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By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Francis A. Thomson

But little has been written concerning the camp of Republic. In 1900 Chatard and Whitehead 1 reported the results of some experiments with samples of ore from the Republic mine, and a few years later Fritz Cirkel2 described the construction, operation, and results attained in the mill at the Mountain Lion mine. From time to time brief articles, mostly of a semi-technical nature, have appeared in the Engineering and Mining Journal and other mining periodicals. The general geology of the camp, especially in regard.to its areal features, has recently been ably described by Joseph B. Umpleby.3 To bring to mind the general features of the district it may perhaps be well to review briefly some facts in regard to it, before discussing the treatment of the ore. I. History and Production. The town of Republic is situated in the NW. corner of Ferry county, about 25 miles south of the International Boundary, on the head-waters of the San Poi1 river, in what was formerly the " north-half" of the Colville Indian reservation. On Washington's birthday, 1896, this portion of the reservation was thrown open to mineral location, and within a few weeks important discoveries had been made. The present Eureka mining-district was organized, the camp grew apace, and consignments of ore were shipped by wagon to Grand Forks, 30 miles away; or to Marcus, a somewhat greater distance. It is reported that the first 1,500 tons shipped from the Republic mine uetted the owners $160 per ton, after being hauled

Jan 1, 1913

By Frederick O?Neil

SCOPE OF THIS REPORT THE object of this paper is to describe the present status and possibilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the; iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. X. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Witherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 2, 1926

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By W. M. Reilly, Martin E. True, O&apos

A technique, equipment, and a compound have been developed and field tested for sealing tubing joint thread leaks without removing the tubing from the well. This eliminates the necessity of killing the well with possible damage to the producing formation, which could result if it were exposed to drilling mud. A thread sealing compound, developed and tested in the laboratory, is introduced into the tubing and squeezed into the joint to eliminate the leak. A high percentage of successful field applications have eflected an appreciable cost reduction in repairing leaking tubing strings in East Texas and in the Louisiana Gulf Coast area. INTRODUCTION In producing oil and gas wells the industry has been plagued with a never ending problem of tubing connection leakage. This situation is becoming increasingly more significant as more gas wells are placed on production and as higher pressures are encountered at greater depths of current drilling. Substantial progress has been made in minimizing thread leaks by careful handling and cleaning of joints and by the use of improved sealing compounds in combination with controlled makeup. But even with the use of the best known methods and sealing materials during initial makeup, occasional leaks through tubing joint threads appear inevitable. In some instances, tubing joints in high-pressure gas wells have been found to leak gas at relatively less pressure than that at which the tubing had been tested satisfactorily using liquid. Many expedients have been employed to prevent the physical replacement of tubing when leaks have developed. Perhaps the most commonly used is the sodium silicate treatment in which the solution is lubricated into the tubing to form a crystalline plug in the leak. Generally, any benefit realized is of a temporary nature. In addition to field studies on handling and makeup of tubing, extensive laboratory work has been undertaken on the development and testing of thread dopes.' Also, substantial effort has been devoted to testing tubing joints using high-pressure gas as a pressure medium.' The results of this work have emphasized that tubing joints are susceptible to occasional leaks, especially when subjected to relatively high differential pressures. To cope with the problem of leaking connections, an extensive investigation was undertaken to devise means of sealing leaks without removing the tubing from the well and without reducing the inside diameter of the tubing. The purpose of this paper is to present a technique, together with the associated equipment and compound, which have been developed for effecting a seal of leaking tubing in place. DISCUSSION Work was initiated simultaneously on two ventures: (1) to develop a satisfactory leak sealing compound and (2) to develop tools necessary to find the leak and place the compound. Leak Sealing Compound In the development of a sealing compound, tests were conducted on those compounds commercially available which include: (1) conventional thread lubricants, (2) thermo-setting resins and (3) other materials which held promise of effecting a seal. Although none proved completely satisfactory in their available form, two commercial compounds proved nearly equally effective in sealing leaks during laboratory tests after proportioned quantities of graded silica had been added. Field usage has indicated that the preferred compound is one prepared of an aluminum-stearate base thinned to the proper constituency and carrying a mixture of fine mesh graphite and graded silica. The compound developed by Humble Oil & Refining Co. is designated as Tubing Thread Leak Sealant 800. Placement Tools and Technique In developing tools to detect joint leaks and to place the sealing compound, work was done initially on wireline equipment. Preliminary designs were completed of a tool somewhat on the order of a pressure bomb to test individual joints with gas at high pressure to determine if the joint was leaking. An entirely different tool equipped with opposed packers was intended for placement of the sealing compound at high pressures in each leaking joint. The application of these tools

Jan 1, 1958

By W. A. White

UNDERCLAY squeeze is the plastic flowing of underclay below coal pillars into mined-out entries and rooms. Squeezes may be caused either by wet mine conditions where the moisture is taken up by the clay—making it more plastic—or by the presence of certain clay minerals, such as mont-morillonite, which are plastic when there is enough natural moisture. Under either condition, sufficient stress will cause the underclay to flow. Squeezes may fill an entry or room within several hours, or it may be several months before movement stops. Squeeze areas commonly cover hundreds or thousands of square yards. The Coal Div. of the Illinois State Geological Survey has collected samples of underclays from various mines and from cores drilled by coal companies in the state. From these samples natural moisture content, particle size and particle size distribution, and clay mineralogy are determined. Data from samples collected from the underclay below Herrin (No. 6) coal in the Lumaghi Coal Co. mine near Collinsville, Ill., are used in this report to clarify points in the discussion. Data from samples taken from other mines lead to the same conclusions. A generalized geological section for the area is given in Table I. The underclay below coal No. 6 ranges from a few inches to 3 or 4 ft thick. The upper 6 to 18 in. are noncalcareous; the lower part becomes more calcareous with depth. Limestone nodules become larger with depth, almost grading into the limestone below. In areas where the clay is nearly absent the limestone may thicken to take its place; thus they may complement each other in thickness. There are two types of squeeze areas in a mine. In one type up to 3 or 4 ft of underclay lie in what appears to be a depression in the limestone underneath. This is suggested by a rim surrounding the squeeze area where the underclay is thin and the limestone lies within a few inches of the coal. In the second type the underclay of the squeeze area is surrounded by underclay of similar thicknesses which does not squeeze. Test Methods: Natural moisture content, particle size and particle size distribution, and clay mineralogy were determined by the following methods: Natural moisture is the moisture content a clay contains in its natural environment, expressed in percentage of the weight of ovendried clay (110°C or 230°F). To obtain the natural moisture content, given in Table 11, the clay samples were sealed in containers as soon as the samples were taken in the mines. Particle size and particle size distribution were determined by the pipette method,' and the data were plotted as cumulative curves, Fig. 1, on semi-logarithmic paper. Particle size was plotted on the logarithmic scale and percentage on the arithmetic scale. The quartiles (diameters that correspond to frequencies of 25 and 75 pct) and medians (diameters that correspond to the frequency of 50 pct) of the samples were determined from these curves. The clay minerals were identified from the data obtained by differential thermal' and X-ray powder" techniques. The differential thermal analyses were made on the whole samples, whereas the X-ray analyses were made on fractions of less than 2p. Data and Discussion Moisture Content: After the sealed jars had stood for 24 hr, those that contained squeeze samples had perspired, so that droplets of water had accumulated on the insides of the jars. Table II shows the moisture in the clay after it had perspired for 24 hr. (This perspiring was not noted in samples from nonsqueeze areas.) After perspiration one of the squeeze samples still had a higher moisture content than the samples that did not squeeze. Clay Mineralogy: The thermal analysis, Figs. 2 and 3, indicates that the clay minerals are chiefly micaceous in type; the low-temperature endothermal

Jan 1, 1957

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By Carl F. Dietz, Dyke V. Keedy

The problem of drying ores is one that most mill-engvineers are sooner or later called upon to meet, and it may be timely to point out some of the difficulties resulting from such operations from purely a metallurgical and economic standpoint. We mean, in the following pages, to discuss primarily the effect of such operations on the ore. itself, without particular reference to the mechanical or cost features of the subject. That an appreciable tonnage of the ore fed to the usual form of drier, either rotary or stack, is lost, is fairly well appreciated, but we believe that only a few mill-managers know just what their drier-losses amouilt to, and we have found that in most cases they console themselves with the fact that the drier-smoke is not very much discolored, and it is generally believed that the draft is not sufficient to carry away more than a negligible percentage of the values.

Jan 1, 1913

By M. L. Requa

In the fall of 1910, the Nevada Petroleum Co., operating in the Coal-inga field in California, determined to drill a number of wells with rotary tools, in order to prove conclusively the relative value of the rotary as compared with the standard rig. At that time, the rotary was but little known in California and its proposed introduction met with considerable criticism on the part of the operators and quiet opposition among the standard drilling crews. There were few men available who were competent to handle a rotary outfit, and these few had had but little experience in California fields. Machines as then built were much inferior to those now used, being lighter in construction and of a poorer quality of material. The shells encountered at depths between 1,700 and 2,000 ft. seemed to be too hard to permit of successful drilling, and at these depths the rig was changed over to standard tools and by them completed. Because of the heavy depreciation, the time lost in converting from rotary to standard, and the comparatively small profit, it was concluded that unless in the future there was some material improvement in rotary rigs, nothing would be gained by drilling with rotary tools upon this property. Little or no drilling has been done upon the property since that time, but in the meantime a large number of men have been trained in the use of the rotary; in fact, many standard-tool men have abandoned standard drilling and, starting in as roustabouts, have become thoroughly competent rotary operators. The improvements in the machinery have been such as to remove many of the objections and the rotary drilling of to-day is in every way superior to that of 1910. In contrast, a well drilled recently by the Kern Trading & Oil Co., in the east side Coalinga field may be cited. The first 2,500 ft. was drilled in 24 days and it is confidently expected that the water string will be set with a rotary at 3,400 ft.—a record obviously far beyond that made in 1910 by the Nevada Petroleum Co. The records herewith are published with the hope that some one having more recent data will publish them so that comparison may be

Jan 1, 1915

By R. W. Young, Arthur F. Taggart

The tests herein described are part of an extended series of expel<ments, performed by the authors together with J. F. McClelland and L. W. Bahney, on the reclamation of metallics from foundry and manufacturing-plant scrap. The most obstinate problem encountered was the proper cleaning of the metal. Introduction In the manufacture of brass and brass products the weight of the finished product leaving the plant is much less than the total weight of. copper and zinc entering. A small part of this discrepancy is due to the unavoidable oxidation of the metals in melting, but by far the largest part of the loss is in the form of metallic particles of copper,. zinc, and brass. These losses occur principally at three points in the process: (a) in the casting-shop ashes; (b) in the slags from furnaces melting scrap brass; (c) in material spilled on the floor throughout the manufacturing process. The amount of these products in some plants is nearly 100 tons per 24 hours. Casting-shop ashes contain the metal spilled from the crucibles during melting and pouring, and the metal included in the slags formed in the melting process. The ashes also contain pieces of broken crucibles with adhering metal; 20 to 30 per cent. of unburned coal is also present. The metal in casting-shop ashes contains clean pieces of zinc or copper ingots weighing 1 to 2 lb., jagged pieces of metal of all shapes ranging in size from several inches down to the finest dust, and shot and botryoidal shapes ranging in size from 2 or 3 in. down to 0.01 mm. or less in diameter. Slags from furnaces melting scrap brass contain metal in the form of small shot. Floor sweepings occur in all shapes: spirals, thin shavings, pins and pin-like pieces, wire, rods, and buffing-wheel dust are the commonest.

Jan 1, 1916

THE following letter from the Rector of Louvain University, addressed to Mr. Adams and the other delegates of the Founder Societies, will be of interest to members of the Institute. It is my duty, in the name of the University of Louvain and in my own personal name, to thank you and the representatives of the Founder Societies of the "United Engineering Society" for the very kind letter of congratulations which you sent to me from Brussels on the 5th of July.

