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By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By D. G. Wilder

D.G. Wilder I found the suggestion that the amount of displacement of a fault can be numerically related to the thickness of gouge or breccia to be both intuitively satisfying and intriguing. I have long agreed that there is some type of relationship between the amount of gouge and the amount of displacement of faults. I congratulate the author for developing a numerical relationship between them. However, I am concerned that the limits for applying this relationship be fully understood. An underlying assumption in this approach is that there is either a uniform thickness of gouge or breccia along a given fault or the thickness does not vary widely. Since it is not always possible to confirm this, the displacements derived by this method should be viewed with caution unless significant fault extent can be observed. At the Nevada Test Site, in drifts constructed in granite for test emplacement of spent nuclear reactor fuel, we found a fault with 0.3 to 0.4 m (12 to 16 in.) of clay gouge. Within a few meters of this location, the fault had no clay gouge, but rather consisted of a highly fractured zone with significantly altered rock and some slickensides. Based on Fig. 1, the 0.3 to 0.4 m (12 to 16 in.) thickness of gouge would indicate a displacement in excess of 30 m (98 ft). However, no gouge thickness would indicate essentially no displacement. Based on a quartz vein that terminated on the fault, and is not identified nearby, an estimated displacement of more than a few meters was made. This estimate is consistent with that obtained using the regression line proposed in the paper if the 0.3 to 0.4 m (12 to 16 in.) thickness for the gouge is used. However, using the regression curves with zero thickness would not yield results consistent with what was observed in the field. Therefore, it is important to recognize that the suggested procedure would properly yield a range of probable displacements. ? *Work performed under the auspices of the US Department of Energy by the Lawrence Livermore National Laboratory under Contract W-7405-Eng-48. Reply by E.C. Robertson It is certainly true that the t (thickness) of gg-bx (gouge and breccia) on a fault does vary along the fault. My observations have been that near the termination of a fault, the displacement d is small and the t is also small, whereas the maximum d and t will usually be found in the central part of the fault. The information on gg-bx and t of the fault found in granite in the NTS tunnel by Mr. Wilder could be interpreted somewhat differently than he does. He speaks of the fault changing within a few meters from 0.3 to 0.4 m (12 to 16 in.) of clay gg to "a highly fractured zone with significantly altered rock and some slickensides," but no gg. The highly fractured rock may be taken to be bx, rock not so finely ground as gg but still crushed by the fault movement, equivalent to the gg in my usage, and probably occupying about the same t. Mr. Wilder's estimates for the fault in the NTS tunnel for t of 0.3 to 0.4 m (12 to 16 in.) and for d of a quartz vein, in excess of "a few meters," would place the point on the low side of the central trend line in my Fig. 1, at the lower limit. There is, of course, a problem with determining d using displacement of only one planar surface. It would be greater or lesser depending on the rake of the movement. Finally, estimating the d of a fault from its t should be made with awareness of our present uncertainties, as pointed out by Mr. Wilder. Although the central trend line in my Fig. 1 has a ratio of d/t of 100, I have put the limiting ratios at 10 and 1000. Understanding of the values of the ratio will be improved only with collection of more data, for which the discussion of Mr. Wilder is much appreciated. ? G.C. Waterman E.C. Robertson's paper provides significant information to a geologist attempting to deduce fault offset by noting the products of structural dislocation. However, considerable mapping in underground and open-pit mines, and examination of structures produced in different geological settings, have convinced me that gouge and breccia thickness are controlled by geological conditions and fault movement. The following paragraphs suggest geological variables that control them. 1. Depth of Loading A near-surface fault resulting from tensional stress has more breccia/gouge than is produced by a similar stress at considerable depth. A deep-loaded compressional stress may produce a linear zone of schist, or structural dislocation may occur along an earlier formed belt of schist. Such "shear zones" are common in Canadian mines in precambrian rocks. In neither case can offset be directly deduced by an analysis of the minimal gouge/breccia in the shistose rocks. At greater depth, stress may be partially to wholly relieved by flowage. I vividly recall first noting the regional "Midas Thrust" in the Lark mine, Bingham Mining District, UT (where we called the structure the North Fault). My recorded notes, as I remember them, showed a narrow gouge streak separated the "Jordan" and "Commercial" limestone units from impure, muddy limestone beds of uncertain stratigraphic position. The visible structure did not indicate the great importance of this premineral fault

Jan 1, 1985

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 Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By B. J. Kochanowsky

The idea of a portable crusher is not new. Many such crushers are available but they are small and designed for construction work. For many years the author has suggested, both in this country and in Europe, the building of larger portable crushers intended expressly for use in quarries or open pits. Although not applicable under all conditions, there are mining operations where a mobile crusher arrangement could be more profitable than the facilities now used. The primary use of a portable crusher, i.e., a crusher mounted on crawlers or tires, in the rock and mining industries is to reduce costs by permitting the substitution of conveyor belt haulage for truck or track haulage. The usual sequence of operations in surface mining is drilling, blasting, loading, haulage, and crushing. Haulage is normally accomplished by truck or track-mounted cars, the latter method being used for the longer distances. However, by using a portable crusher in the pit, the sequence of operations would be changed so that the crushing stage would occur before haulage (Fig. 1). Such a sequence would permit the use of conveyors to replace the more expensive truck or track haulage methods. Since most quarry and open pit operations normally require a crushing stage, the only additional costs incurred will be due to the investment required to purchase or construct a mobile arrangement for a crusher. But this factor has to be weighed against the advantages to be gained by conveyor haulage. As shown in Fig. 2, transportation of material by belt conveyor over short distances is less expensive than by truck. The inclination of the belt has no effect on belt speed; consequently, the hourly tonnage moved remains the same. Conversely, the output rate of trucks as expressed in tons or ton-miles per shift decreases proportionally to the haulage speed, which is considerably slowed by the steepness of the road (Fig. 3, left). Although maximum possible grades and maximum economic grades of haulage are greater for a belt than for a truck (over the same total lift), the longer haulage distances favor the use of trucks. Although power consumption for hauling on a grade increases for both conveyances, the rate of power consumption increases faster for trucks than for conveyor belts (Fig. 3, right). Since the output rate and related fixed costs are affected by the travel speed, total haulage costs with trucks would increase with the grade more rapidly than the similar costs of conveyor belts (Fig. 4). Travel distance, road grade, speed, size and number of pieces of equipment, efficiency of operation, and many other factors affect such haulage costs. In general terms it can be said that the shorter the distance, the steeper the grade, and the greater the output, the more advantageous the belt becomes in comparison to truck or track haulage. In addition to potential cost savings in haulage procedures, a portable crusher would allow better utilization and performance of shovels. Loading operations would not be interrupted as often by the necessity of waiting for cars or trucks. Unfortunately, the application of belts in open pits for haulage from bench sites is generally not practical under existing conditions because a belt fed directly by a mechanical shovel can be torn, damaged, or worn out quickly by the large rock fragments falling on it during loading. However, by using a mobile crusher this situation can be avoided. As shown in Fig. 1 (b), the shovel feeds rock into the crusher located behind it. The crushed material is initially transported by an extensible and/or movable belt, thence by a longer stationary conveyor to the plant where the material is subjected to further treatment by secondary crushing, screening, etc. The first-mentioned conveyor, needed to bridge the distance between the shovel and the stationary conveyor, is necessarily variable in length owing to the continuous movement of the shovel and the desire to keep the stationary belt at a safe distance from the bench during blasting operations. The remarkable part of mobile crusher operations is the extra-ordinarily high output per man-shift, the low maintenance and power requirements for haulage, and the increased output of the loading shovel. A cement quarry which has been using a portable crusher and conveyor since 1956 requires only three men to operate the shovel and crusher and to transport the crushed rock by belt from the quarry face to the screening plant. If truck haulage

Jan 1, 1961

By Claude P. Heiner

mountain region to M tht Coast points for domestic consumption and for export are shown in Table 11. There is considerable disparity in rates from both Rock Springs, Wyo., and Castle Gate, Utah, to the four coast cities where the slack coal is to be used for purposes other than export. The rate on coal to be exported is the same from either starting point to any of the four coast cities even though there is a difference of as much as 341 miles in the shipping distance. It is interesting to note that the freight rate between Sunnyside, Utah, and Fontana, Calif., on coking coal is $5.05 per ton and that coal up to 8 in. can be moved on this rate if it is suitable for coking. This rate was published late in 1942 on a contemplated annual movement of more than 500,000 tons. There have been decreases in freight rates since 1923 on movements of slack coal from Utah into Seattle and Portland due to pressure on the railroads and to greater. quantity of coal shipped. It is the author,', opinion that a movement of slack coal in excess of 3 million tons of coal per year from Utah to any point in central California would justify a freight rate equal to that puhlished for Fontana, Calif.. or $5.05 per ton. The movement of 3 1/2 million tons of coal per year on the basis of 240 mine working days per year would require that 14,600 tons be handled each mine working day. If it is assumed that shipments could be arranged for a 6-day week, the average railway movement would he 11,200 tons, or approximately 3 trains containing fifty-five 70-ton coal cars per day. Such movements of coal would require railroad equipment represented by the investment amounts stated in Table 12 and entail the services of 250 men. Table 12 ... Railroad Equipment and Investment Required To Move 11,200 Tons of Coal a Day from Utah to California Railroad Equipment Cost 2800. 70-ton coal cara at $6.000 each $16,800.000 32 locomotives at $310.000 each. 9.920.000 Miscellaneous eauiument:.......... .5;000:000 Total........................ $31,720,000 It therefore appears that, under presently known mining methods, the lowest price at which coal could be sold f.0.b. the mine in amounts of 3 1/2 million tons per year for generation of power in central California would be $4.60. It also appears that the lowest freight rate that could be expecled between intermountain points and the central California area would be $5.05 per ton, making a total cost of coal delivered at a plant site of $9.65 per ton. Conelusions The following are the author's conclusions: 1. Coal mines in Utah and in the Kemmerer and Rock Springs districts of Wyoming could increase annual production by 6 1/2 million tons per year. 2. Under present conditions coal could probably be delivered to any steam electric plant in central California at a price not to exceed $9.65 per ton. 3. The use of coal at such a price, while higher than the equivalent present price of fuel oil, is entirely feasible. 4. There are adequate railroad facilities for movements of large quantities of coal from the intermountain region to the Rest Coast. 5. In a national emergency it probably would be extremely difficult, if not impossible, to obtain sufficient oil to meet requirements of the greatly expanded West Coast steam electric generatsing capacity. 6. The intermountain region contains ample coal reserves to supply all conceivable demands for West Coast power generation for a number of generations. 7. Increasing demands of labor threaten to lessen, if not eliminate, savings in cost of coal production through the use of new mining machinery. 8. Continuation of experiments in socialism by the Federal Government through construction of hydroelectric generating plants, particularly those unrelated to land-use reclamation, defies justification. Rates under this concept of a governmental function are subsidized through greater taxation of its people. Private capital is available to construct steam plants, or hydro plants where feasible, and should be permitted to continue in order to preserve the principles of our free enterprise system. DISCUSSION (L. C. McCabe and Robert P. Koenig, presiding) C. C;. BALl*—I was asked to lead off the discussion, but it is not with the thought that I might be able to add anything to the paper. The thoroughness with which it was prepared rather forestalls the asking of many questions. Your treatment, Mr. Heiner, is a very valuable contribution. I do want to suggest—that although you have limited your study to this specific question, with certain geographic limitations, many of the things in your paper apply just as well to the eastern coals. I want to agree 100 pct with your final conclusion concerning government-subsidized construction. Id. C. McCabe*—It is certainly worthwhile to take stock occasionally to see where we are going in problems of this nature. I agree with Mr. Heiner that ultimately the only reliable source of fuel that the West Coast has is coal hut the time factor is the difficult element to evaluate. Just before I came here I discussed this subject with N. B. Hinson, Vice President and Executixe Engineer of the Southern California Edison Company, and Chairman of the West Coast Inter-Power Exchange Committee. He has given much thought to utilities' fuel supply and it was very helpful to me in preparing a discussion of the paper to talk with him beforehand. Stock taking and forecasting of future development are essential to the continuing success of any enterprise. Mr. Heiner has called attention to the unprecedented growth of central and southern California and to the increased demands for fuel and power which have accompanied it. He discusses the increased fuel oil and natural gas requirements and the probable limits on the future use of these fuels and of hydroelectric power. In contrast to the calculable limits of these sources of electric energy, the author points to the availability of enormous reserves of coal in the Rocky Mountain States adjacent to the Pacific Coast which can be utilized for power generation. That there will be increased use of coal for power generation in the area under discussion is generally accepted hut it is in the timetable of such development that there is not complete agreement. In a recent report, Mr. Hinson reviewed the future power outlook for the Pacific southwest area. He pointed out that the use of steam plants in connection with water power plants in this region has made the maximum use of hydroelectric energy possible, and that the correct balance between hydro and steam generating plants produces the most economical overall system. Steam plants in the area which had been installed to protect against deficiency in hydro energy in dry years were used to carry war loads. Fortunately, no dry

Jan 1, 1950

By J. R. Dawson, J. A. Glunt

VESTA No. 4 and 5 mines supply most of the high volatile coal required for Jones & Laughlin's byproduct coke plants. Until 1944 all coal produced in these mines was loaded by hand. Pressure to mechanize at Vesta was brought on by the manpower shortage in World War 11, and in 1943 a decision was made to change to mechanical loading. It was the opinion of those concerned that by use of selective mining the coal would be clean enough to be processed by the existing preparation plants. At that time coal cleaning at Jones & Laughlin consisted of hand picking the larger sizes at the mine tipples and wet washing at plants located at the Pittsburgh and Aliquippa Works. A typical section of the Pittsburgh seam as it occurs at Vesta is shown in Fig. 1. The 14 to 16 in. of drawslate immediately over the coal is too soft to be used for roof and must be taken down, leaving the rooster coal just above for roof. In selective mining an attempt is made to mine the coal under the drawslate first and then load out the drawslate separately as refuse. In full seam mining slate and coal are shot down at the same time and loaded out. Mechanical loading at Vesta created new problems. It was found that selective mining, even when carefully applied, increased the refuse in the raw coal to such an extent that the washers at the mills were unable to handle it. Large tonnages of refuse were being transported, a reject disposal problem was created, and good metallurgical coal was being loaded out and lost. In addition, the selective method handicapped operation of the loading machines. Fig. 2 shows how the ash content of the raw coal increased as mechanization proceeded at No. 5 mine. New Preparation Plant: After an exhaustive study of this situation by J & L management, is was decided that a preparation plant should be constructed at the mines, capable of handling full seam mined coal and large enough to process full production of both No. 4 and No. 5 mines. It was decided that from the standpoint of inside operation and haulage the new plant should be located as near as possible to the old No. 5 tipple on the Monongahela River near Vestaburg. Full seam mining at Vesta could be expected to produce a tremendous volume of refuse along with the coal, since 14 to 16 in. of slate would be mined with an average 78 in. of coal. Disposal of this refuse required serious consideration in selecting a plant site. The only area near Vestaburg large enough for disposal of the plant refuse was across the Monongahela River at LaBelle. Ample space was available here, and construction at this location would not interfere with operation at the No. 5 tipple. It had been noted over the years that the sulfur content of the coal produced at Vesta was gradually increasing, and there was every indication that this increase could be expected to continue as the mines developed further from the river. It was decided to construct a three-part separation plant with complete blending facilities to produce both metallurgical and steam coal. In this system an attempt is made to reduce the sulfur in the metallurgical coal in a secondary cleaning process. Construction of the new preparation plant got under way early in 1947 and continued until the spring of 1950. The plant was designed to handle 2400 tph of raw coal containing 30 to 35 pct refuse. Cost of outside buildings and equipment was about $14 million. Total cost of the plant, together with improvements and changes made at this time, was approximately $21 million.

Jan 1, 1957

By A. D. Hughes

A relatively small area in Malaya, about 200 miles long by 40 miles wide, is the most important source of tin in the world. Some tin is recovered in other parts of the peninsula. Of the tin mined, 98 pct is recovered from alluvial deposits. From 1935 to 1941 the average annual world production of tin was 190,000 tons. The average annual production from Malaya during the same period was 62,000 tons or about one third of the total. Other producing countries, in order of importance, were the Netherlands East Indies 34,000 tons, Bolivia 30,000, Belgian Congo, Nigeria, Siam, Burma, China, and a few others with smaller amounts. The serious shortage of tin during the war period was due to the fact that the Japanese were occupying Malaya, Netherlands East Indies, Siam, Burma, and China which, together, formerly were producing 65 pct of the world supply. Because of the importance of tin in the world economy, and because of the fact that little is generally known in this country regarding the methods of recovering the tin in Malaya, it is believed that a short description of the industry, as carried on there, may be of interest to many of the readers. In addition you may be interested in the effect of the Japanese occupation, subsequent recovery of the properties and conditions existing at that time. The Malay Peninsula lies at the southeast tip of Asia. Singapore, a British colony, is situated on a small island at the southern end of the peninsula. It is a city of nearly a million population, an important world port, the site of a large British naval base and of one of the tin smelters. The Federation of Malaya consists of nine states, plus Penang, Malacca, and other small areas formerly part of the Straits Settlements, and it now covers the entire peninsula. The civil administration is controlled by the British. A constitution was adopted recently after reaching agreement with the Malay Sultans of the various states, who retain control of religious matters. The Capital is at Kuala Lumpur, a city of about 200,000 population, 250 miles north of Singapore and about half way to Penang. The country covers an area of 51,000 square miles, an area about equal to that of Florida and about one third that of California. It has a population of about seven million consisting of Malays, Chinese, East Indians, and a relatively small number of Europeans. The principal products are tin and rubber. There are over three million acres of planted rubber. The country is not self-supporting agriculturally as about one third of the necessary food supplies is imported. Rice is the principal food of the Asiatic population and some of the recent unrest is caused by a shortage of rice and the consequent high price. Good highways have been built through the settled part of the country. A railway, Government owned, extends from Singapore northward through the entire peninsula. The climate is tropical but health conditions are good for a tropical country. I was in Malaya from 1939 until January 1942, during the time of the simultaneous air attacks on Pearl Harbor, Manila, Hongkong, and Singa-

