumes technology because any resource is exploitable at some cost; the role of technology is to bring cost down.) The latter dimension is expressed in the terms potential or sub-marginal &apos;ore,&apos; and is logically quite independent of the former. For example, we have relatively good measurements of the tonnage of manganese in low-grade deposits in this country, though they are too lean to be considered reserves; on the other hand, we are much less certain of our measurements of new lead and zinc deposits in Missouri, though there is no question but that there is a sizable reserve. Thus, it may be uncommon but is not a contradiction to talk of measured submarginal ore or inferred potential ore.

Jan 1, 1968

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide