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By W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.' This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.' This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By B. M. Larsen, T. E. Brower

An increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely, that which presumably is present in diffusible form in the solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent Oz in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,'who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By Nathaniel Herz

The formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D'Arey, as follows: D = cV w1l Where, D = the volume of compressed air delivered in cubic feet per minute, at the final pressure. c = an experimental coefficient determined for the various sizes of pipe, d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. p, = the initial gauge-pressure in pounds per square inch, p2 = the final gauge-preesure in pounds per square inch. w1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p1. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, cd5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the density of the air, w1, and often, for convenience, a table giving the values of the expressions p1-p2 and c J I hare constructed a graphic chart, Fig. 1, for the solution of

Jan 1, 1913

By G. W. Hodges

The Basic Oxygen Process shop at Gary Works is a three vessel shop tapping 220 ton heats. The larger portion of the heats are teemed into ingot molds with the remaining heats being continuously cast in a single strand continuous slab caster. Ingot production includes a wide range of carbon, alloy, and high-strength steels in many ingot sizes for bar, structural, plate and sheet and tin products. Individual ingot weights vary with the number of ingots per heat ranging from a high of 48 to a low of five. Caster production is primarily Riband, a proprietary low carbon grade for sheet and tin applications developed by United States Steel for continuous casting; some Riband steel is vacuum degassed prior to casting. Maintaining a satisfactory level of ladle performance on both ingot and caster heats with a high production rate and widely varied product mix is a demanding and exacting job requiring the best of equipment, materials, and, most importantly, personnel. The improving trend in ladle performance in the No. 1 BOP shop at Gary is due to a combination of factors, which will be described in the following presentation.

Jan 1, 1972

By Ralph Arnold

LESS than eight months ago at the annual meeting of the American Institute of Mining and Metallurgical Engineers, attention was called to the demoralizing effect of the abnormal oil production of Mexico on the oil situation in the United States, and it was predicted that this unstabilizing influence would probably become impotent in 18 to 24 months through ' the exhaustion of the principal producing fields of Mexico, unless new fields were found in- the meantime. When this statement was made, the daily production of Mexico was about 600,000 bbl. of crude oil; now it is about 350,000 bbl. No new pools of consequence have been opened, although extensions have been made to two old pools. Over 200,000 bbl., or more than half of the present daily production, comes from Los Naranjos, Amatlan and North Zacamixtle fields, in which practically every well is so affected by salt water that the potential production dropped 50 per cent. in the month of September, clearly indicating that these fields are moving rapidly toward extinction. How much longer the one remaining important pool will last is a matter of conjecture.

Jan 1, 1921

By R. W. Raymond

AT the Pittsburg meeting of the Institute, in March, 1910, the death of Mr. Metcalf was announced, and Col. H. P. Bope, of Pittsburg, delivered in memory of him a brief but eloquent address, which, though expressing the sorrow of Mr. Metcalf's friends, and, in general terms,. the debt of gratitude which his country and his profession owed to him, was not intended to be a complete survey of his life and work. With Colonel Bope's permission, and with the aid of some of the statements in his address, I substitute for it, in our Transactions, this more detailed, yet still inadequate memorial. As Colonel Bope justly remarked, the men who could do justice to this theme-such men, as Jones, Chalfant, Bennett, Oliver, and Park-passed away before Metcalf, leaving him almost the last of the generation of great steel-makers who made Pittsburg the Sheffield of America, and who discharged a double function, as the rear-guard of the old metallurgical practice and the van-guard of the new. I knew many of them; would that I were better qualified to celebrate their achievements. William Metcalf was born Sept. 3, 1838, at Pittsburg, Pa., where his father, Orlando Metcalf, was an eminent member of the bar. At the age, of sixteen, he entered the Rensselaer Polytechnic Institute, at Troy, N. Y., from which he was graduated in June, 1858. Returning to his native city, he became an assistant engineer in the Fort Pitt Foundry, of which. he was made Superintendent in 1859. This famous establishment produced the largest castings and heaviest machinery then known in the United States;-and Mr. Metcalf's intense, intelligent and incessant study of his business prepared him as a manufacturer for a patriotic service to his country more valuable than, as a soldier, he could have rendered in the field. The call came in 1862, when the government needed, above all things, a supply of field, naval and siege artillery. The