Jan 1, 1950

By R. I. Lahring, C. G. Inks

A surfactant waterflood, using a block copolymer of ethylene and propylene oxide (PLURONIC L64*), wa., started in 1956 in Kansas to determine the commercial feasibility of such a process. The production formation was the Bartlesville sand at a depth of 1,400 ft. Leares in the test area had attained both primary and secondary production peaks, and were on a normal decline when the tests were initiated. The injection wells were taking water at a reasonable pressure and none of the operating conditions were particularly unusual. The leases were selected primarily because of normal operating conditions, and not because of any serious problems demanding remedie>,. Oil production and water injection data were recorded during the 10-year test period, and their compilation indicates that the surfactant resulted in an increase of about 9 percent in secondary oil production. Other benefits derived from the surfactant injection were lower injection pressure that resulted in reduced power consumption and reduced erosion of the pumps; and lower calcium scale buildup. These fringe benefits more than offset the cost of the surfactant used. Introduction During the past several decades, considerable research has been carried out on secondary recovery of crude oil that remains in the producing formation despite the most efficient, current primary production practices. Methods are constantly sought of increasing recovery of oil, while at the same time improving the economic efficiency of operations. One method that has received intensive study over the years is the use of a surfactant as a waterflood additive. Laboratory tests show conclusively that dilute solutions of surfactants remove considerably more oil from uncon-solidated sand cores than does water alone.'- The loss of surfactant by adsorption at solid-liquid interfaces has caused serious doubt that surfactants can be used economically as waterflooding additives. This is especially true with anionic and cationic surfactants, and to a lesser extent with nonionic surfactants. This work was undertaken to determine the effectiveness in increasing oil production by injecting water containing small quantities of a nonionic surfactant. The surfactant selected was PLURONIC L64*, a block copolymer based on ethylene and propylene oxide, having the following structure The selection of the test site, a typical shoe-string sandstone type of field located at Batesville pool, Toronto District of Woodson County, Kans., was made because of its normal primary and secondary recovery operating conditions, and not because of any serious operating problems. When the tests were begun, the field was experiencing the customary post-peak production decline of a waterflood. Using for the tests a field that was on a normal production decline, while maintaining constant all variables other than the addition of the surfactant. was of varamount importance if success or failure was to be attributed to a particular cause. It was reasoned that if a surfactant was added to the injection waters and nothing else was done to influence the oil production or injection of water, the effects of the surfactant on the flood could be determined precisely. Production History The first well in the tested field was drilled in 1935. Gas repressurization began immediately, but it was not until Aug., 1938, that the major portion of the field was developed. During the period of repressurization, 1,700 MMcf of gas was injected. As can be seen from the curves of Fig. 1, the production peak from gas injection was attained in 1937 and a normal production decline followed. Early in 1942, water injection wells were drilled and injection of water Was initiated. The amount of water injected increased as more injection wells were drilled until a peak injection rate of 2,700 BID was reached in