Jan 1, 1928

By J. Parke Channing

The Miami orebody occurs in an altered Pinal schist. It is popularly known as one of the &apos;(porphyry " deposits but, as at Inspiration and Ray, the ore is an altered mincralized Pinal schist. The orebody mined is the zone of secondary enrichment. Speaking in general terms, the area of the orebody at Miami may be considered as 1000 ft. long and 800 ft. wide. The vertical thickness varies from 200 to 400 ft., so that it is an extremely irregular mass. The study of the ground movement and resulting subsidence at Miami is complicated by the fact that the formation is not homogeneous throughout the mining area, the orebody terminating on its eastern extremity at a fault plane adjoining the Gila conglomerate. This conglomerate is a recent sedimentary deposit somewhat analogous to glacial drift and consists of boulders of granite, schist, and other material cemented with clay, and at times is quite hard. The fault dips eastward at an angle of 45". The original method of mining was top slicing, the slices being 10 ft. thick. At first, there was a good deal of experimenting with mining methods. Some undercut rooms were tried, and the stopes were filled with broken ore with the idea of removing intervening pillars by top slicing. The adoption of the top-slicing method in itself involved considerable experimenting, including some experiments with a long-wall system. The method finally adopted involved the operation of top slicing areas 250 ft. square, each with a central supply raise and ore-gathering raises, each block being worked as a unit. Mining operations in the Captain orebody, which connects with the boundary of the Inspiration property, were started by the room-and-pillar system, the rooms extending across the orebody, with widths of 10 to 15 ft., with 15- to 10-ft. pillars between. The intent was to operate the rooms as shrinkage stopes, permitting the pillars to crush when the ore was drawn from the rooms. It was found that the shrinkage stoping was unnecessary, so a system of block caving was adopted. This system was so successful in the Captain orebody that, about three years ago, the method of mining in the orebody was changed from top slicing to block caving, the method now in use. The block caving system, as practiced

Jan 1, 1923

By J. Parke Channing

The Miami orebody occurs in an altered Pinal schist. It is popularly known as one of the &apos;(porphyry " deposits but, as at Inspiration and Ray, the ore is an altered mincralized Pinal schist. The orebody mined is the zone of secondary enrichment. Speaking in general terms, the area of the orebody at Miami may be considered as 1000 ft. long and 800 ft. wide. The vertical thickness varies from 200 to 400 ft., so that it is an extremely irregular mass. The study of the ground movement and resulting subsidence at Miami is complicated by the fact that the formation is not homogeneous throughout the mining area, the orebody terminating on its eastern extremity at a fault plane adjoining the Gila conglomerate. This conglomerate is a recent sedimentary deposit somewhat analogous to glacial drift and consists of boulders of granite, schist, and other material cemented with clay, and at times is quite hard. The fault dips eastward at an angle of 45". The original method of mining was top slicing, the slices being 10 ft. thick. At first, there was a good deal of experimenting with mining methods. Some undercut rooms were tried, and the stopes were filled with broken ore with the idea of removing intervening pillars by top slicing. The adoption of the top-slicing method in itself involved considerable experimenting, including some experiments with a long-wall system. The method finally adopted involved the operation of top slicing areas 250 ft. square, each with a central supply raise and ore-gathering raises, each block being worked as a unit. Mining operations in the Captain orebody, which connects with the boundary of the Inspiration property, were started by the room-and-pillar system, the rooms extending across the orebody, with widths of 10 to 15 ft., with 15- to 10-ft. pillars between. The intent was to operate the rooms as shrinkage stopes, permitting the pillars to crush when the ore was drawn from the rooms. It was found that the shrinkage stoping was unnecessary, so a system of block caving was adopted. This system was so successful in the Captain orebody that, about three years ago, the method of mining in the orebody was changed from top slicing to block caving, the method now in use. The block caving system, as practiced

Jan 1, 1923

By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,&apos;-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker&apos;s data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication&apos;, a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949