Apr 1, 1911

By Edward K. Landis

Our Transactions contain so many suggestions of apparently trivial, yet really important, contrivances for the saving of time and

Jan 1, 1893

By Ronald W. Klusman, Erik B. Nelson

The Front Range portion of the Colorado Mineral Belt is an extensive area of mineralization with mining activity dating from 1859 with the discovery of large gold deposits. After an initial boom period and gradual diminishing production, present activity is restricted to molybdenum in Clear Creek County, uranium in Jefferson County, and several small operations extracting gold and silver in Clear Creek and Gilpin Counties. Gold and silver have dominated the production in the Front Range, though the complex mineralization created milling and smelting problems and it is postulated that considerable amounts of precious metals remain in the mine dumps. This area is plagued by a severe mine drainage problem, with Clear Creek most impacted by many draining mines and tailings in the basin. Boyles et al. Moran and Wentz, Wentz, Wildeman et al., have examined various aspects of the impact of mine drain¬age in the Clear Creek basin. The primary objective of this study was to collect data on the tailings, drainages, and leaching experiments in order to make preliminary suggestions for reducing the impact while recovering metal values to offset treatment costs. A variety of leaching experiments were performed on tailings from the Nevada Gulch area in the Central City mining district. Leachings were performed in vertical tubes indoors and wooden boxes exposed to the outside environment. In the leaching experiments, the leaching solution, grain size, and residence times were varied, while forced aeration was used in some experiments. Bacterial nutrient 9K° and mine drainage were used in some of the experiments. A total of 14 additional tailings samples were analyzed for base and precious metals. The composition of the mine drainage and tailings used in the leaching experiments, as well as data on the additional samples are shown in [Table 1]. Leachate samples were taken periodically for analysis until compositions leveled off. Results and Discussion Leaching with distilled water was used as a control and best illustrates the basic behavior of the leaching process for zinc in a vertical tube [(Fig. 1)]. More acidic leachings increased concentrations of metals as did smaller grain sizes, though the time required increased significantly. Mine drainage with its high concentration of dissolved iron sometimes decreased the heavy-metal concentration in the leachate due to oxidation of Fe 2 and precipitation of Fe(OH)9 which absorbs some of the dissolved heavy metals. In the larger scale experiment carried out in the simulated leaching pad, substantial concentrations of metals were attained in the final leachate after one month. In this experiment the leachate was not recycled, but allowed to saturate the tailings continually with evaporation loss made up by additions of Quartz Hill drainage and nutrient 9K. The concentration of the metals in the leachate and the increase over the input solution are given in [Table 2]. Heap leaching of low-grade copper and uranium ores is successfully carried out in many districts, enhanced by the metabolism of autotrophic bacteria of the Thiobacillus-Ferrobacillus group. These ubiquitous organisms enhance metal leaching, and general aspects of heap leaching are discussed by Malouf, Trudinger, Pings, and Duncan et al. Conclusions and Recommendations Returning to the primary objective, how to reduce the mine drainage impact and recover metal values, we need to consider how the data may suggest avenues toward this objective. Boyles, et al., considered various

Jan 1, 1977

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy's flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,' in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.' Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe's treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.' This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By R. G. Weavind, R. S. Young, I. Wolf