Jan 1, 1969

By Arcy A., J. G. Davis, D&apos Shock

Results of a pilot operation in the Carlsbad Basin are discussed. After hydrafracing between wells, a block of potash was removed by solution techniques. The distance between frac wells was about 200 ft, the thickness of potash mineralization, 5 ft. By proper manipulation, a feed of concentrate brine was obtained. The ex-periment showed that the thin-bedded potash could be removed by the solution techniques. The details of well construction, method of operation, and removal rates are discussed. Continental Oil Co.'s laboratory research on the fundamentals of potash solution mining has been expanded by means of a series of field tests, and subjects such as well completion and hydraulic fracturing were added to the investigation. Both single-well and multi-well systems were studied in the field work. Discussion Background: The current paper discusses one field test in which potash was solution mined by a two-well system from a thin sylvinite zone. The potential economic value of solution mining evolves from (1) the use of drilled holes and solution techniques instead of excavated shafts and caverns and (2) the ability to mine both land and marine deposits through any type of overburden geology and below conventional mining depths. Recent interest has been focused on potash' and other soluble minerals, such as trona. Solution extraction minerals, such as copper and uranium, are also worthy of important consideration. In addition, many of the techniques are directly applicable to the construction of horizontal underground storage carverns in salt. There are two general approaches to potash solution mining. The first is to mine on a single-well basis, in which the same well bore is used for both injection and production. This method is slow, and the areal extent may be quite limited in other than very thick ore zones. The second, and the preferred approach, is to mine on a multi-well basis in which the solvent is circulated between wells. This technique, if applied in a manner which allows the ore zone to be mined from the bottom upward, results in nearly all the solution taking place from the cavern roof. Salt removal rates, therefore, are very much higher than from a single-well system.l Wells can be interconnected into a multi-well pattern by several means. One is to join single-well caverns in the lower part of an ore zone. Another is to use the hydraulic fracturing techniques developed in the oil fields.' We preferred the fracture approach because of its potential for creating the greatest area of salt exposure. Test Site Description: The field tests were conducted in New Mexico's Carlsbad Basin, where the potash deposits are flat and uniform over reasonable distances. Here, 12 potash zones are present in the massive Salado Salt section. The specific target was the Third Ore Zone which is about 4 ft thick at our location and about 1150 ft deep. The test pattern was designed in the shape of an equilateral triangle with a fourth well located in the center, 200 ft from each of the vertex wells. This configuration allowed the ore zone to be hydraulically fractured from the center well with good assurance that the fracture would intersect the bore of at least one outside well. Several multi-well test patterns would be available if the fracture connected all wells. Well Completion: Surface casing was set in the top of the Salado Salt at 600 ft to shut off water flows from the surface sands, and the salt section was drilled and diamond-cored to a point below the Third Ore Zone. A drilling fluid made of diesel oil with a small amount of emulsified water was used to drill and core the salt. This fluid was highly successful in preventing enlargement of the drilled hole and in promoting good core recovery. The three outside wells were completed by setting 51/2-in. casing at the base of a streak of anhydrite about 20 ft above the ore zone. Pipe was set high so that the intersection point of the fracture could be detected even if the fracture migrated above the ore zone as it progressed outward from the center well. The center well itself was completed by cementing 51/2-in. casing through the Third Ore Zone. Cement bond logs run on the center well have shown excellent bonding. Fracturing Practice: A mechanical tool was used to cut a notch through the casing and into the salt at a point about 1 ft below the ore zone in the center well. The purpose of this notch was to fix the point of fracture entry into the salt. The fracturing was done with water at injection rtaes as high as 30 bbl per min. The salt parted at 1450 psi; and it required only 5 min for the fracture to reach the well which was 200 ft to the south. It took about 5 min more to reach the other two wells. Caliper surveys were run to locate the point of fracture entry in the three outside wells. The fracture appears to have drifted downward slightly, entering the outside wells at the top of a streak of carnallite 8 or 9 ft below the ore zone. A cross section of the wells selected for the multi-well test is shown in Fig. 1. The figure includes KC1 values based on core analysis and the trace of the fracture plane between the wells.

Jan 1, 1971

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geophysics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining. Geophysics in Petroleum Exploration During the past twenty years, the petroleum industry has established an effective exploration technique. Geology is the basic tool in those areas where reliable predictions can be made from surface conditions. In the other areas, where the geological studies are inadequate, they must be supplemented with geophysics or direct exploration, such as drilling. Since geophysical work is far less costly than any form of direct explbration, it is used almost exclusively as the means for obtaining the desired subsurface information. The geological and geophysical techniques are credited with locating sites which yielded one producer for three dry holes during the year 1947.' For the wells located without geology or geophysics, there is a ratio of one producing well to sixteen dry holes. From these figures it is seen that the geological and geophysical techniques are more than four times as successful as the nontechnical exploration. It will be in order to consider further this ratio of one producer to three dry holes. The geophysical methods in use today† do not pretend to locate oil directly; their function is to locate anomalies or structures favorable for the accumulation of oil. For a producing oil well we must have not only structure, but also other favorable conditions, namely: petroliferous source beds, the required porosity and permeability in the reservoir rocks, an impermeable cap rock over the reser- voir, and the necessary water or gravity drive to force the oil into the bore hole. Since the geophysical work can only detect and sometimes delimit the anomaly, these other necessary conditions can be determined only by direct exploration. The success of modern geophysical work in locating and limiting the structure itself is remarkably high, probably over 95 pct accurate. Geophysical work renders an important service in the delineation of the structurally unfavorable areas and their elimination from the drilling phase of the exploration program. When attempting to locate any material of scarce occurrence in the earth, it is of paramount importance to know where not to dig. This elimination of barren areas is the least appreciated but is of great economic importance. For illustration, the difference between one producer to three dry holes, and one producer to sixteen dry holes, represents a saving of thirteen drilled wells, which would require an expenditure many times the cost of the geophysical work that might have revealed the nonfavorable structural conditions. The percentage of geophysically-located wells necessarily will continue to increase in the statistics of future years, as the search for oil is extended