ONE of the most important fields of investigation at the Diamond Research Laboratory in Johannesburg is concerned with improvements in metallurgical practices for the diamond mining companies, with particular reference to increased recoveries of the smaller industrial stones. Considerable work has been done on the possible application of flotation processes to the diamond industry. From the viewpoint of recovery processes, diamonds in their natural state may be grouped into two classes, the water-repellent diamonds, which adhere to a grease surface, and the water-avid diamonds, which, because of their wettability, will not adhere to a grease surface and must be recovered by means other than the grease tables used for water-repellent diamonds. Experiments in the flotation of small diamonds from both kimberlite and alluvial deposits indicate the following conclusions: Water-repellent diamonds: Satisfactory flotation of —16 mesh diamonds, which are naturally water-repellent, may be accomplished using either Aero-float 25 together with cresylic acid, or Du Pont B23 as frother together with kerosine as auxiliary oily conditioner or froth stiffener. The quantities of reagents required are of the order of 0.15 lb per ton Aerofloat and 0.18 lb per ton cresylic acid. The use of acid circuits is detrimental, and for best results a pH between 7 and 9 should be maintained. R. G. WEAVIND and I. WOLF are with the Diamond Research Laboratory, Johannesburg, South Africa, and R. S. YOUNG, Member AIME, is Director of Research, Diamond Research Laboratory. TN 76B. Manuscript, March 23, 1951. A flotation period of 5 to 10 min is necessary to insure that all floatable diamonds are removed. Diamonds larger than 16 mesh cannot be recovered satisfactorily by flotation. Xanthates do not act as collectors for diamonds, and this is probably associated with their inability to impart a water-repellent surface to this mineral. Water-repellent diamonds smaller than 28 mesh can be floated quite well by the addition of a frother alone, such as pine oil or Du Pont B23. Water-avid diamonds: Partial flotation of the smaller sizes of wettable diamonds can be achieved by preconditioning with fatty acid soaps, cationic amines, and similar reagents, which will impart a water-repellent film to diamonds. Washing to remove excess reagent, followed by flotation, will result in a fair recovery, but the latter is much lower than for water-repellent diamonds. Crushed boart: Recovery of crushed boart from the waste products of industrial uses is best accomplished by first conditioning the diamonds present in the mixture with fatty acids, cationic amines, etc., removing the conditioning agent by washing, and floating in a cell of the pneumatic type. Flotation reagents found to be most suitable are Du Pont B23, and Aerofloat 25 together with cresylic acid. The optimum quantities are 1.2 g Du Pont B23, and 0.55 g Aerofloat plus 1.4 g cresylic acid, per liter of pulp in the cell. A solids-to-water ratio of 1 to 4 is found to be the most suitable, and alkaline circuits are necessary for best results. Diamonds larger than 28 mesh are not recovered satisfactorily by this procedure, but for finer sizes flotation offers an excellent procedure for the reclamation of this strategic industrial material.

Jan 1, 1952

By Edgar G. Tuttle

The accompanying figures show a jig arranged for separating the middle product or middlings obtained in the concentration of certain ores, minerals, coal, etc. In the preparation for sizing, prior to jigging, of ore-bearing minerals, coal, etc., with their impurities, it is generally desirable to avoid reducing them to unnecessarily small sizes. Where the impurities adhere to the mineral particles or are disseminated through its mass, it is generally necessary to crush to such a fineness as will unlock the minerals from the gangue. If a considerable proportion of the material consists of mixtures of the minerals and gangue, each in large size, and a lesser proportion consists of a mixture of the two, in smaller sizes of various dimensions, it is not always desirable to reduce the whole to such size as would be required to liberate completely the pieces of ore and gangue in the finest mixtures. In such a case it is preferable to reduce all the material to such an

Jan 1, 1897

By Carl W. Volz

NORWAY'S metallurgical development, which has extended over many centuries, is intimately associated with that country's unique topography and climatic conditions. It is a rugged mountainous country, with a most irregular shore line, bordered by thousands of islands forming a natural protection for shipping. There are an endless number of lakes, and innumerable rivers and waterfalls, many fed by glaciers and melting snow. Rainfall is abundant. Though half of the country is north of the Arctic Circle, it is warmed by the Gulf Stream, so that the average temperature is about 45°, or 20° higher than other parts of the world in the same latitude. A sub-

Jan 1, 1935

By William Y. Mo

The OPEC oil embargo and the subsequent higher prices for oil have drawn public attention to the critical problems associated with security of supply of oil and other key industrial materials, especially nonfuel minerals. This concern has stimulated the interest of decisionmakers in analyzing policy options to cope with the emergency situations resulting from a sudden foreign- induced supply interruption or a cartel price increase. Several policy options are available to counteract foreign-initiated embargoes or cartel price actions. The type of response will differ depending on the commodity action intiated. A mathematical model that measures the impact of foreign-induced commodity actions on the domestic economy is formulated. The paper also presents a computer method that can be used to determine the optimum policy response to counteract such actions.

Jan 1, 1977

Albert Arents, Alameda, Cal.: From Mr. Furman's description of his crucible-assays I infer that he regards iron nails as a necessary or advisable adjunct. Against such a notion I must beg leave to protest. Nails should not be used in

Jan 1, 1896