Jan 1, 1950

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963

By Walter W. Lilly, Issa S. Oweis

Application of rock engineering in geotechnial consulting practice considered herein is in areas of: (a) bedrock verification for foundation support, (b) bearing capacity and settlements, and (c) excavations. A routine geotechnical investigation usually provides data on depth to rock, rock classification, and rock quality. In cases of rock outcrop, such outcrops are mapped for geologic structures and rock mass description. In addition, the regional geology and the general aspects of the groundwater regime are usually known from either published literature or previous experience. The predominant technique for ground and site investigation are usually drilling and geologic reconnaissance. Other techniques involving seismic and geophysical soundings, borehole camera, and oriented cores are used by by no means routine. Performing laboratory strength and compressibility tests is often made to be considered as routine. The use of the point load test is gaining increasing use in the United States and would, perhaps, become a routine field or laboratory test due to its simplicity and, more importantly, its relatively low cost. The purpose of this paper is to describe cases where mostly routine investigation and testing were used to arrive at engineering decisions. Bearing Capacity and Settlements The allowable bearing values for foundation support on rock is usually dictated by local building codes which presumably should reflect local experience. The interpretation of the code, however, can present a problem, especially if the interpretation is made by a designer under the delusion of knowledge in rock engineering. For

Jan 1, 1982

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets.1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741.3 Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name &apos;and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832.4 Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead," the zinc, and the rock or waste materials. The first record of zinc production from -the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons&apos; in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with, considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1952

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses&apos;-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7&apos;* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4&apos;5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By D. Geiselman, A. G. Guy

Single cvystals were grown from high-purity magnesium containing known amounts of nitvogen in the range 0.0008 to 0.0048 wt pet. Crystals of known ovientation were tested in tension in an Instron ma chine to determine the yield strength and to obsevue wheather a yield point occurred. Slowly cooled crystals or those given a solution heat treatment did not show a yield point. However, crystals that were aged following a solution treatment showed a yield point for all of the nitrogen contents studied. It was concluded that nitrogen caused the yield point by the Cottrell mechanism. NITROGEN has been shown to produce sharp yield points in single crystals of cadmium, zinc,2&apos;3 ß-brass,4 and iron,5,6 as well as in polycrystalline iron7 and molybdenum.8,9 Since magnesium has a structure similar to zinc and cadmium, it seemed reasonable that magnesium should also exhibit a sharp yield point provided it contained sufficient nitrogen. Bobalek and Shrader10 reported a total nitrogen content of 0.002 to 0.0065 wt pct in com- mercial magnesium alloys, an amount well in excess of that required by theory. However. magnesium differs from cadmium and zinc in that it forms a stable nitride, Mg3N2, which has a standard free energy of formation of -95,480 cal per mole at 25" c." If rather than being in solid solution, the nitrogen were predominantly combined as the nitride, it could not act to produce a yield point. This type of behavior is the basis for the elimination of strain aging and a yield point in steel by the addition of strong nitride formers such as titanium,12 columbium,13 aluminum,14 vanadium,15 and boron.16,17 Thus, there appeared to be factors both favorable and unfavorable to the production by nitrogen of a sharp yield point in magnesium, and the purpose of this investigation was to determine the actual behavior of magnesium crystals containing known amounts of nitrogen.

Jan 1, 1960

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.&apos; At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2&apos;4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz&apos;s work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.&apos; Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970